WO2016109257A1 - Use of picolinamide compounds as fungicides - Google Patents

Use of picolinamide compounds as fungicides Download PDF

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Publication number
WO2016109257A1
WO2016109257A1 PCT/US2015/066764 US2015066764W WO2016109257A1 WO 2016109257 A1 WO2016109257 A1 WO 2016109257A1 US 2015066764 W US2015066764 W US 2015066764W WO 2016109257 A1 WO2016109257 A1 WO 2016109257A1
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WO
WIPO (PCT)
Prior art keywords
nmr
mhz
cdc1
plant
calcd
Prior art date
Application number
PCT/US2015/066764
Other languages
French (fr)
Inventor
Karla BRAVO-ALTAMIRANO
Yu Lu
Brian Loy
Zachary BUCHAN
David Jones
Jeremy Wilmot
Jared RIGOLI
Kyle DEKORVER
John Daeuble
Jessica HERRICK
Xuelin Wang
Chenglin Yao
Kevin Meyer
Original Assignee
Dow Agrosciences Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020237018859A priority Critical patent/KR20230086808A/en
Priority to NZ732820A priority patent/NZ732820A/en
Priority to KR1020177018609A priority patent/KR102541601B1/en
Priority to BR122021009864-6A priority patent/BR122021009864B1/en
Priority to EP15875996.9A priority patent/EP3240424B1/en
Priority to CN201580074652.2A priority patent/CN107205405B/en
Priority to CR20170307A priority patent/CR20170307A/en
Priority to AU2015374427A priority patent/AU2015374427C1/en
Priority to US15/036,316 priority patent/US10182568B2/en
Priority to ES15875996T priority patent/ES2838774T3/en
Priority to UAA201707049A priority patent/UA121561C2/en
Priority to JP2017534552A priority patent/JP6684810B2/en
Priority to CA2972405A priority patent/CA2972405A1/en
Priority to RU2017123622A priority patent/RU2702088C2/en
Priority to MX2017008440A priority patent/MX2017008440A/en
Priority to EP20195960.8A priority patent/EP3808181A1/en
Priority to PL15875996.9T priority patent/PL3240424T3/en
Priority to BR122019023756-5A priority patent/BR122019023756B1/en
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Priority to BR112017013676-7A priority patent/BR112017013676A2/en
Publication of WO2016109257A1 publication Critical patent/WO2016109257A1/en
Priority to IL253120A priority patent/IL253120B/en
Priority to PH12017501197A priority patent/PH12017501197A1/en
Priority to ZA2017/04554A priority patent/ZA201704554B/en
Priority to CONC2017/0006857A priority patent/CO2017006857A2/en
Priority to HK18104480.9A priority patent/HK1245019A1/en
Priority to AU2018206798A priority patent/AU2018206798B2/en
Priority to US16/176,664 priority patent/US10595531B2/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/20—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/52—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
  • the present disclosure relates to picolinamides and their use as fungicides.
  • the compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
  • One embodiment of the resent disclosure may include compounds of Formula I:
  • X is hydrogen or C(0)R 5 ;
  • Y is hydrogen, C(0)R 5 , or Q;
  • Z is N or CH
  • Ri is hydrogen or alkyl, each optionally substituted with 0, 1 or multiple R 8 ;
  • R 2 is methyl;
  • R 3 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple
  • R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy
  • R 5 is chosen from alkoxy or benzyl oxy, each optionally substituted with 0, 1, or multiple Rs;
  • 5 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
  • R 7 is chosen from hydrogen, -C(0)R 9 , or -CH 2 OC(0)R 9 ;
  • Rs is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted with O, 1, or multiple R 10;
  • R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple Rs;
  • Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl;
  • R 11 is chosen from hydrogen or alkyl, substituted with 0, 1, or multiple Rs;
  • Ri 2 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple
  • Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.
  • Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.
  • alkyl refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • alkenyl refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.
  • alkynyl refers to a branched or unbranched carbon chain containing one or more triple bonds including, but not limited to, propynyl, butynyl, and the like.
  • aryl and “Ar” refer to any aromatic ring, mono- or bi-cyclic, containing 0 heteroatoms.
  • heterocyclyl refers to any aromatic or non-aromatic ring, mono- or bi- cyclic, containing one or more heteroatoms.
  • alkoxy refers to an -OR substituent.
  • acyloxy refers to an -OC(0)R substituent.
  • cyano refers to a -C ⁇ N substituent.
  • hydroxyl refers to an -OH substituent.
  • amino refers to a -N(R) 2 substituent.
  • arylalkoxy refers to -0(CH 2 ) StrukturAr where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.
  • haloalkoxy refers to an -OR-X substituent, wherein X is CI, F, Br, or I, or any combination thereof.
  • haloalkyl refers to an alkyl, which is substituted with CI, F, I, or Br or any combination thereof.
  • halogen refers to one or more halogen atoms, defined as F, CI, Br, and I.
  • nitro refers to a -N0 2 substituent.
  • thioalkyl refers to an -SR substituent.
  • Formula I is read as also including all stereoisomers, for example diastereomers, enantiomers, and mixtures thereof.
  • Formula I is read as also including salts or hydrates thereof.
  • Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.
  • additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.
  • Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.
  • composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
  • the compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds.
  • the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants.
  • the materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.
  • the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier.
  • Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment.
  • the formulations can be prepared according to procedures that are conventional in the agricultural chemical art.
  • the present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide.
  • formulations are applied as aqueous suspensions or emulsions.
  • Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates.
  • any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
  • Wettable powders which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants.
  • concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent.
  • the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like.
  • the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
  • Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate.
  • the compounds may be dissolved in an inert carrier, which is either a water-mi scible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
  • the concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions.
  • Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2- ethoxyethanol.
  • Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers.
  • nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene.
  • Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts.
  • Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
  • Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the «-butyl ether, ethyl ether or methyl ether of di ethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; vegetable oils
  • Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases.
  • Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds.
  • the formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
  • Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension.
  • Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • Other components such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.
  • the compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil.
  • Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance.
  • Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm.
  • a suitable solvent is a solvent in which the compound is substantially or completely soluble.
  • Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
  • Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
  • a suitable dusty agricultural carrier such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
  • the formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism.
  • adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix.
  • the amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent.
  • Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzyl cocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9 - Cn
  • alkylpolyglycoside phosphated alcohol ethoxylate; natural primary alcohol (C 12 - C 16 ) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate
  • the formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
  • the formulations may optionally include combinations that contain other pesticidal compounds.
  • additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds.
  • the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use.
  • the compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1 : 100 to 100 : 1.
  • the compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases.
  • the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungi cide(s) or applied sequentially with the other fungicide(s).
  • Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,
  • BABS benzylaminobenzene-sulfonate
  • hydrochloride pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.
  • the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests.
  • the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s).
  • Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, afidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensul
  • dimethylvinphos dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC- ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethy
  • tetrachlorvinphos tetramethrin, tetramethylfluthrin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tioxazafen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumezopyrim, triflumuron, trimethacar
  • the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants.
  • the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s).
  • Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, ben
  • cyclopyrimorate cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlo rop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,
  • sulfentrazone sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenur
  • Another embodiment of the present disclosure is a method for the control or prevention of fungal attack.
  • This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungi ci dally effective amount of one or more of the compounds of Formula I.
  • the compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity.
  • the compounds may be useful both in a protectant and/or an eradicant fashion.
  • the compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.
  • the compounds have broad ranges of activity against fungal pathogens.
  • exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch ⁇ Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald
  • the compounds are effective in use with plants in a disease-inhibiting and
  • phytologically acceptable amount refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m 2 ).
  • the compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
  • Compounds of Formula 1.1 wherein R 3 and R12 are as originally defined and are equivalent, can be prepared by the methods shown in Scheme 1, step a.
  • the compound of Formula 1.0 can be treated with an organometallic nucleophile such as phenylmagnesium bromide (PhMgBr) in a polar aprotic solvent such as tetrahydrofuran (THF) at a temperature of about 0 °C to 23 °C to afford compounds of Formula 1.1, wherein R 3 and R i2 are as previously defined, as shown in a.
  • organometallic nucleophile such as phenylmagnesium bromide (PhMgBr)
  • a polar aprotic solvent such as tetrahydrofuran (THF)
  • Compounds of Formula 2.2 wherein R 3 is as originally defined and may or may not be equal to Ri 2 , can be prepared by the methods shown in Scheme 2, steps a - c.
  • Compounds of Formula 2.2, wherein R 3 and R i2 are as previously defined but not an electron-deficient aryl or heteroaiyl group and may or may not be equivalent can be obtained by treating the compounds of Formula 2.0, wherein R 3 and Ri 2 are as previously defined but not an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, with a mixture of a hydride reagent, such as triethylsilane (Et 3 SiH), and an acid, such as 2,2,2-trifluoroacetic acid (TFA) in a halogenated solvent such as dichloromethane (DCM) at a temperature of about 0 °C to 23 °C, as depicted in a.
  • a hydride reagent such as triethylsilane
  • compounds of Formula 2.1 wherein R 3 and Ri 2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.0, wherein R 3 and R i2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, with a base, such as sodium hydride (NaH), and a catalyst, such as imidazole, in a polar aprotic solvent such as TFIF at a temperature of about 23 °C, followed by sequential addition of carbon disulfide (CS 2 ) and an alkyl iodide, such as iodomethane (Mel), as depicted in b.
  • a base such as sodium hydride (NaH)
  • a catalyst such as imidazole
  • Compounds of Formula 2.2, wherein R 3 and R i2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.1, wherein R 3 and Ri 2 are as previously defined and may or may not be equivalent, with a tin reagent, such as tributyltin hydride, and a radical initiator, such as azobisisobutyronitrile (AIBN), in a nonpolar solvent such as toluene at a temperature of about 115 °C, as depicted in c.
  • a tin reagent such as tributyltin hydride
  • a radical initiator such as azobisisobutyronitrile (AIBN)
  • a base such as NaH
  • an alkyl halide such as Mel
  • a fluorination reagent such as (diethylamino)sulfur trifluoride (DAST)
  • DAST diethylamino)sulfur trifluoride
  • R 3 may or may not be equivalent to R 12 , can be prepared according to the methods outlined in Scheme 5, steps a - c.
  • Compounds of Formula 5.3, wherein R 3 , R4, and R 12 are as originally defined and R 3 may or may not be equivalent to R i2 can be prepared from compounds of Formula 5.0, wherein R 3 , R4, and R 12 are as originally defined and R 3 may or may not be equivalent to R 12 , by treating with a catalyst such as palladium on carbon (Pd/C) in a mixture of an unsaturated hydrocarbon solvent, such as cyclohexene, and a polar protic solvent, such as ethanol (EtOH), at an elevated temperature of about 65 °C, as shown in a.
  • a catalyst such as palladium on carbon (Pd/C) in a mixture of an unsaturated hydrocarbon solvent, such as cyclohexene, and a polar protic solvent, such as ethanol (EtOH)
  • compounds of Formula 5.3 wherein R 3 and R i2 are an electron-deficient aryl or heteroaryl group and may or may not be equivalent and R4 is hydroxyl (OH) or alkoxy
  • R 3 and R i2 are an electron-deficient aryl or heteroaryl group and may or may not be equivalent and R4 is hydroxyl (OH) or alkoxy
  • R 3 , R4, and R 12 are as previously defined and R 3 may or may not be equivalent to R 12 , with a mixture of a hydride reagent, such as Et 3 SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as indicated in b.
  • compounds of Formula 5.3 wherein R 3 and R 12 are as originally defined but not an electron-deficient aryl or heteroaryl group and may or may not be equivalent, and R 4 is a proton (H), can be obtained by treating the compounds of Formula 5.2, wherein R 3 , R 4 , and R i2 are as previously defined and R 3 may or may not be equivalent to R i2 , with a mixture of a hydride reagent, such as Et 3 SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as depicted in c.
  • Scheme 5
  • Compounds of Formula 6.2, wherein R 3 and R 12 are an electron-deficient aryl or heteroaryl group and equivalent, can be prepared according to the methods outlined in Scheme 6, steps a - b.
  • Compounds of Formula 6.1, wherein R 3 and R 12 are as described previously, can be prepared from compound of Formula 6.0, by treating with an aryl bromide, such as 4- bromobenzonitrile, in the presence of a Pd catalyst, such as XPhos Pd G3 (CAS # 1445085-55-1, commercially available from Sigma-Aldrich), in a polar aprotic solvent such as TFIF at a temperature of about 55 °C, as indicated in a.
  • a Pd catalyst such as XPhos Pd G3 (CAS # 1445085-55-1, commercially available from Sigma-Aldrich)
  • a polar aprotic solvent such as TFIF at a temperature of about 55 °C, as indicated in a.
  • Compounds of Formula 6.2, wherein R 3 and R 12 are as described previously, can be prepared from compound of Formula 6.1, wherein R 3 and R 12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (R)-(+)-2-Methyl-CBS-oxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 0 °C, as indicated in b.
  • a hydride reagent such as borane dimethyl sulfide complex
  • a catalyst such as (R)-(+)-2-Methyl-CBS-oxazaborolidine
  • a polar protic solvent such as methanol (MeOH)
  • Compounds of Formula 7.2 wherein R 3 and R 12 are as originally defined and equivalent, can be prepared according to the methods outlined in Scheme 7, steps a - b.
  • Compounds of Formula 7.1, wherein R 3 and R 12 are as described previously, can be prepared from compounds of Formula 7.0, by treating with a catalyst, such as SbCl 5 , in a halogenated solvent such as DCM at a temperature of about 23 °C, as indicated in a.
  • Compounds of Formula 7.2, wherein R 3 and R 12 are as described previously, can be prepared from compound of Formula 7.1, wherein R 3 and R 12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (R)-(+)-2-Methyl-CBS- oxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 23 °C, as indicated in b.
  • a hydride reagent such as borane dimethyl sulfide complex
  • a catalyst such as (R)-(+)-2-Methyl-CBS- oxazaborolidine
  • a polar protic solvent such as methanol (MeOH)
  • Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH 2 or O can be prepared according to the method outlined in Scheme 8, step a.
  • Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH 2 or O can be prepared from compounds of Formula 8.0, wherein n is either 0 or 1, and W is either CH 2 or O, by treating with a base, such as «-butyllithium ( «-BuLi), and an aldehyde, such as acetaldehyde, in a polar aprotic solvent such as TFIF at a temperature of about -78 °C to 23 °C, as indicated in a.
  • a base such as «-butyllithium ( «-BuLi)
  • an aldehyde such as acetaldehyde
  • a polar aprotic solvent such as TFIF
  • Compounds of Formula 9.1, wherein R 3 and R 12 are as originally defined can be prepared according to the method outlined in Scheme 9, step a.
  • Compounds of Formula 9.1, wherein R 3 and R 12 are as originally defined can be prepared from compounds of Formula 9.0, wherein R 3 is as originally defined (Formula 9.0 is either commerically available, or could be prepared from asymmetric Shi epoxidation of the corresponding i -olefin precursor, as reported in Wang, Z.-X.; Tu, Y.; Frohn, M; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc.
  • Compounds of Formula 10.2, wherein Ri, R 2 , R 3 , R 4 and R 12 are as originally defined can be prepared according to the method outlined in Scheme 10, step a.
  • Compounds of Formula 10.0, wherein Ri is as originally defined can be treated with alcohols of Formula 10.1, wherein R 2 , R 3 , R4 and R 12 are as originally defined, and a coupling reagent such as 3- (ethyliminomethyleneamino)-N,N-dimethylpropan-l -amine hydrochloride (EDC), and a catalyst such as N,N-dimethylpyridin-4-amine (DMAP) in a halogenated solvent like DCM to afford compounds of Formula 10.2, wherein Ri, R 2 , R 3 , R 4 and R i2 are as previously defined, as shown in a.
  • a coupling reagent such as 3- (ethyliminomethyleneamino)-N,N-dimethylpropan-l -amine hydrochloride (ED
  • Compounds of Formula 11.0 wherein Ri, R 2 , R 3 , R 4 and Ri 2 are as originally defined, can be treated with compounds of Formula 11.1, wherein R 6 and Z are as originally defined, in the presence of a base, such as diisopropylethylamine (DIPEA), and a peptide coupling reagent, such as benzotriazol-l-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), in an halogenated solvent like DCM, to afford compounds of Formula 11.2, wherein Ri, R 2 , R 3 , R4, R5, R12 and Z are as originally defined, as shown in b.
  • DIPEA diisopropylethylamine
  • PyBOP benzotriazol-l-yl-oxytripyrrolidinophosphonium hexafluorophosphate
  • Example 1 Preparation of (,S)-2-(benzyloxy)-l,l-bis(4-fluorophenyl)propan-l-ol.
  • Example 2C Preparation of (S)-(2-(benzyloxy)- 1 -fluoropropane- 1 , 1 -diyl)dibenzene.
  • the reaction mixture was diluted with Et 2 0 (5 mL) and quenched with sat. aq. NH 4 CI (10 mL). The layers were separated, and the aq. layer was extracted with Et 2 0 (3 x 10 mL). The combined organic layers were dried over magnesium sulfate (MgS0 4 ), filtered and concentrated to afford an orange/brown oil.
  • AIBN azobisisobutyromtrile
  • Example 3A Preparation of (S)-l,l-bis(4-fluorophenyl)propan-2-ol.
  • Example 3B Preparation of (S)- 1 , 1 -bis(2-fluorophenyl)propane- 1 ,2-diol .
  • Example 3C Preparation of (S)-l,l-bis(4-bromophenyl)propan-2-ol.
  • Example 3D, Step 2 Preparation of (S)-l,l-bis(4-ethynyl phenyl )propan-2-ol.
  • Example 3D, Step 3 Preparation of (S)-l,l-bis(4-ethylphenyl)propan-2-ol.
  • Example 3E Preparation of 1 -(9H-xanthen-9-yl)ethanol .
  • Example 3F Preparation of (l,S',2 ) S)-l-phenyl-l-(4-(trifluoromethyl)phenyl)propan-2- ol.
  • Example 3G, Step 2 Preparation of (S)-4,4'-(2-hydroxypropane-l, 1- diyl)dibenzonitrile.
  • Example 3H, Step 1 Preparation of 3,3-diphenylbutan-2-one.
  • Example 3H, Step 2 Preparation of (S)-3,3-diphenylbutan-2-ol.
  • the reaction was cooled to 0 °C in an ice water bath, diluted with water (20 mL), brine (20 mL), and Et 2 0 (40 mL), and was quenched with 1 N HC1 (8 mL). The phases were separated, and the aqueous phase was extracted with Et 2 0 (20 mL). The organic phases were combined, dried over MgS0 4 , filtered, and concentrated to provide an oil.
  • Example 31, Step 2 Preparation of l, l-bis(2,3-dimethoxyphenyl)propan-2-one.
  • Example 4A Preparation of (S)-(S)- 1 , 1 -diphenylpropan-2-yl 2- ⁇ tert- butoxycarbonyl)amino)-propanoate.
  • Example 5 Preparation of (S)- 1 -(((S)- 1 , 1 -diphenylpropan-2-yl)oxy)- 1 - oxopropan-2-aminium chloride.
  • Example 5 Preparation of 0S)-(S l, l-diphenylpropan-2-yl 2-(3-hydroxy-4- methoxypicolinamido)propanoate.
  • Example 6A Preparation of (S)-(S)- l,l-diphenylpropan-2-yl 2-(3-acetoxy-4- methoxypicolinamido)propanoate.
  • Example 6B Preparation of (,S)-(S)-l, l-diphenylpropan-2-yl 2-(3-(acetoxymethoxy)- 4-methoxypicolinamido)propanoate.
  • Example 6C Preparation of (S)-(S)-l,l-diphenylpropan-2-yl 2-(3- ((i sobutyry 1 oxy )methoxy )-4-methoxypi colinamido)propanoate .
  • Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Zymoseptoria tritici; Bayer code SEPTTR):
  • Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50%) soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100%) relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. When disease symptoms were fully expressed on the 1 st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.
  • Example B Evaluation of Fungicidal Activity: Wheat Brown Rust ⁇ Puccinia triticina; Synonym: Puccinia recondita f. sp. tritici; Bayer code PUCCRT):
  • Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50%) soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 h after fungicide treatments. After inoculation the plants were kept in 100%) relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
  • Example D Evaluation of Fungicidal Activity: Apple Scab ⁇ Venturia inaequalis; Bayer code VENTIN):
  • Apple seedlings (variety Mcintosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 h after fungicide treatment and kept in a 22 °C dew chamber with 100% relative humidity for 48 h, and then moved to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
  • Example E Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer code CERCBE):
  • Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22 °C and 100% relative humidity then transferred to a growth room at 23 °C for disease to develop. Disease severity was assessed on the sprayed leaves.
  • Example G Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer code RHYNSE):
  • Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when the first leaf was fully emerged.
  • Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22°C with 100% relative humidity for 48 h. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
  • Example H Evaluation of Fungicidal Activity: Rice Blast (Pyricularia oryzae; Bayer code PYRIOR):
  • Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
  • Example I Evaluation of Fungicidal Activity: Tomato Early Blight ⁇ Alternaria solani; Bayer code ALTESO):
  • Tomato plants (variety Outdoor Girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
  • Example J Evaluation of Fungicidal Activity: Cucumber Anthracnose
  • Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
  • Example 2A Colorless Oil Example 3A;
  • Example 2A Colorless Oil Example 3A;
  • Example 2A Colorless Oil Example 3A;
  • Example 2A Cloudy Example 3A; Colorless Example 4A. Viscous Oil
  • Example 2A Cloudy Example 3A; Colorless Example 4A. Viscous Oil
  • Example 2A Semisolid Example 3A;
  • Example 2A Colorless Oil Example 3A;
  • Example 2A Colorless Oil Example 3A;
  • Example 2A Colorless Oil Example 3A;

Abstract

This disclosure relates to picolinamides of Formula I and their use as fungicides. Fungicides are compounds, of natural or synthetic origin which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less The present disclosure relates to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

Description

USE OF PICOLINAMIDE COMPOUNDS AS FUNGICIDES
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application Serial Nos. 62/098120 filed December 30, 2014 and 62/098122 filed December 30, 2014, which are expressly incorporated by reference herein.
BACKGROUND & SUMMARY
[0002] Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
[0003] The present disclosure relates to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
[0004] One embodiment of the resent disclosure may include compounds of Formula I:
Figure imgf000002_0001
I
in which: X is hydrogen or C(0)R5;
Y is hydrogen, C(0)R5, or Q;
Q is
Figure imgf000002_0002
wherein: Z is N or CH;
Ri is hydrogen or alkyl, each optionally substituted with 0, 1 or multiple R8;
R2 is methyl; R3 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple
R8;
R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy;
R5 is chosen from alkoxy or benzyl oxy, each optionally substituted with 0, 1, or multiple Rs;
5 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
R7 is chosen from hydrogen, -C(0)R9, or -CH2OC(0)R9;
Rs is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted with O, 1, or multiple R10;
R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple Rs;
Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; R11 is chosen from hydrogen or alkyl, substituted with 0, 1, or multiple Rs; Ri2 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple
Re.
[0005] Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.
[0006] Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.
[0007] It will be understood by those skilled in the art that the following terms may include generic "R"-groups within their definitions, e.g., "the term alkoxy refers to an -OR substituent". It is also understood that within the definitions for the following terms, these "R" groups are included for illustration purposes and should not be construed as limiting or being limited by substitutions about Formula I.
[0008] The term "alkyl" refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. [0009] The term "alkenyl" refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.
[0010] The term "alkynyl" refers to a branched or unbranched carbon chain containing one or more triple bonds including, but not limited to, propynyl, butynyl, and the like.
[0011] The terms "aryl" and "Ar" refer to any aromatic ring, mono- or bi-cyclic, containing 0 heteroatoms.
[0012] The term "heterocyclyl" refers to any aromatic or non-aromatic ring, mono- or bi- cyclic, containing one or more heteroatoms.
[0013] The term "alkoxy" refers to an -OR substituent.
[0014] The term "acyloxy" refers to an -OC(0)R substituent.
[0015] The term "cyano" refers to a -C≡N substituent.
[0016] The term "hydroxyl" refers to an -OH substituent.
[0017] The term "amino" refers to a -N(R)2 substituent.
[0018] The term "arylalkoxy" refers to -0(CH2)„Ar where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.
[0019] The term "haloalkoxy" refers to an -OR-X substituent, wherein X is CI, F, Br, or I, or any combination thereof.
[0020] The term "haloalkyl" refers to an alkyl, which is substituted with CI, F, I, or Br or any combination thereof.
[0021] The term "halogen" or "halo" refers to one or more halogen atoms, defined as F, CI, Br, and I.
[0022] The term "nitro" refers to a -N02 substituent.
[0023] The term thioalkyl refers to an -SR substituent.
[0024] Throughout the disclosure, reference to the compounds of Formula I is read as also including all stereoisomers, for example diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula I is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethane sulfonate. [0025] It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.
[0026] Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.
[0027] Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
DETAILED DESCRIPTION
[0028] The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.
[0029] Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.
[0030] The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
[0031] Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
[0032] Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-mi scible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2- ethoxyethanol.
[0033] Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether. [0034] Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the «-butyl ether, ethyl ether or methyl ether of di ethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
[0035] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.
[0036] The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
[0037] Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
[0038] The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzyl cocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9 - Cn
alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12- C16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate
(8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
[0039] The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1 : 100 to 100 : 1. [0040] The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungi cide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,
bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), coumoxystrobin, cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim,
dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dipymetitrone, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminostrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam- potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picarbutrazox, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triazoxide, triclopyricarb, tricyclazole, tridemo h, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (i¾)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)- succinimide, 1,2-dichloropropane, 1,3-dichloro-l, 1, 3, 3-tetrafluoroacetone hydrate, l-chloro-2,4- dinitronaphthalene, l-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-l-yl)ethanol, 2,3- dihydro-5 -phenyl- 1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2- methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5- methylrhodanine, 4-(2-nitroprop-l-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril, benzamacril- isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,
chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5- dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4- toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury
dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb, prothiocarb
hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.
[0041] Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, afidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta- cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, broflanilide, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlo hoxim, chlo razophos, chlo yrifos, chlo yrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, clacyfos, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclaniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton- S, demeton- S -methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicloromezotiaz, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin,
dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC- ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucofuron, fluey cloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprole, fluhexafon, flupyradifurone, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptafluthrin, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kappa-bifenthrin, kappa-tefluthrin, kelevan, kinoprene, lambda- cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecaφhon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, momfluorothrin, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron,
noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para- dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyflubumide, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyriminostrobin, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos,
teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,
tetrachlorvinphos, tetramethrin, tetramethylfluthrin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tioxazafen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumezopyrim, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.
[0042] Additionally, the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate,
cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlo rop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrione, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodom ethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop- P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotnone, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ort/zo-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate,
sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.
[0043] Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungi ci dally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.
[0044] The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.
[0045] It will be understood by those skilled in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.
[0046] The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch {Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald
(Rhynchosporium secalis), blast of rice (Pyricularia oryzae), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp.tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Colletotrichum lagenarium), leaf spot of beet (Cercospora beticola), early blight of tomato (Alternaria solani), and spot blotch of barley (Cochliobolus sativus). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
[0047] The compounds are effective in use with plants in a disease-inhibiting and
phytologically acceptable amount. The term "disease-inhibiting and phytologically acceptable amount" refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m2).
[0048] Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.
[0049] The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
GENERAL SCHEMES
[0050] The following schemes illustrate approaches to generating picolinamide compounds of Formula I. The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.
[0051] Compounds of Formula 1.1, wherein R3 and R12 are as originally defined and are equivalent, can be prepared by the methods shown in Scheme 1, step a. The compound of Formula 1.0 can be treated with an organometallic nucleophile such as phenylmagnesium bromide (PhMgBr) in a polar aprotic solvent such as tetrahydrofuran (THF) at a temperature of about 0 °C to 23 °C to afford compounds of Formula 1.1, wherein R3 and Ri2 are as previously defined, as shown in a.
Scheme 1
Figure imgf000018_0001
[0052] Compounds of Formula 2.2, wherein R3 is as originally defined and may or may not be equal to Ri2, can be prepared by the methods shown in Scheme 2, steps a - c. Compounds of Formula 2.2, wherein R3 and Ri2 are as previously defined but not an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.0, wherein R3 and Ri2 are as previously defined but not an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, with a mixture of a hydride reagent, such as triethylsilane (Et3SiH), and an acid, such as 2,2,2-trifluoroacetic acid (TFA) in a halogenated solvent such as dichloromethane (DCM) at a temperature of about 0 °C to 23 °C, as depicted in a. Alternatively, compounds of Formula 2.1, wherein R3 and Ri2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.0, wherein R3 and Ri2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, with a base, such as sodium hydride (NaH), and a catalyst, such as imidazole, in a polar aprotic solvent such as TFIF at a temperature of about 23 °C, followed by sequential addition of carbon disulfide (CS2) and an alkyl iodide, such as iodomethane (Mel), as depicted in b. Compounds of Formula 2.2, wherein R3 and Ri2 are an electron-deficient aryl or heteroaiyl group and may or may not be equivalent, can be obtained by treating the compounds of Formula 2.1, wherein R3 and Ri2 are as previously defined and may or may not be equivalent, with a tin reagent, such as tributyltin hydride, and a radical initiator, such as azobisisobutyronitrile (AIBN), in a nonpolar solvent such as toluene at a temperature of about 115 °C, as depicted in c.
Scheme 2
Figure imgf000019_0001
[0053] Compounds of Formula 3.1, wherein R3 and Ri2 are as originally defined and may or may not be equivalent, can be prepared according to the method outlined in Scheme 3, step a. Compounds of Formula 3.1, wherein R3 and Ri2 are as originally defined and may or may not be equivalent, can be prepared from compounds of Formula 3.0, wherein R3 and Ri2 are as previously defined and may or may not be equivalent, by treating with a base, such as NaH and an alkyl halide, such as Mel, in a polar aprotic solvent like N,N-dimethylformamide (DMF) at a temperature of about 0 °C to 23 °C, as depicted in a.
Scheme 3
Figure imgf000019_0002
3.0 3.1
[0054] Compounds of Formula 4.1, wherein R3 and Ri2 are as originally defined and may or may not be equivalent, can be prepared according to the method outlined in Scheme 4, step a. Compounds of Formula 4.1, wherein R3 and Ri2 are as originally defined and may or may not be equivalent, can be prepared from compounds of Formula 4.0, wherein R3 and Ri2 are as previously defined and may or may not be equivalent, by treating with a fluorination reagent, such as (diethylamino)sulfur trifluoride (DAST), in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as depicted in a. Scheme 4
Figure imgf000020_0001
4.0 4.1 [0055] Compounds of Formula 5.3, wherein R3, R4, and R12 are as originally defined and
R3 may or may not be equivalent to R12, can be prepared according to the methods outlined in Scheme 5, steps a - c. Compounds of Formula 5.3, wherein R3, R4, and R12 are as originally defined and R3 may or may not be equivalent to Ri2, can be prepared from compounds of Formula 5.0, wherein R3, R4, and R12 are as originally defined and R3 may or may not be equivalent to R12, by treating with a catalyst such as palladium on carbon (Pd/C) in a mixture of an unsaturated hydrocarbon solvent, such as cyclohexene, and a polar protic solvent, such as ethanol (EtOH), at an elevated temperature of about 65 °C, as shown in a. Alternatively, compounds of Formula 5.3, wherein R3 and Ri2 are an electron-deficient aryl or heteroaryl group and may or may not be equivalent and R4 is hydroxyl (OH) or alkoxy, can be obtained by treating compounds of Formula 5.1, wherein R3, R4, and R12 are as previously defined and R3 may or may not be equivalent to R12, with a mixture of a hydride reagent, such as Et3SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as indicated in b. Additionally, compounds of Formula 5.3, wherein R3 and R12 are as originally defined but not an electron-deficient aryl or heteroaryl group and may or may not be equivalent, and R4 is a proton (H), can be obtained by treating the compounds of Formula 5.2, wherein R3, R4, and Ri2 are as previously defined and R3 may or may not be equivalent to Ri2, with a mixture of a hydride reagent, such as Et3SiH, and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0 °C to 23 °C, as depicted in c. Scheme 5
Figure imgf000021_0001
[0056] Compounds of Formula 6.2, wherein R3 and R12 are an electron-deficient aryl or heteroaryl group and equivalent, can be prepared according to the methods outlined in Scheme 6, steps a - b. Compounds of Formula 6.1, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 6.0, by treating with an aryl bromide, such as 4- bromobenzonitrile, in the presence of a Pd catalyst, such as XPhos Pd G3 (CAS # 1445085-55-1, commercially available from Sigma-Aldrich), in a polar aprotic solvent such as TFIF at a temperature of about 55 °C, as indicated in a. Compounds of Formula 6.2, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 6.1, wherein R3 and R12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (R)-(+)-2-Methyl-CBS-oxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 0 °C, as indicated in b.
Scheme 6
Figure imgf000021_0002
6.0 6.1 6.2 [0057] Compounds of Formula 7.2, wherein R3 and R12 are as originally defined and equivalent, can be prepared according to the methods outlined in Scheme 7, steps a - b. Compounds of Formula 7.1, wherein R3 and R12 are as described previously, can be prepared from compounds of Formula 7.0, by treating with a catalyst, such as SbCl5, in a halogenated solvent such as DCM at a temperature of about 23 °C, as indicated in a. Compounds of Formula 7.2, wherein R3 and R12 are as described previously, can be prepared from compound of Formula 7.1, wherein R3 and R12 are as described previously, by treating with a hydride reagent, such as borane dimethyl sulfide complex, in the presence of a catalyst, such as (R)-(+)-2-Methyl-CBS- oxazaborolidine, in a polar protic solvent, such as methanol (MeOH), at a temperature of about 23 °C, as indicated in b.
Scheme 7
Figure imgf000022_0001
7.0 7.1 7.2
[0058] Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH2 or O, can be prepared according to the method outlined in Scheme 8, step a. Compounds of Formula 8.1, wherein n is either 0 or 1, and W is either CH2 or O, can be prepared from compounds of Formula 8.0, wherein n is either 0 or 1, and W is either CH2 or O, by treating with a base, such as «-butyllithium («-BuLi), and an aldehyde, such as acetaldehyde, in a polar aprotic solvent such as TFIF at a temperature of about -78 °C to 23 °C, as indicated in a.
Scheme 8
Figure imgf000022_0002
8.1 [0059] Compounds of Formula 9.1, wherein R3 and R12 are as originally defined, can be prepared according to the method outlined in Scheme 9, step a. Compounds of Formula 9.1, wherein R3 and R12 are as originally defined, can be prepared from compounds of Formula 9.0, wherein R3is as originally defined (Formula 9.0 is either commerically available, or could be prepared from asymmetric Shi epoxidation of the corresponding i -olefin precursor, as reported in Wang, Z.-X.; Tu, Y.; Frohn, M; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc. 1997, 119, 11224), by treating with a pre-mixed suspension of a copper(I) salt, such as copper iodide (Cul), and an organometallic nucleophile, such as 4-(trifluoromethyl)phenylmagnesium bromide in a polar aprotic solvent such as TFIF, at a temperature of about -78 °C to 23 °C, as shown in a.
Scheme 9
Figure imgf000023_0001
9.0 9.1 [0060] Compounds of Formula 10.2, wherein Ri, R2, R3, R4 and R12 are as originally defined, can be prepared according to the method outlined in Scheme 10, step a. Compounds of Formula 10.0, wherein Ri is as originally defined, can be treated with alcohols of Formula 10.1, wherein R2, R3, R4 and R12 are as originally defined, and a coupling reagent such as 3- (ethyliminomethyleneamino)-N,N-dimethylpropan-l -amine hydrochloride (EDC), and a catalyst such as N,N-dimethylpyridin-4-amine (DMAP) in a halogenated solvent like DCM to afford compounds of Formula 10.2, wherein Ri, R2, R3, R4 and Ri2 are as previously defined, as shown in a.
Scheme 10
Figure imgf000023_0002
10.0 10.1 10.2 [0061] Compounds of Formula 11.2, wherein Rh R2, R3, R4, R6, Ri2 and Z are as originally defined, can be prepared according to the methods outlined in Scheme 11, steps a - b. As depicted in a, compounds of Formula 11.2, wherein Ri, R2, R3, R4 and Ri2 are as originally defined, can be subjected to an acid, such as a 4 normal (N) solution of hydrogen chloride (HC1) in dioxane, in a halogenated solvent such as DCM to afford compounds of Formula 9.0, wherein Ri, R2, R3, R4 and Ri2 are as originally defined, as shown in a.
[0062] Compounds of Formula 11.0, wherein Ri, R2, R3, R4 and Ri2 are as originally defined, can be treated with compounds of Formula 11.1, wherein R6 and Z are as originally defined, in the presence of a base, such as diisopropylethylamine (DIPEA), and a peptide coupling reagent, such as benzotriazol-l-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), in an halogenated solvent like DCM, to afford compounds of Formula 11.2, wherein Ri, R2, R3, R4, R5, R12 and Z are as originally defined, as shown in b.
Scheme 11
Figure imgf000024_0001
11.1
[0063] Compounds of Formula 12.0, wherein Ri, R2, R3, R4, R6, R7, R12 and Z are as originally defined, can be prepared according to the method outlined in Scheme 12, step a. As shown in a, compounds of Formula 11.2, wherein Ri, R2, R3, R4, R6, R12 and Z are as originally defined, can be treated with an appropriate alkyl halide with or without a reagent such as sodium iodide (Nal) and an alkali carbonate base, such as sodium carbonate (Na2C03) or potassium carbonate (K2C03), in a solvent like acetone at a temperature of about 55 °C, or by treatment with an acyl halide in the presence of an amine base, such as pyridine, triethylamine (Et3N), DMAP, or mixtures thereof, in an aprotic solvent such as DCM, at a temperature of about 23 °C, to afford compounds of Formula 12.0 wherein Ri, R2, R3, R4, R6, R7, R12 and Z are as originally defined. heme 12
Figure imgf000025_0001
EXAMPLES
[0050] The chemistry in the following examples may be conducted using either enantiomer of 2-((tert-butoxycarbonyl)amino)propanoic acid (Boc-Ala-OH) or either protected (PMB or Bn) or unprotected enantiomer of ethyl lactate.
[0051] Example 1: Preparation of (,S)-2-(benzyloxy)-l,l-bis(4-fluorophenyl)propan-l-ol.
Figure imgf000025_0002
[0052] To a solution of (S)-ethyl 2-(benzyloxy)propanoate (2.08 grams (g), 10.0 millimoles (mmol)) in tetrahydrofuran (THF; 20 milliliters (mL)) at 0 °C was slowly added (4- fluorophenyl)magnesium bromide (31.3 mL, 25.0 mmol, 0.8 molar (M) in THF) over a 10 minute (min) period. The reaction vessel was allowed to warm slowly to room temperature over 2 hours (h), and the reaction mixture was quenched by careful addition of saturated (sat.) aqueous (aq.) ammonium chloride (N¾Q; 50 mL). The mixture was diluted with diethyl ether (Et20; 50 mL), the phases were separated, and the aq. phase was extracted with Et20 (2 x 50 mL). The combined organic phases were washed with sat. aq. sodium chloride (NaCl, brine; 100 mL), dried over sodium sulfate (Na2S04), filtered, and concentrated. The resulting oil was purified by flash column chromatography (silica gel (Si02), 0- 5% acetone in hexanes) to afford the title compound (3.28 g, 93%) as a colorless oil: 1H MR (300 MHz, CDC13) δ 7.47 - 7.38 (m, 2H), 7.38 - 7.27 (m, 5H), 7.17 - 7.09 (m, 2H), 7.04 - 6.89 (m, 4H), 4.64 (dd, J= 11.4, 0.7 Hz, 1H), 4.51 - 4.38 (m, 2H), 3.12 (s, 1H), 1.11 (d, J= 6.1 Hz, 3H); 19F NMR (376 MHz, CDC13) δ -116.19, -116.41; ESFMS m/z 377 ([M+Na]+). [0053] Example 2A: Preparation of (S)-4,4'-(2-(benzyloxy)propane- 1,1- diyl)bis(fluorobenzene).
Figure imgf000026_0001
[0054] To a solution of (S)-2-(benzyloxy)- 1 , 1 -bis(4-fluorophenyl)propan- 1 -ol (709 milligrams (mg), 2.00 mmol) in dichloromethane (DCM; 20 mL) at 0 °C was added triethylsilane (Et3SiH; 3.19 mL, 20.0 mmol) followed by 2,2,2-trifluoroacetic acid (TFA; 1.53 mL, 20.0 mmol). The mixture was stirred at 0 °C for 1 h. The resulting solution was quenched by careful addition of sat. aq. sodium bicarbonate (NaHC03; 20 mL). The phases were separated, and the aq. phase was extracted with DCM (2 x 30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (627 mg, 92%) as a white solid: 1H NMR (400 MHz, CDC13) δ 7.31 - 7.22 (m, 5H), 7.21 - 7.16 (m, 2H), 7.10 - 7.03 (m, 2H), 7.00 - 6.91 (m, 4H), 4.54 (dd, J= 11.5, 0.7 Hz, 1H), 4.31 (dd, J= 11.6, 0.8 Hz, 1H), 4.14 (dq, J= 8.1, 6.1 Hz, 1H), 3.93 (d, J= 8.1 Hz, 1H), 1.18 (d, J= 6.0 Hz, 3H); 19F NMR (376 MHz, CDC13) δ -116.60, -117.10; ESFMS (m/z) 361 ([M+Na]+). [0055] Example 2B: Preparation of (,S)-(2-(benzyloxy)- 1 -methoxypropane- 1,1- diyl)dibenzene.
Figure imgf000027_0001
[0056] To a suspension of sodium hydride (NaH; 52.0 mg, 1.30 mmol, 60% weight per weight (w/w) in mineral oil) in N,N-dimethylformamide (DMF; 3 mL) at 0 °C was added a solution of (S)-2-(benzyloxy)-l,l-diphenylpropan-l-ol (318 mg, 1 mmol) in DMF (1 mL). The reaction mixture was stirred at room temperature for 30 min and then cooled to 0 °C. lodomethane (Mel; 93.0 microliters (μί), 1.50 mmol) was added, and the reaction mixture was stirred at room temperature for 1 h. The resulting solution was quenched by careful addition of sat. aq. NaHC03 (10 mL). The mixture was diluted with diethyl ether (Et20; 10 mL), the phases were separated, and the aq. phase was extracted with Et20 (2 x 10 mL). The combined organic phases were washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 5% acetone in hexanes) to afford the title compound (295 mg, 89%) as a colorless oil: 1H MR (400 MHz, CDC13) δ 7.47 - 7.41 (m, 2H), 7.40 - 7.35 (m, 2H), 7.33 - 7.18 (m, 11H), 4.69 (d, J= 11.9 Hz, 1H), 4.54 (d, J= 12.3 Hz, 1H), 4.50 (q, J= 6.1 Hz, 1H), 3.13 (s, 3H), 1.10 (d, 7= 6.1 Hz, 3H); 13C MR (101 MHz, CDC13) δ 142.96, 141.31, 138.79, 129.13, 128.54, 128.14, 127.61, 127.16, 127.08, 126.95, 126.69, 99.99, 85.35, 78.13, 70.80, 52.46, 13.65; ESFMS (m/z) 333 ([M+H]+).
[0057] Example 2C: Preparation of (S)-(2-(benzyloxy)- 1 -fluoropropane- 1 , 1 -diyl)dibenzene.
Figure imgf000027_0002
[0058] To a solution of (S)-2-(benzyloxy)-l,l-diphenylpropan-l-ol (300 mg, 0.942 mmol) in DCM (5 mL) at 0 °C was added (diethylamino)sulfur trifluoride (DAST; 1.88 mL, 1.88 mmol, 1 M in DCM). The reaction was slowly warmed to room temperature over 3 h. The resulting solution was quenched by careful addition of sat. aq. NaHC03 (5 mL). The phases were separated, and the aq. phase was extracted with DCM (2 x 10 mL). The combined organic phases were washed with brine (10 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (300 mg, 98%) as a colorless oil: 1H MR (400 MHz, CDC13) δ 7.58 - 7.49 (m, 2H), 7.43 - 7.37 (m, 2H), 7.36 - 7.20 (m, 9H), 7.09 - 6.99 (m, 2H), 4.47 (d, J= 11.7 Hz, 1H), 4.37 - 4.25 (m, 2H), 1.26 (dd, J = 6.3, 1.3 Hz, 3H); 13C MR (101 MHz, CDC13) δ 142.23 (d, J= 22.7 Hz), 141.00 (d, J= 23.5 Hz), 138.03, 128.21, 128.16, 127.90 (d, J= 1.5 Hz), 127.80, 127.72 (d, J= 1.7 Hz), 127.52, 127.42 (d, J = 1.3 Hz), 126.23 (d, J= 9.6 Hz), 125.93 (d, J= 8.7 Hz), 99.96 (d, J= 180.8 Hz), 78.91 (d, J= 26.9 Hz), 71.68, 14.47 (d, J= 3.6 Hz); 19F NMR (376 MHz, CDC13) δ -159.80. [0059] Example 2D, Step 1: Preparation of (5)-O-(2-(benzyloxy)-l,l-bis(3,4,5- trifluorophenyl ropyl) ^-methyl carbonodithioate.
Figure imgf000028_0001
[0060] To a solution of (,S)-2-(benzyloxy)-l,l-bis(3,4,5-trifluorophenyl)propan-l-ol (496 mg, 1.16 mmol) in anhydrous THF (5.8 mL) was added NaH (93.0 mg, 2.33 mmol), followed by imidazole (3.96 mg, 0.0580 mmol), and the reaction mixture was stirred at ambient temperature for 1 h. Carbon disulfide (562 μΐ^, 9.30 mmol) was added via syringe in one portion, followed by Mel (579 μΐ^, 9.30 mmol), and the reaction mixture was stirred at ambeint temperature for 2 h. The reaction mixture was diluted with Et20 (5 mL) and quenched with sat. aq. NH4CI (10 mL). The layers were separated, and the aq. layer was extracted with Et20 (3 x 10 mL). The combined organic layers were dried over magnesium sulfate (MgS04), filtered and concentrated to afford an orange/brown oil. The crude oil was purified by flash column chromatography (Si02, 0- 50% ethyl acetate (EtOAc) in hexanes) to afford the title compound (627 mg, 94%) as a clear, bright yellow colored oil: 1H MR (400 MHz, CDC13) δ 7.40 - 7.27 (m, 3H), 7.24 - 7.16 (m, 2H), 7.02 (dd, J = 9.1, 6.6 Hz, 2H), 6.96 (dd, J= 8.8, 6.5 Hz, 2H), 5.44 (q, J= 6.1 Hz, 1H), 4.66 (d, J= 11.6 Hz, 1H), 4.51 (d, J= 11.6 Hz, 1H), 2.49 (s, 3H), 1.16 (d, 7= 6.1 Hz, 3H); 19F NMR (376 MHz, CDC13) δ - 133.89 (d, 7= 20.7 Hz), -134.73 (d, 7= 20.6 Hz), -159.83 (t, 7= 20.6 Hz), -160.56 (t, 7= 20.7 Hz); (Thin film) 2922, 1721, 1622, 1595, 1526, 1436, 1344, 1241, 1217, 1197, 1119, 1088, 1040, 965, 908, 861, 822, 730, 712, 697, 672 cm"1. [0061] Example 2D, Step 2: Preparation of (S)-5,5'-(2-(benzyloxy)propane-l,l- diyl)bis(l,2,3-trifluorobenzene).
Figure imgf000029_0001
[0062] A solution of (,S)-O-(2-(benzyloxy)-l,l-bis(3,4,5-trifluorophenyl)propyl) S-methyl carbonodithioate (598 mg, 1.16 mmol) in toluene (200 mL) was degassed by a freeze-pump-thaw procedure (3 cycles using liquid nitrogen (N2)) under an atmosphere of N2. Tributyltin hydride (3.12 mL, 11.6 mmol) was then added, the reaction flask was fitted with a reflux condenser, and the reaction mixture was heated to a light reflux (115 °C). A solution of azobisisobutyromtrile (AIBN; 0.200 g, 1.22 mmol) in degassed toluene (3 cycles via liquid N2; 32 mL) was added via syringe down the reflux condenser over 3 h. Once slow addition of the AIBN was complete, the reaction mixture was stirred at reflux overnight. The solvent was removed in vacuo to provide a pale yellow oil. The crude oil was purified by flash column chromatography (Si02, 0- 30% EtOAc in hexanes) to afford the title compound (358 mg, 72%) as a clear, colorless oil: 1H NMR (400 MHz, CDC13) δ 7.28 (d, 7= 6.6 Hz, 3H), 7.17 - 7.06 (m, 2H), 6.92 (dd, 7= 8.5, 6.5 Hz, 2H), 6.79 (dd, 7= 8.3, 6.4 Hz, 2H), 4.59 (d, J= 11.7 Hz, 1H), 4.31 (d, J= 11.7 Hz, 1H), 4.02 (p, J= 6.2 Hz, 1H), 3.76 (d, J= 6.8 Hz, 1H), 1.19 (d, J = 6.1 Hz, 3H); 19F NMR (376 MHz, CDC13) δ -133.80 (d, J = 20.5 Hz), -134.34 (d, J= 20.5 Hz), -162.54 (t, J= 20.5 Hz), -162.84 (t, J= 20.5 Hz); (Thin film) 2871, 1621, 1526, 1445, 1345, 1262, 1235, 1116, 1096, 1043, 859, 802, 728, 698, 679 cm"1.
[0063] Example 3A: Preparation of (S)-l,l-bis(4-fluorophenyl)propan-2-ol.
Figure imgf000030_0001
[0064] To a solution of (,S)-4,4'-(2-(benzyloxy)propane-l,l-diyl)bis(fluorobenzene) (575 mg, 1.70 mmol) in ethanol (EtOH; 11 mL) and cyclohexene (5.5 mL) at room temperature was added palladium on carbon (Pd/C; 362 mg, 0.0850 mmol, 2.5% w/w of Pd). The reaction mixture was stirred at 65 °C for 2 h, cooled to room temperature, filtered through a plug of Celite®, and concentrated to afford the title compound (415 mg, 98%) as a colorless oil: 1H NMR (400 MHz, CDCI3) δ 7.36 - 7.29 (m, 2H), 7.25 - 7.18 (m, 2H), 7.09 - 6.93 (m, 4H), 4.47 (dqd, J= 8.2, 6.1, 3.3 Hz, 1H), 3.80 (d, J= 8.3 Hz, 1H), 1.55 (d, J= 3.3 Hz, 1H), 1.19 (d, J= 6.1 Hz, 3H); 13C MR (101 MHz, CDC13) 5 162.90 (d, J= 23.3 Hz), 160.46 (d, J= 23.1 Hz), 138.15 (d, J= 3.1 Hz), 136.94 (d, J= 3.6 Hz), 130.14 (d, J= 7.8 Hz), 129.55 (d, J= 7.8 Hz), 115.70 (d, J= 18.8 Hz), 115.49 (d, J = 18.8 Hz), 70.07, 58.61, 21.63; 19F NMR (376 MHz, CDC13) δ -115.84, -116.19.
[0065] Example 3B: Preparation of (S)- 1 , 1 -bis(2-fluorophenyl)propane- 1 ,2-diol .
Figure imgf000030_0002
[0066] To a solution of (S)- 1 , 1 -bi s(2-fluorophenyl)-2-((4-methoxybenzyl)oxy)propan- 1 -ol (790 mg, 2.06 mmol) in DCM (20 mL) at 0 °C was added Et3SiH (3.28 mL, 20.6 mmol) followed by TFA (1.57 mL, 20.6 mmol). The mixture was stirred at 0 °C for 1 h. The resulting solution was quenched by careful addition of sat. aq. NaHC03 (20 mL). The phases were separated, and the aq. phase was extracted with DCM (2 x 30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (388 mg, 71%) as a colorless oil: 1H MR (400 MHz, CDC13) δ 7.90 - 7.77 (m, 1H), 7.70 (tt, J= 8.2, 1.5 Hz, 1H), 7.31 - 7.10 (m, 4H), 6.97 (ddd, J= 12.7, 8.1, 1.3 Hz, 1H), 6.88 (ddd, J= 11.8, 8.0, 1.4 Hz, 1H), 5.11 (qd, J= 6.3, 2.3 Hz, 1H), 3.49 (s, 1H), 2.27 (s, 1H), 1.09 (d, J= 6.3 Hz, 3H); 19F NMR (376 MHz, CDC13) δ -112.90 (d, J= 8.3 Hz), -113.92 (d, J= 8.4 Hz); ESIMS (m/z) 551
([2M+Na]+).
[0067] Example 3C: Preparation of (S)-l,l-bis(4-bromophenyl)propan-2-ol.
Figure imgf000031_0001
[0068] To a solution of (S)- 1 , 1 -bis(4-bromophenyl)-2-((4-methoxybenzyl)oxy)propan- 1 -ol
(1.80 g, 3.56 mmol) in DCM (18 mL) at 0 °C was added Et3SiH (5.68 mL, 35.6 mmol) followed by TFA (2.72 mL, 35.6 mmol). The mixture was warmed slowly to room temperature over 3 h. The resulting solution was quenched by careful addition of sat. aq. NaHC03 (20 mL). The phases were separated, and the aq. phase was extracted with DCM (2 x 30 mL). The combined organic phases were washed with brine (50 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (742 mg, 56%) as a colorless oil: 1H MR (300 MHz, CDC13) δ 7.51 - 7.36 (m, 4H), 7.25 - 7.17 (m, 2H), 7.18 - 7.06 (m, 2H), 4.48 (dq, J= 8.2, 6.1 Hz, 1H), 3.76 (d, J= 8.2 Hz, 1H), 2.80 (s, 1H), 1.19 (d, J= 6.2 Hz, 3H); 13C MR (75 MHz, CDC13) δ 140.94, 139.85, 131.98, 131.85, 130.39, 129.84, 121.06, 120.72, 69.82, 58.91, 21.65; (Thin film) 3390, 3024, 2969, 2900, 1486, 1072 cm"1. [0069] Example 3D, Step 1: Preparation of (,S)-l,l-bis(4-((trimethylsilyl)ethynyl)- phenyl)propan-2-ol .
Figure imgf000032_0001
[0070] To a solution of (S)-l, l-bis(4-bromophenyl)propan-2-ol (1.01 g, 2.72 mmol) in THF
(9 mL) was added bis(triphenylphosphine)palladium dichloride (0.095 g, 0.136 mmol) and copper(I) iodide (Cul; 0.026 g, 0.136 mmol). The mixture was sparged with N2 for 20 min, and triethylamine (Et3N; 4.53 mL) was added dropwise. To the resulting mixture was added
ethynyltrimethylsilane (1.15 mL, 8.15 mmol) dropwise, and the mixture was heated to reflux and stirred overnight. The mixture was cooled to room temperature, and the reaction was quenched with sat. aq. NaHC03. The products were extracted with EtOAc (2x), and the combined organic layers were washed with brine, dried over Na2S04, filtered and concentrated. The crude residue was then purified by flash column chromatography (Si02, 0- 20% acetone in hexanes) to provide the title compound (495 mg, 45%) as a brown foam: 1H MR (400 MHz, CDC13) δ 7.48 - 7.42 (m, 2H), 7.42 - 7.37 (m, 2H), 7.33 - 7.27 (m, 2H), 7.24 - 7.17 (m, 2H), 4.51 (dqd, J= 12.2, 6.1, 3.5 Hz, 1H), 3.81 (d, J= 8.3 Hz, 1H), 1.60 (d, J= 3.8 Hz, 1H), 1.18 (d, J= 6.1 Hz, 3H), 0.26 (s, 9H), 0.26 (s, 9H); 13C MR (101 MHz, CDC13) δ 142.55, 141.48, 132.42, 132.29, 128.69, 128.15, 121.90, 121.57, 104.76, 104.71, 94.49, 94.33, 69.76, 59.96, 21.55, 0.00; (Thin film) 3397, 2960, 2156, 1501, 1248, 861, 840 cm"1; HRMS-ESI (m/z) [M+H]+ calcd for C25H33OSi2, 405.2064; found, 405.2070.
[0071] Example 3D, Step 2: Preparation of (S)-l,l-bis(4-ethynyl phenyl )propan-2-ol.
Figure imgf000033_0001
[0072] To a solution of S)-l, l-bis(4-((trimethylsilyl)ethynyl)phenyl)propan-2-ol (0.470 g, 1.16 mmol) in methanol (MeOH; 5.8 mL) was added potassium carbonate (K2C03; 0.482 g, 3.48 mmol). The mixture was stirred for 1 h at room temperature and then filtered through Celite®. The filter cake was washed with MeOH, and the filtrate was concentrated. The crude material was purified by flash column chromatography (Si02, 0- 20% acetone in hexanes) to provide the title compound (288 mg, 95%) as a yellow oil: 1H NMR (300 MHz, CDC13) δ 7.48 - 7.43 (m, 2H), 7.43 - 7.39 (m, 2H), 7.35 - 7.29 (m, 2H), 7.24 - 7.19 (m, 2H), 4.51 (dqd, J= 8.3, 6.1, 3.7 Hz, 1H), 3.82 (d, J= 8.3 Hz, 1H), 3.05 (s, 1H), 3.04 (s, 1H), 1.63 - 1.55 (m, 1H), 1.18 (d, J= 6.1 Hz, 3H); 13C NMR (101 MHz, CDC13) δ 142.84, 141.82, 132.60, 132.48, 128.74, 128.22, 120.87, 120.57, 83.31, 83.29, 77.39, 77.29, 69.73, 59.96, 21.66; (Thin film) 3436, 3280, 2968, 2106, 1499, 1075, 825 cm"1; HRMS-ESI (m/z) [M+H]+ calcd for C19H17O, 261.1274; found, 261.1272.
[0073] Example 3D, Step 3: Preparation of (S)-l,l-bis(4-ethylphenyl)propan-2-ol.
Figure imgf000033_0002
[0074] To a solution of (S)-l,l-bis(4-ethynylphenyl)propan-2-ol (0.144 g, 0.553 mmol) in EtOAc (2.8 mL) was added palladium (5% weight (wt) on carbon, dry basis; 0.235 g, 0.055 mmol). The mixture was stirred under a balloon of hydrogen overnight. The mixture was filtered through Celite®, and the filter cake was washed with EtOAc. The combined filtrate was then concentrated, and the crude residue was purified by flash column chromatography (Si02, 0- 25% acetone in hexanes) to provide the title compound (97.0 mg, 65%) as a clear oil: 1H NMR (400 MHz, CDC13) δ 7.33 - 7.25 (m, 2H), 7.22 -7 .15 (m, 2H), 7.18 - 7.11 (m, 2H), 7.10 (d, J= 8.1 Hz, 2H), 4.51 (dqd, J = 8.7, 6.1, 2.5 Hz, 1H), 3.74 (d, J= 8.9 Hz, 1H), 2.65 - 2.53 (m, 4H), 1.68 (d, J= 2.8 Hz, 1H), 1.23 - 1.14 (m, 9H); 13C NMR (101 MHz, CDC13) δ 142.74, 142.33, 139.94, 138.91, 128.48, 128.40, 128.07, 128.02, 70.19, 60.02, 28.41, 28.39, 21.37, 15.47, 15.46; (Thin film) 3421, 2963, 1510, 1110, 821 cm"1; HRMS-ESI (m/z) ([M+Na]+) calcd for Ci9H24NaO, 291.1719; found, 291.1725.
[0075] Example 3E : Preparation of 1 -(9H-xanthen-9-yl)ethanol .
Figure imgf000034_0001
[0076] To a solution of 9H-xanthene (364 mg, 2.00 mmol) in THF (10 mL) at -78 °C was added «-butyllithium (2.5 M in hexanes; 0.880 mL, 2.20 mmol). The mixture was stirred at -78 °C for 30 min. Acetaldehyde (0.226 mL, 4.00 mmol) was added, and the reaction mixture was warmed slowly to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. NH4C1 (10 mL). The phases were separated, and the aq. phase was extracted with Et20 (2 x 15 mL). The combined organic phases were washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (216 mg, 48%) as a colorless oil: 1H NMR (400 MHz, CDC13) δ 7.33 - 7.22 (m, 4H), 7.17 - 7.04 (m, 4H), 3.99 (d, J= 5.1 Hz, 1H), 3.96 - 3.82 (m, 1H), 1.54 (d, J= 6.0 Hz, 1H), 1.00 (d, J= 6.3 Hz, 3H); 13C NMR (101 MHz, CDC13) δ 152.94, 152.65, 129.54, 129.30, 128.19, 128.17, 123.18, 123.14, 122.48, 121.73, 116.59, 116.41, 73.07, 47.06, 18.81; ESIMS (m/z) 475 ([2M+Na]+).
[0077] Example 3F: Preparation of (l,S',2)S)-l-phenyl-l-(4-(trifluoromethyl)phenyl)propan-2- ol.
Figure imgf000035_0001
[0078] To a mixture of magnesium turnings (102 mg, 4.20 mmol) in Et20 (4 mL) was added l-bromo-4-(trifluoromethyl)benzene (0.588 mL, 4.20 mmol) at room temperature, followed by Mel (5 μν). Upon warming to a gentle boil using a heat gun, the mixture turned a yellow/brown color. The reaction was then stirred in a water bath at room temperature for 30 min until almost all the magnesium was consumed. This was added to a suspension of copper(I) iodide (Cul; 400 mg, 2.10 mmol) in Et20 (4 mL) at -78 °C. The reaction was stirred at -20 °C for 30 min, then cooled to -78 °C, and (2,S',3)S)-2-methyl-3-phenyloxirane (0.201 mL, 1.50 mmol) was added. The resulting mixture was warmed slowly to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. LCl (10 mL). The phases were separated, and the aq. phase was extracted with Et20 (2 x 15 mL). The combined organic phases were washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 10% acetone in hexanes) to afford the title compound (390 mg, 94%) as a light yellow oil: 1H MR (400 MHz, CDC13) δ 7.60 - 7.50 (m, 2H), 7.48 - 7.38 (m, 2H), 7.38 - 7.33 (m, 4H), 7.30 - 7.23 (m, 1H), 4.58 (dqd, J= 8.4, 6.1, 3.5 Hz, 1H), 3.88 (d, J= 8.5 Hz, 1H), 1.65 (d, J= 3.6 Hz, 1H), 1.20 (d, J= 6.1 Hz, 3H); 19F MR (376 MHz, CDC13) δ -62.49; ESIMS (m/z) 263 ([M-OH]+). [0079] Example 3G, Step 1: Preparation of 4,4'-(2-oxopropane-l, l-diyl)dibenzonitrile.
Figure imgf000035_0002
[0080] To a suspension of 4-bromobenzonitrile (546 mg, 3.00 mmol) and cesium carbonate (977 mg, 3.00 mmol) in THF (10 mL) under an N2 atmosphere was added acetone (1.10 mL, 15.00 mmol), followed by X-Phos Pd G3 (50.8 mg, 0.060 mmol). Then, the vial was sealed and heated to 55 °C for 4 days. The reaction was diluted with EtOAc (30 mL) and washed with sat. H4C1 (3 x 10 mL), water (15 mL), and brine (15 mL). Then the organic phase was dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 40% EtOAc in hexanes) to afford the title compound (174 mg, 22%) as a colorless oil: 1H NMR (400 MHz, CDC13) δ 7.66 (d, J= 8.4 Hz, 4H), 7.34 (d, J= 8.3 Hz, 4H), 5.21 (s, 1H), 2.29 (s, 3H); 13C NMR (101 MHz, CDC13) δ 203.68, 142.15, 132.75, 129.64, 118.21, 112.00, 64.25, 30.43; ESIMS m/z 261 ([M+H]+).
[0081] Example 3G, Step 2: Preparation of (S)-4,4'-(2-hydroxypropane-l, 1- diyl)dibenzonitrile.
Figure imgf000036_0001
[0082] To a solution of 4,4'-(2-oxopropane-l, l-diyl)dibenzonitrile (174 mg, 0.668 mmol) in toluene (4.5 mL) was added (R)-l-methyl-3,3-diphenylhexahydropyrrolo[l,2- c][l,3,2]oxazaborole (1 M solution in toluene, 66.8 μΕ, 0.067 mmol). Then, the reaction was cooled to 0 °C and a solution of BH3-DMS (69.8 μΐ, 0.735 mmol) in 0.5 mL toluene was added over 2 min. The flask was left to stir at 0 °C. After 2 h, the reaction was quenched with methanol (0.5 mL), diluted with EtOAc and added water. Phases were separated and the aqueous phase was extracted with EtOAc x 2. The combined organic phases were washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 50% EtOAc in hexanes) to afford the title compound (99.7 mg, 57%) as a colorless oil: 1H NMR (400 MHz, CDC13) δ d 7.60 (dd, J= 8.4, 6.8 Hz, 4H), 7.51 - 7.46 (m, 2H), 7.43 - 7.37 (m, 2H), 4.63 - 4.47 (m, 1H), 3.97 (d, J= 7.5 Hz, 1H), 1.97 (d, J= 3.8 Hz, 1H), 1.21 (d, J= 6.2 Hz, 3H).13C NMR (101 MHz, CDC13) δ 146.91, 145.86, 132.60, 132.45, 129.90, 129.19, 118.58, 118.51, 110.96, 110.92, 69.19, 59.56, 22.27; ESIMS m/z 263 ([M+H]+).
[0083] Example 3H, Step 1: Preparation of 3,3-diphenylbutan-2-one.
Figure imgf000037_0001
[0084] To a magnetically stirred mixture of 2,3-diphenylbutane-2,3-diol (500 mg, 2.06 mmol) in DCM (10 mL) was added antimony pentachloride (26.5 μΐ^, 0.206 mmol) under air atmosphere. The reaction mixture was stirred at 25 °C for 1 h and then was quenched by slow addition of sat. aq. NaHC03. The resulting mixture was diluted with water and additional DCM, and the organic layer was separated by passing through a phase separator. The resulting oil was purified by flash column chromatography (Si02, 0- 5% acetone in hexanes) to afford the title compound (330 mg, 71%) as a colorless oil: 1H MR (400 MHz, CDC13) δ 7.36 - 7.31 (m, 4H), 7.30 - 7.25 (m, 2H), 7.23 - 7.15 (m, 4H), 2.11 (s, 3H), 1.87 (s, 3H); 13C MR (101 MHz, CDC13) δ 209.16, 143.59, 128.36, 126.91, 62.32, 27.62, 26.42; ESIMS m/z 225 ([M+H]+).
[0085] Example 3H, Step 2: Preparation of (S)-3,3-diphenylbutan-2-ol.
Figure imgf000037_0002
[0086] To a solution of 3,3-diphenylbutan-2-one (150 mg, 0.669 mmol) in toluene (4.5 mL) was added (R)-l-methyl-3,3-diphenylhexahydropyrrolo[l,2-c][l,3,2]oxazaborole (1 M solution in toluene, 134 μί, 0.134 mmol). Then, a solution of BH3-DMS (70.2 μί, 0.702 mmol) in 0.5 mL of toluene was added to the reaction mixture over 2 min. The flask was left to stir at room temperature. After 1 h, the reaction was quenched with methanol (0.5 mL). DCM and water were added, and the phases were separated. The aqueous phase was extracted with DCM (2x). The combined organic phases were washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The resulting oil was purified by flash column chromatography (Si02, 0- 20% acetone in hexanes) to afford the title compound (150 mg, 99%) as a colorless oil: 1H MR (400 MHz, CDC13) δ d 7.39 - 7.17 (m, 10H), 4.70 - 4.61 (m, 1H), 1.67 (s, 3H), 1.51 (d, J= 4.9 Hz, 1H), 1.11 (d, J= 6.3 Hz, 3H); 13C MR (101 MHz, CDC13) δ 147.30, 145.86, 128.40, 128.15, 128.05, 127.79, 126.20, 126.01, 72.28, 51.77, 23.26, 18.39; ESIMS m/z 227 ([M+H]+). [0087] Example 31, Step 1 : Preparation of S)- 1 , 1 -bis(2,3 -dimethoxyphenyl)propane- 1 ,2- diol.
Figure imgf000038_0001
[0088] To a solution of isopropylmagnesium lithium chloride (1.3 M in THF, 6.1 mL, 8.00 mmol) was added THF (2 mL) and l-bromo-2,3-dimethoxybenzene (1.74 g, 8.00 mmol). The resulting brown solution was heated to a gentle reflux (75 °C external temp) for 2.5 h, then cooled to 0 °C in an ice water bath. (S)-methyl 2-hydroxypropanoate (0.191 ml, 2 mmol) was then added dropwise via syringe. The reaction was stirred at 0 °C for 1 h, then removed from the cold bath and stirred overnight at rt. The reaction was cooled to 0 °C in an ice water bath, diluted with water (20 mL), brine (20 mL), and Et20 (40 mL), and was quenched with 1 N HC1 (8 mL). The phases were separated, and the aqueous phase was extracted with Et20 (20 mL). The organic phases were combined, dried over MgS04, filtered, and concentrated to provide an oil. Purification by automated silica gel column chromatography (5-50% EtOAc in hexanes) provided the title compound (568 mg, 82%) as a yellow, crystalline solid: 1H NMR (300 MHz, CDC13) δ 7.43 (td, J= 8.0, 1.5 Hz, 2H), 7.11 (td, 7= 8.1, 4.9 Hz, 2H), 6.83 (dd, 7= 8.1, 1.4 Hz, 2H), 5.06 - 4.82 (m, 1H), 4.74 (d, 7= 1.2 Hz, 1H), 3.81 (s, 3H), 3.80 (s, 3H), 3.20 (s, 3H), 3.04 (s, 3H), 2.86 (d, 7= 9.5 Hz, 1H), 0.97 (d, 7 = 6.4 Hz, 3H); 13C NMR (126 MHz, CDC13) δ 152.89, 152.82, 146.94, 145.53, 139.56, 138.92, 123.32, 123.26, 122.01, 1 19.01, 111.30, 79.20, 77.22, 60.07, 59.26, 55.77, 55.64, 18.34; HRMS-ESI (m/z) ([M+Na]+) calcd for
Figure imgf000038_0002
371.1465; found, 371.1456.
[0089] Example 31, Step 2: Preparation of l, l-bis(2,3-dimethoxyphenyl)propan-2-one.
Figure imgf000039_0001
[0090] To a solution of (S)-l,l-bis(2,3-dimethoxyphenyl)propane-l,2-diol (560 mg, 1.61 mmol) in anhydrous CH2CI2 (8 mL) at 0 °C was added triethylsilane (770 μΐ, 4.82 mmol) and trifluoroacetic acid (TFA, 124 μΐ., 1.61 mmol). The resulting solution was stirred at 0 °C for 2 h, then removed from the cold bath and stirred for 2 h. TFA (248 [iL, 3.2 mmol) was added, and the reaction was then stirred overnight at rt. The reaction was diluted with water (25 mL) and extracted with CH2CI2 (3x 25 mL). The organic extracts were dried over Na2S04, filtered, and concentrated to provide an oil. Purification by automated silica gel column chromatography (5-25% acetone in hexanes) provided the title compound (396 mg, 75%) as a white solid: 1H NMR (300 MHz, CDC13) δ 6.99 (t, J= 8.0 Hz, 2H), 6.87 (dd, J= 8.2, 1.5 Hz, 2H), 6.67 - 6.54 (m, 2H), 5.86 (s, 1H), 3.87 (s, 6H), 3.75 (s, 6H), 2.25 (s, 3H); 13C NMR (126 MHz, CDC13) δ 207.18, 152.69, 147.02, 132.23, 123.74, 121.61, 111.64, 60.36, 55.74, 51.96, 29.80; HRMS-ESI (m/z) ([M+Na]+) calcd for
Ci9H2205Na, 353.1359; found, 353.1353. [0091] Example 31, Step 3: Preparation of l,l-bis(2,3-dimethoxyphenyl)propan-2-ol.
Figure imgf000039_0002
[0092] To a solution of l,l-bis(2,3-dimethoxyphenyl)propan-2-one (356 mg, 1.08 mmol) in methanol (3.5 mL) was added sodium borohydride (61 mg, 1.6 mmol). The resulting solution was stirred at rt for 20 h, then was quenched with sat'd NH4CI (1 mL), diluted with water (20 mL) and extracted with CH2CI2 (3x 20 mL). The organic extracts were combined, dried over Na2S04, filtered, and concentrated to provide the title compound (360 mg, 100%) as an oil: 1H NMR (300 MHz, CDCI3) δ 7.16 - 6.88 (m, 4H), 6.79 (ddd, J= 9.6, 7.8, 1.9 Hz, 2H), 4.81 (d, J= 8.3 Hz, 1H), 4.53 - 4.32 (m, 1H), 3.84 (s, 3H), 3.84 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H), 2.04 (d, J= 4.2 Hz, 1H), 1.22 (d, J= 6.2 Hz, 3H); 13C NMR (126 MHz, CDC13) δ 152.98, 152.83, 147.71, 147.04, 136.17, 135.33, 123.94, 123.62, 120.96, 120.84, 110.76, 110.48, 70.32, 60.26, 60.20, 55.66, 55.63, 45.11, 21.80; IR (neat film) 3451, 2935, 2833, 1582, 1473, 1428, 1266, 1215, 1167, 1125, 1088, 1068, 1004, 964, 908, 835, 809, 787, 748, 728.
[0093] Example 4A: Preparation of (S)-(S)- 1 , 1 -diphenylpropan-2-yl 2-{{tert- butoxycarbonyl)amino)-propanoate.
Figure imgf000040_0001
[0094] To a solution of (S)-l,l-diphenylpropan-2-ol (317 mg, 1.493 mmol) in DCM (15 mL) at 0 °C were added (S)-2-((fert-butoxycarbonyl)amino)propanoic acid (Boc-Ala-OH; 311 mg, 1.64 mmol) and N,N-dimethylpyridin-4-amine (DMAP; 18.2 mg, 0.149 mmol) followed by Nl- ((ethylimino)methylene)-N3,N3-dimethyl propane- 1,3 -diamine hydrochloride (EDC; 573 mg, 2.99 mmol), and the reaction mixture was stirred at room temperature overnight and concentrated to give a yellow oil. The crude material was purified by flash column chromatography (Si02, 1 -M0% acetone in hexanes) to afford the title compound (433 mg, 75%) as a colorless oil: 1H NMR (400 MHz, CDCI3) δ 7.42 - 7.07 (m, 1 OH), 5.80 (dq, J= 10.1, 6.1 Hz, 1H), 4.97 (d, J= 8.0 Hz, 1H), 4.19 - 4.06 (m, 1H), 4.03 (d, J= 10.1 Hz, 1H), 1.41 (s, 9H), 1.23 (d, J= 6.1 Hz, 3H), 0.76 (d, J= 7.2 Hz, 3H); 13C MR (101 MHz, CDC13) δ 172.83, 154.96, 141.52, 141.26, 128.79, 128.50, 128.10, 128.08, 126.91, 126.67, 79.62, 73.10, 57.98, 49.21, 28.33, 19.31, 17.98; ESIMS w/ 384 ([M+H]+).
[0095] Example 5, Step 1 : Preparation of (S)- 1 -(((S)- 1 , 1 -diphenylpropan-2-yl)oxy)- 1 - oxopropan-2-aminium chloride.
Figure imgf000040_0002
[0096] To a solution of (S)-(S)- 1 , 1 -diphenylpropan-2-yl 2-((tert- butoxycarbonyl)amino)propanoate (Cmpd 2; 433 mg, 1.13 mmol) in DCM (6 mL) was added a 4 N solution of HC1 in dioxane (2.8 mL, 1 1.3 mmol), and the mixture was stirred for 3 h at room temperature. The solvent was evaporated under a stream of N2 to provide the title compound (360 mg, 100%) as a white solid: ESIMS (mlz) 284 ([M+H]+).
[0097] Example 5, Step 2: Preparation of 0S)-(S l, l-diphenylpropan-2-yl 2-(3-hydroxy-4- methoxypicolinamido)propanoate.
Figure imgf000041_0001
[0098] To a solution of (S)- 1 -(((S)- 1 , 1 -diphenylpropan-2-yl)oxy)- 1 -oxopropan-2-aminium chloride (Cmpd 46; 361 mg, 1.13 mmol) and 3-hydroxy-4-methoxypicolinic acid (210 mg, 1.24 mmol) in DCM (1 1 mL) were added benzotriazol-l-yl-oxytripyrrolidinophosphonium
hexafluorophosphate (PyBOP; 646 mg, 1.24 mmol) and N-ethyl-N-isopropylpropan-2-amine
(DIPEA; 0.651 mL, 3.72 mmol), and the reaction mixture was stirred for 2 h at room temperature. The solvent was evaporated and the crude oil was purified by flash column chromatography (Si02, 1 - 50% acetone in hexanes) to afford the title compound (340 mg, 70%) as a white foam: 1H NMR (400 MHz, CDC13) δ 12.10 (s, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, 1H), 7.38 - 7.06 (m, 10H), 6.86 (d, J= 5.3, 1H), 5.83 (dq, J= 10.1, 6.1 Hz, 1H), 4.52 (dq, J= 8.1, 7.2 Hz, 1H), 4.06 (d, J= 10.2 Hz, 1H), 3.93 (s, 3H), 1.26 (d, J= 6.1 Hz, 3H), 0.97 (d, J= 7.2 Hz, 3H); 13C NMR (101 MHz, CDC13) 5 171.67, 168.53, 155.34, 148.72, 141.38, 141.13, 140.40, 130.48, 128.80, 128.50, 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93, 56.07, 47.85, 19.24, 17.61; HRMS-ESI (mlz) ([M+H]+) calcd for C25H27N2O5, 435.1920; found, 435.1925.
[0099] Example 6A: Preparation of (S)-(S)- l,l-diphenylpropan-2-yl 2-(3-acetoxy-4- methoxypicolinamido)propanoate.
Figure imgf000042_0001
[00100] To a solution of (S)-(S)-l, l-diphenylpropan-2-yl 2-(3-hydroxy-4- methoxypicolinamido)-propanoate (Cmpd 90; 70.0 mg, 0.161 mmol), Et3N (44.9 μΐ^, 0.332 mmol), and DMAP (3.94 mg, 0.032 mmol) in DCM (3.2 mL) was added acetyl chloride (17.2 jiL, 0.242 mmol) at room temperature, and the reaction mixture was stirred for 2 h. The solvent was evaporated, and the resulting crude oil was purified by flash column chromatography (Si02, l - 40% acetone in hexanes) to afford the title compound (75.0 mg, 97%) as a colorless oil: 1H NMR (400 MHz, CDC13) δ 8.41 (d, J= 7.8 Hz, 1H), 8.30 (d, J= 5.4 Hz, 1H), 7.38 - 7.10 (m, 10H), 6.97 (d, J= 5.4 Hz, 1H), 5.82 (dq, J= 10.0, 6.2 Hz, 1H), 4.52 (dt, J= 8.2, 7.1 Hz, 1H), 4.05 (d, J= 10.1 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.24 (d, J= 6.1 Hz, 3H), 0.89 (d, J= 7.1 Hz, 3H); 13C NMR (101 MHz, CDC13) δ 172.23, 168.89, 162.28, 159.42, 146.66, 141.55, 141.44, 141.25, 137.45, 128.77, 128.50, 128.13, 128.1 1, 126.89, 126.67, 109.73, 73.32, 57.90, 56.27, 47.85, 20.75, 19.25, 17.92; HRMS-ESI (mlz) ([M+H]+) calcd for C27H29N206, 477.2025; found, 477.2019.
[00101] Example 6B: Preparation of (,S)-(S)-l, l-diphenylpropan-2-yl 2-(3-(acetoxymethoxy)- 4-methoxypicolinamido)propanoate.
Figure imgf000042_0002
[00102] To a suspension of (S)-(S)- l,l-diphenylpropan-2-yl 2-(3-hydroxy-4- methoxypicolinamido)-propanoate (Cmpd 90; 100 mg, 0.230 mmol) and K2C03 (63.6 mg, 0.460 mmol) in acetone (4.6 mL) was added bromomethyl acetate (33.9 iL, 0.345 mmol) at room temperature, and the mixture was heated to 55 °C for 3 h and then cooled to room temperature. The solvent was evaporated and the resulting crude material was purified by flash column
chromatography (Si02, l - 40% acetone in hexanes) to afford the title compound (94.0 mg, 80% yield) as a colorless oil: 1H MR (400 MHz, CDC13) δ 8.25 (d, J= 5.4 Hz, 1H), 8.22 (d, J= 7.9 Hz, 1H), 7.34 - 7.09 (m, 10H), 6.92 (d, J= 5.4 Hz, 1H), 5.83 (dq, J= 10.1, 6.2 Hz, 1H), 5.72 (d, J= 0.7 Hz, 2H), 4.60 - 4.49 (m, 1H), 4.06 (d, J= 10.1 Hz, 1H), 3.88 (s, 3H), 2.05 (s, 3H), 1.25 (d, J= 6.1 Hz, 3H), 0.91 (d, J= 7.2 Hz, 3H); 13C NMR (101 MHz, CDC13) δ 172.33, 170.25, 162.88, 160.24, 145.70, 143.91, 142.54, 141.48, 141.25, 128.76, 128.49, 128.12, 128.09, 126.89, 126.65, 109.56, 89.50, 73.27, 57.92, 56.17, 48.07, 20.86, 19.25, 17.73; HRMS-ESI (mlz) [M+H]+ calcd for
C28H3iN207, 507.2131; found, 507.2125.
[00103] Example 6C: Preparation of (S)-(S)-l,l-diphenylpropan-2-yl 2-(3- ((i sobutyry 1 oxy )methoxy )-4-methoxypi colinamido)propanoate .
Figure imgf000043_0001
[00104] To a solution of (S)-(S)-l,l-diphenylpropan-2-yl 2-(3-hydroxy-4- methoxypicolinamido)-propanoate (Cmpd 90; 100 mg, 0.230 mmol) in acetone (4.6 mL) were added sodium carbonate (Na2C03; 73.2 mg, 0.690 mmol), sodium iodide (Nal; 6.90 mg, 0.046 mmol) and chloromethyl 2-ethoxyacetate (62.9 mg, 0.460 mmol). The mixture was heated to 55 °C overnight and then cooled to room temperature, and the solvent was evaporated. The resulting residue was purified by flash column chromatography (Si02, 2- 30% acetone in hexanes) to afford the title compound (79.0 mg, 64%) as a colorless oil: 1H NMR (400 MHz, CDC13) δ 8.28 (d, J= 7.9 Hz, 1H), 8.25 (d, J= 5.3 Hz, 1H), 7.36 - 7.08 (m, 10H), 6.92 (d, J= 5.4 Hz, 1H), 5.83 (dq, J= 10.1, 6.2 Hz, 1H), 5.79 - 5.69 (m, 2H), 4.62 - 4.44 (m, 1H), 4.06 (d, J= 10.1 Hz, 1H), 3.86 (s, 3H), 2.53 (hept, J= 7.0 Hz, 1H), 1.25 (d, J= 6.2 Hz, 3H), 1.13 (d, J= 7.0 Hz, 6H), 0.91 (d, J= 7.2 Hz, 3H); ijC MR (101 MHz, CDC13) δ 176.22, 172.34, 162.85, 160.23, 145.55, 144.16, 142.18, 141.48, 141.26, 128.76, 128.49, 128.12, 128.09, 126.89, 126.65, 109.48, 89.90, 73.26, 57.93, 56.12, 48.07, 33.85, 19.26, 18.68, 17.74; HRMS-ESI (m/z) (|M+H]+) calcd for C30H35N2O7, 535.2444; found, 535.2431.
[00105] Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Zymoseptoria tritici; Bayer code SEPTTR):
[00106] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water (H20) containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases, unless stated otherwise. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Try col 5941 in the spray solutions.
[00107] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50%) soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100%) relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. When disease symptoms were fully expressed on the 1st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.
[00108] Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust {Puccinia triticina; Synonym: Puccinia recondita f. sp. tritici; Bayer code PUCCRT):
[00109] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%> mineral soil/50%) soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22 °C with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A. [00110] Example C: Evaluation of Fungicidal Activity: Wheat Glume Blotch {Leptosphaeria nodorum; Bayer code LEPTNO):
[00111] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50%) soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 h after fungicide treatments. After inoculation the plants were kept in 100%) relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20 °C) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
[00112] Example D: Evaluation of Fungicidal Activity: Apple Scab {Venturia inaequalis; Bayer code VENTIN):
[00113] Apple seedlings (variety Mcintosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 h after fungicide treatment and kept in a 22 °C dew chamber with 100% relative humidity for 48 h, and then moved to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00114] Example E: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer code CERCBE):
[00115] Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 h after fungicide treatments. Inoculated plants were kept in a dew chamber at 22 °C for 48 h then incubated in a greenhouse set at 24 °C under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A. [00116] Example F: Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer code PHAKPA):
[00117] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of H20 containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off All sprayed plants were allowed to air dry prior to further handling.
[00118] Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22 °C and 100% relative humidity then transferred to a growth room at 23 °C for disease to develop. Disease severity was assessed on the sprayed leaves.
[00119] Example G: Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer code RHYNSE):
[00120] Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when the first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22°C with 100% relative humidity for 48 h. The plants were then transferred to a greenhouse set at 20 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00121] Example H: Evaluation of Fungicidal Activity: Rice Blast (Pyricularia oryzae; Bayer code PYRIOR):
[00122] Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00123] Example I: Evaluation of Fungicidal Activity: Tomato Early Blight {Alternaria solani; Bayer code ALTESO):
[00124] Tomato plants (variety Outdoor Girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 h after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 h to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
[00125] Example J: Evaluation of Fungicidal Activity: Cucumber Anthracnose
{Colletotrichum lagenarium; Bayer code COLLLA):
[00126] Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22 °C with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22 °C for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Table 1. Compound Structure, Preparation Method, and Appearance
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
88
Figure imgf000090_0001

Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
235 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
236 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
237 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
Figure imgf000107_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
238 Example 1; Slightly
Example 2A; Cloudy Example 3A; Colorless Example 4A. Viscous Oil
239 Example 1; Slightly
Example 2A; Cloudy Example 3A; Colorless Example 4A. Viscous Oil
240 Example 1; White Foam
Example 2A;
Example 3A;
Example 4A.
241 Example 3H Colorless Oil
Steps 1-2;
Example 4A.
Figure imgf000108_0001
Figure imgf000109_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
245 Example 1; White Foam
Example 3C;
Example 4A.
246 Example 1; White Foam
Example 2A;
Example 3A;
Example 4A.
247 Example 1; White Foam
Example 3C;
Example 4A.
Figure imgf000110_0001
Figure imgf000111_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
252 Example 1 ; White
Example 2A; Semisolid Example 3A;
Example 4A.
253 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
254 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
255 Example 1 ; Clear,
Example 2A; Colorless Oil Example 3A;
Example 4A.
Figure imgf000112_0001
Figure imgf000113_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
260 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A.
261 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A.
262 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A.
263 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A.
Figure imgf000114_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
264 Example 1; White Foam
Example 2A;
Example 3A;
Example 4A.
265 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A.
Figure imgf000115_0001
266 Example 1; Sticky Wax
Example 2A;
Example 3A;
Example 4A.
Figure imgf000115_0002
Prepared
^Cmpd. According
Structure Appearance No. To
Example
267 Example 1; Sticky Wax.
Example 2A;
Example 3A;
Example 4A.
268 Example 31,
Example 4A
269 Example 31,
Example 4A
Figure imgf000116_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
270 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
271 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
272 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
273 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
Figure imgf000117_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
274 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
275 Example 3F; Colorless Oil
Example 4A
276 Example 3F; Colorless Oil
Example 4A
277 Example 3F; Colorless Oil
Example 4A
Figure imgf000118_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
278 Example 3F; Colorless Oil
Example 4A
279 Example 3F; Colorless Oil
Example 4A
280 Example 3F; Colorless Oil
Example 4A
281 Example 3F; Colorless Oil
Example 4A
Figure imgf000119_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
282 Example 3F; Colorless Oil
Example 4A
283 Example 3F; Colorless Oil
Example 4A
284 Example 3F; Colorless Oil
Example 4A
285 Example 3F; Colorless Oil
Example 4A
Figure imgf000120_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
286 Example 3F; Colorless Oil
Example 4A
287 Example 3F; Colorless Oil
Example 4A
288 Example 3F; White Foam
Example 4A
289 Example 3F; Yellow Sticky
Example 4A Wax
Figure imgf000121_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
290 Example 3F; White Foam
Example 4A
291 Example 3F; Yellow Sticky
Example 4A Wax
292 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
293 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
Figure imgf000122_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
294 Example 1; Colorless Oil
Example 2A;
Example 3A;
Example 4A
295 Example 3F; Colorless Oil
Example 4A
296 Example 3F; Colorless Oil
Example 4A
297 Example 3F; Colorless Oil
Example 4A
Figure imgf000123_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
298 Example 3F; Colorless Oil
Example 4A
299 Example 3F; Colorless Oil
Example 4A
300 Example 3F; Colorless Oil
Example 4A
301 Example 3F; Colorless Oil
Example 4A
Figure imgf000124_0001
Prepared
*Cmpd. According
Structure Appearance No. To
Example
302 /CH3 Example 3F; Colorless Oil
0 C H3 Example 4A CH3 0 CH3
303 Example 3F; Colorless Oil
Example 4A
304 Example 3F; Colorless Oil
Example 4A
305 Example 3F; Colorless Oil
Example 4A
Figure imgf000125_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
306 Example 3F; Colorless Oil
Example 4A
307 Example 3F; Colorless Oil
Example 4A
308 Example 3F; Thick Oil
Example 4A
309 Example 3F; Colorless Oil
Example 4A
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
463 Example 6B. Slightly
Opaque Colorless Viscous Oil
464 Example 6B. Yellow Oil
465 Example 6B. Clear,
Colorless Oil
Figure imgf000173_0001
Figure imgf000174_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
469 Example 6A. Clear,
Colorless Oil
470 Example 6A. Clear,
Colorless Oil
Figure imgf000175_0001
471 I H3C^ _ 0^ /CH3 Example 6A. Clear,
Colorless Oil
Prepared
^Cmpd. According
Structure Appearance No. To
Example
472 Example 6B. White Foam
473 Example 6B. Sticky Wax
474 Example 6B. Colorless Oil
Figure imgf000176_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
475 Example 6A. White Foam
476 Example 6B. White Foam
477 Example 6A. White Foam
Figure imgf000177_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
478 Example 6A. White Foam
479 Example 6A. White Foam
480 Example 6B. White Foam
Figure imgf000178_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
481 Example 6B. White Foam
482 Example 6B. White Foam
483 Example 6B. White Foam
Figure imgf000179_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
484 Example 6B. White Foam
485 Example 6A Colorless Oil
486 Example 6A Colorless Oil
Figure imgf000180_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
487 Example 6B Colorless Oil
488 Example 6A. White Foam
489 Example 6A. White Foam
Figure imgf000181_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
490 Example 6A. White Wax
491 Example 6A. White Foam
492 I Example 6A. White Foam
Figure imgf000182_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
493 Example 6B White Foam
494 Example 6C White Foam
495 I Example 6A White Foam
Figure imgf000183_0001
Figure imgf000184_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
499 Example 6A. White Foam
500 Example 6A. White Foam
501 Example 6A. White Foam
502 Example 6A. White Foam
Figure imgf000185_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
503 Example 6A. White Foam
504 Example 6A. White Foam
Figure imgf000186_0001
505 Example 6A. Clear,
Colorless Oil
Figure imgf000186_0002
Prepared
*Cmpd. According
Structure Appearance No. To
Example
506 Example 6A. Clear,
Colorless Oil
507 Example 6A. Clear,
Colorless Oil
508 Example 6A. Clear,
Colorless Oil
Figure imgf000187_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
509 Example 6A. Clear,
Colorless Oil
510 Example 6A. Clear,
Colorless Oil
511 Example 6A. Clear,
Colorless Oil
Figure imgf000188_0001
Prepared
*Cmpd. According
Structure Appearance No. To
Example
512 Example 6A. Clear,
Colorless Oil
513 Example 6B. Clear,
Colorless Oil
514 Example 6B. Clear,
Colorless Oil
Figure imgf000189_0001
Prepared
*Cmpd. According
Structure Appearance No. To
Example
515 Example 6B. Clear,
Colorless Oil
516 Example 6B. Clear,
Colorless Oil
517 Example 6B. Clear,
Colorless Oil
Figure imgf000190_0001
Prepared
*Cmpd. According
Structure Appearance No. To
Example
518 Example 6B. Clear,
Colorless Oil
519 Example 6B. Clear,
Colorless Oil
520 Example 6B. Clear,
Colorless Oil
Figure imgf000191_0001
Figure imgf000192_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
524 Example 6A Colorless Oil
525 Example 6A Colorless Oil
526 I Example 6A Colorless Oil
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
533 Example 6A Colorless Oil
534 Example 6A Colorless Oil
535 I Example 6A. White Foam
Figure imgf000196_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
536 Example 6A. White Foam
537 Example 6A. White Foam
538 I Example 6A. White Foam
Figure imgf000197_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
539 Example 6A. White Foam
540 Example 6A. White Foam
541 I Example 6A. White Foam
Figure imgf000198_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
542 Example 6A. White Foam
543 Example 6A. White Foam
544 I Example 6A. White Foam
Figure imgf000199_0001
Prepared
^Cmpd. According
Structure Appearance No. To
Example
545 Example 6A. White Foam
546 Example 6A. White Foam
Figure imgf000200_0001
547 Example 6A. White Foam
Prepared
^Cmpd. According
Structure Appearance No. To
Example
548 Example 6A. White Foam
549 Example 6A. White Foam
550 Example 6A. White Foam
Figure imgf000201_0001
Figure imgf000202_0001
Figure imgf000203_0001
*Cmpd. No. - Compound Number
Table 2. Analytical Data
Figure imgf000204_0001
Figure imgf000205_0001
Figure imgf000206_0001
Figure imgf000207_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 7.30 - 7.22 (m, 4H), 7.22 - 7.15 (m, 4H), 5.71 (dq, J= 9.6, 6.2 Hz, 1H), 4.91 (d, J= 8.0 Hz, lH), 4.21 - 4.06 (m, lH), 4.00 (d, J=
ESIMS
9.8 Hz, lH), 1.42 (s, 9H), 1.22 (d, J= 6.2 in z 452.5
19 — — Hz, 3H), 0.85 (d, J= 7.2 Hz, 3H)
([M+H]+)
13C NMR (101 MHz, CDC13) δ 172.75, 154.96, 139.41, 139.25, 133.03, 132.77, 129.43, 129.35, 129.05, 128.74, 79.81, 72.51, 56.45, 49.17, 28.30, 19.18, 18.09 l NMR (400 MHz, CDC13) δ 7.25 - 7.14 (m, 4H), 7.06 - 6.87 (m, 4H), 5.68 (dq, J= 9.3, 6.2 Hz, lH), 4.83 (s, lH), 4.02 (d, J= 9.3 Hz, 1H), 3.82 (dd, J= 18.2, 5.9 Hz, 1H), 3.56 (dd, J= 18.2, 5.2
ESIMS Hz, lH), 1.43 (s, 9H), 1.22 (d, J= 6.2 Hz, m/z 406.5 3H)
20 — —
([M+H]+)
13C NMR (101 MHz, CDC13) δ 169.66, 161.74 (d, J= 245.9 Hz), 161.63 (d, J= 245.7 Hz), 155.45, 136.74, 129.65 (d, J= 7.9 Hz), 115.70 (d, J= 21.3 Hz), 115.41 (d, J= 21.2 Hz), 79.97, 77.21, 73.15, 55.84, 42.44, 28.29, 19.17
l NMR (400 MHz, CDC13) δ 7.30 - 7.15 (m, 4H), 7.06 - 6.89 (m, 4H), 5.75 - 5.62 (m, lH), 4.90 (d, J= 8.4 Hz, lH), 4.11 (q, J= 6.7 Hz, 1H), 4.03 (d, J= 9.8
ESIMS Hz, lH), 1.49 - 1.33 (m, lOH), 1.30 - in z 434.6 1.08 (m, 4H), 0.54 (t, J= 7.4 Hz, 3H)
21 — —
([M+H]+)
13C NMR (101 MHz, CDC13) δ 172.10, 161.70 (d, J= 245.6 Hz), 155.20, 136.97, 129.52, 115.71 (d, J= 21.3 Hz), 115.44 (d, J= 21.2 Hz), 79.73, 73.12, 56.08, 54.46, 28.30, 25.40, 19.26, 8.95
Figure imgf000209_0001
Figure imgf000210_0001
Figure imgf000211_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 7.24 (dd, J = 10.4, 8.1 Hz, 2H), 7.09 (dd, J= 5.5, 2.2 Hz, 2H), 7.02 (td, J= 8.6, 2.3 Hz, 2H), 5.69 (dq, J= 10.1, 6.1 Hz, IH), 4.94 (d, J = 7.9 Hz, IH), 4.13 (t, J= 7.5 Hz, IH), 3.92 (d, J= 10.0 Hz, IH), 2.33 (s, 3H),
ESIMS 2.31 (s, 3H), 1.42 (s, 9H), 1.21 (d, J = 6.1
35 — — m/z 480.6 Hz, 3H), 0.84 (d, J= 7.2 Hz, 3H)
([M]+)
13C NMR (126 MHz, CDC13) δ 172.81, 154.92, 139.66, 139.44, 136.53, 136.10, 133.08, 132.72, 130.69, 130.57, 129.43, 129.12, 126.59, 126.46, 79.77, 72.61, 56.49, 49.17, 28.29, 20.16, 20.09, 19.23, 18.09
l NMR (300 MHz, CDC13) δ 7.82 (ddd,
(Thin
J= 8.6, 7.3, 1.8 Hz, IH), 7.51 (tt, J= 7.9, film)
1.5 Hz, IH), 7.33 - 7.12 (m, 3H), 7.09
3385,
(td, J= 7.6, 1.4 Hz, IH), 6.94 (dd, J= 2980,
36 — — 8.1, 1.4 Hz, IH), 6.90 (dd, J= 8.1, 1.4
1669,
Hz, 1H), 6.23 (qd, J= 6.3, 1.6 Hz, IH), 1486,
5.02 (d, J= 7.9 Hz, IH), 4.30 - 4.13 (m, 1452,
IH), 3.21 (s, IH), 1.42 (s, 9H), 1.26 (d, J 1160, 757
= 6.2 Hz, 3H), 1.07 (d, J= 7.2 Hz, 3H)
(Thin
film)
3375,
2981,
1703,
lH NMR (300 MHz, CDC13) 5 7.18 - 1609,
6.91 (m, 6H), 5.63 (dq, J= 9.4, 6.2 Hz, 1515,
HRMS-ESI IH), 4.92 (d, J= 8.0 Hz, IH), 4.24 - 4.06 1453,
(m/z) (m, IH), 3.98 (d, J= 9.5 Hz, IH), 1.42 (s, 1433,
[M+Na]+ 9H), 1.23 (d, J= 6.1 Hz, 3H), 0.91 (d, J= 1380,
calcd for 7.2 Hz, 3H)
37 — 1367,
C23H25F4NNa04,
1284,
478.1612; 19F NMR (471 MHz, CDC13) δ
1250,
found, -136.25 (dt, J= 20.6, 9.7 Hz),
1208,
478.1624 -136.69 (dt, J= 20.4, 9.9 Hz),
1162,
-139.30 (dd, J= 21.3, 10.5 Hz), 1113,
-139.70 (dd, J= 21.1, 10.1 Hz)
1053,
1023, 967,
909, 873,
821, 754,
731 Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3440,
2981,
1704,
1600,
lH NMR (300 MHz, CDC13) δ 7.32 - 1497,
HRMS-ESI 7.22 (m, 2H), 7.18 - 7.02 (m, 4H), 5.64 1452,
(m/z) (dq, J= 9.6, 6.2 Hz, 1H), 4.93 (d, J= 8.0 1379,
[M+Na]+ Hz, IH), 4.25 - 4.03 (m, IH), 3.98 (d, J= 1367,
calcd for 9.6 Hz, IH), 1.42 (s, 9H), 1.23 (d, J= 6.2
38 — 1306,
C23H25Cl2F2NNa04, Hz, 3H), 0.92 (d, J= 7.2 Hz, 3H) 1250,
510.1021 ;
1210,
found, 19F NMR (471 MHz, CDC13) δ
1162,
510.1033 -1 16.98 (q, J= 6.9 Hz), -117.44 (q, J= 1095,
6.8 Hz)
1054,
1023, 907,
867, 822,
799, 780,
731, 719,
689
(Thin
film)
3364,
2980,
2931,
Ti NMR ^OO MHz, CDC13) 5 7.13 - 1707,
6.98 (m, 4H), 6.90 (td, J= 9.1, 7.4 Hz, 1597,
HRMS-ESI 2H), 5.67 (dq, J= 10.1, 6.1 Hz, IH), 4.93 1501,
(m/z) (d, J= 8.0 Hz, IH), 4.22 - 4.02 (m, IH), 1451,
[M+Na]+ 3.91 (d, J= 10.1 Hz, 1H), 2.23 (d, J= 2.0 1379,
calcd for Hz, 3H), 2.21 (d, J= 2.0 Hz, 3H), 1.42 (s,
39 — 1366,
C25H3iF2NNa04, 9H), 1.21 (d, J= 6.1 Hz, 3H), 0.83 (d, J= 1307,
470.2113; 7.2 Hz, 3H)
1248,
found,
1207,
470.2120 19F NMR (471 MHz, CDC13) δ
1163,
-1 19.99 (q, J= 6.8 Hz), -120.57 (q, J= 1118,
7.0 Hz)
1052,
1023, 959,
908, 881,
821, 781,
731
Figure imgf000214_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 7.38 - 7.28 (m, 2H), 7.06 (dd, J= 10.0, 1.8 Hz, lH), 7.04 - 6.94 (m, 3H), 5.66 (ddt, J= 9.1, 6.9, 5.5 Hz, lH), 4.92 (d, J= 8.0 Hz, lH), 4.22 - 4.08 (m, 1H), 4.01 (d, J= 9.4
HRMS-ESI Hz, lH), 1.42 (d,J= 1.3 Hz, 9H), 1.24
(m/z) (dd,J= 6.2, 1.3 Hz, 3H), 0.92 (d,J= 7.2 [M+Na]+ Hz, 3H)
calcd for
44 — —
C23H25Cl2F2NNa04, 13C NMR (126 MHz, CDC13) δ 172.68, 510.1021; 158.17 (d,J= 250.1 Hz), 158.03 (d,J= found, 250.1 Hz), 154.93, 141.08 (d,J=6.1 510.1030 Hz), 140.95 (d,J=6.1Hz), 131.11,
130.80, 124.51 (d,J=3.3Hz), 124.36 (d, J=3.6Hz), 120.08 (d,J= 17.6 Hz), 119.78 (d, J= 17.6 Hz), 116.48 (d, J= 16.8 Hz), 116.24, 79.92, 72.02, 56.07, 49.15,28.28, 19.10, 18.10
ESIMS
m/z 300
45 — — —
([M+H]+)
ESIMS
m/z 284.3
46 — — —
([M+H]+)
ESIMS
m/z 296.3
47 — — —
([M+H]+)
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3395,
2885,
1741,
1603,
1508, HRMS-ESI lH NMR (400 MHz, CDC13) δ 8.55 (s, 1459, (m/z) 3H), 7.22 (dt, J= 9.0, 4.8 Hz, 4H), 6.98 1381, ([M+H]+) (q,J=8.2Hz,4H),5.71 (dq,J= 11.8, 1324, calcd 6.1Hz, 1H),4.05 (d, J= 9.8 Hz, 2H),
48 — 1224, calcd for 1.23 (d,J=5.9Hz, 3H), 1.13 (d,J=6.7
1159, C18H20F2NO2, Hz, 3H)
1137, 320.1457;
1118, found, 19F NMR (376 MHz, CDC13) δ 1049, 320.1457 -115.32,-115.70
1015,955,
881,826,
793, 779,
755, 746,
721, 693,
666
ESIMS
49 — — 111 z 341.5 —
([M+Na]+)
ESIMS
m/z 314.6
50 — — —
([M+H]+)
ESIMS
m/z 356.4
51 — — —
([M+H]+)
ESIMS
m/z 302.4 19F NMR (376 MHz, CDC13) δ
52 — —
([M+H]+) -169.31
ESIMS
m/z 344.5
53 — — —
([M+H]+) Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
ESIMS
m/z 320.4
54 — — —
([M+H]+)
ESIMS
m/z 352.4
55 — — —
([M+H]+)
ESIMS
m/z 282.4
56 — — —
([M+H]+)
ESIMS
m/z 298.4
57 — — —
([M+H]+)
ESIMS
m z 442.4
58 — — —
([M+H]+)
ESIMS
m/z 324.4
59 — — —
([M+H]+)
ESIMS
m/z 312.3
60 — — —
([M+H]+)
ESIMS
m/z 436
61 — — —
([M+H]+)
ESIMS
63 — — m/z 375.5 —
([M+Na]+)
ESIMS
64 — — m/z 375.5 —
([M+Na]+) Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
ESIMS
m/z 344.5
65 — — —
([M+H]+)
ESIMS
m/z 344.5
66 — — —
([M+H]+)
ESIMS
m/z 348.5
67 — — —
([M+H]+)
ESIMS
m/z 380.5
68 — — —
([M+H]+)
ESIMS
m/z 332.5
69 — — —
([M+H]+)
ESIMS
m/z 340.5
70 — — —
([M+H]+)
(Thin HRMS-ESI
film) (m/z)
2959, ([M+H]+)
1749, calcd
71 — 1508, calcd for —
1401, C17H17F2N02,
1229, 306.1300;
1159, found,
1055, 830 306.1298
Figure imgf000219_0001
Figure imgf000220_0001
Figure imgf000221_0001
Figure imgf000222_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
2879,
1746,
HRMS-ESI
1587,
(m/z)
1561,
([M+H]+)
1517,
calcd
— 1468,
87 calcd for —
1395,
C18H18C14N02,
1227,
420.0086;
1194,
found,
1116,
420.0090
1053,
1029, 871,
822, 747,
727, 669
(Thin
film)
2858,
1747,
1580, HRMS-ESI
1486, (m/z)
1458, ([M+H]+)
1383, calcd
88 — 1368, calcd for —
1278, C18H18C12F2N02,
1236, 388.0677;
1206, found,
1119, 388.0688
1048, 970,
871, 824,
779, 761,
682
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (500 MHz, CDC13) δ 1 1.97 (d, J = 0.5 Hz, 1H), 8.33 (d, J= 8.1 Hz, 1H), 7.96 (d, J= 5.2 Hz, 1H), 7.47 (ddt, J=
HRMS-ESI 8.5, 6.4, 1.3 Hz, 4H), 7.33 - 7.13 (m,
(m/z) 5H), 6.89 - 6.81 (m, 1H), 6.03 (q, J= 6.3 [M]+ Hz, lH), 4.62 - 4.49 (m, 1H), 3.93 (s, calcd for 3H), 2.74 (s, 1H), 1.23 (d, J= 6.3 Hz,
89 — —
C25H26N206, 3H), 1.07 (d, J= 7.2 Hz, 3H)
450.1791 ;
found, 13C NMR (126 MHz, CDC13) δ 171.30, 450.1794 168.61, 155.37, 148.71, 144.85, 142.71,
140.44, 130.29, 128.33, 128.32, 127.22, 127.16, 125.51, 125.45, 109.44, 79.57, 75.54, 56.08, 47.85, 17.62, 14.32 l NMR (400 MHz, CDC13) δ 12.10 (d, J = 0.6 Hz, 1H), 8.34 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, lH), 7.38 - 7.06 (m,
HRMS-ESI
10H), 6.86 (dd, J= 5.3, 0.7 Hz, lH), 5.83
(m/z)
(dq, J= 10.1, 6.1 Hz, lH), 4.52 (dq, J= ([M+H]+)
8.1, 7.2 Hz, 1H), 4.06 (d, J= 10.2 Hz, calcd
lH), 3.93 (s, 3H), 1.26 (d, J= 6.1 Hz,
90 — — calcd for
3H), 0.97 (d, J= 7.2 Hz, 3H)
Figure imgf000224_0001
435.1920;
13C NMR (101 MHz, CDC13) δ 171.67, found,
168.53, 155.34, 148.72, 141.38, 141.13, 435.1925
140.40, 130.48, 128.80, 128.50, 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93, 56.07, 47.85, 19.24, 17.61 l NMR (400 MHz, CDC13) δ 12.10 (d, J = 0.6 Hz, 1H), 8.41 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, lH), 7.18 - 7.16 (m,
HRMS-ESI
2H), 7.01 (ddd, J= 3.6, 1.3, 0.6 Hz, lH),
(m/z)
6.94 - 6.88 (m, 3H), 6.86 (dd, J= 5.3, 0.7 ([M+H]+)
Hz, lH), 5.56 (dq, J= 7.4, 6.2 Hz, 1H), calcd
4.70 - 4.58 (m, 2H), 3.94 (s, 3H), 1.30 (d,
91 — — calcd for
J= 6.2 Hz, 3H), 1.24 (d, J= 7.2 Hz, 3H)
Figure imgf000224_0002
447.1048;
13C NMR (101 MHz, CDC13) δ 171.48, found,
168.62, 155.35, 148.74, 143.75, 142.69, 447.1047
140.43, 130.48, 126.77, 126.57, 126.05, 125.43, 124.61, 124.58, 109.44, 74.83, 56.08, 47.98, 47.42, 18.69, 17.80
Figure imgf000225_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 12.03 (d, J = 0.6 Hz, 1H), 8.31 (d, J= 7.9 Hz, 1H), 7.97 (d, J= 5.2 Hz, IH), 7.35 (td, J= 8.5, 6.2 Hz, IH), 7.23 (td, J= 8.4, 6.2 Hz, IH), 6.91 - 6.74 (m, 4H), 6.69 (ddd, J= 10.4, 8.8, 2.6 Hz, IH), 5.88 - 5.74 (m, IH), 4.69 (d, J= 9.9 Hz, IH), 4.64 - 4.48
96 — — —
(m, IH), 3.95 (s, 3H), 1.30 (d, J= 6.1 Hz, 3H), 1.17 (d, J= 7.2 Hz, 3H)
19F NMR (376 MHz, CDC13) δ
-110.97 (d, J= 7.7 Hz), -111.39 (d, J= 7.6 Hz), -111.98 (dd, J= 7.7, 2.6 Hz), - 112.83 (dd, J= 7.6, 2.6 Hz)
l NMR (400 MHz, CDC13) δ 12.06 (s, IH), 8.31 (d, J= 7.9 Hz, IH), 7.98 (d, J= 5.2 Hz, IH), 7.49 - 7.40 (m, 4H), 7.37 - 7.24 (m, 5H), 7.23 - 7.18 (m, IH), 6.86 (d, J= 5.2 Hz, IH), 6.00 (dq, J= 25 A,
97 — — — 6.4 Hz, IH), 4.63 - 4.51 (m, IH), 3.94 (s,
3H), 1.32 (dd, J= 6.5, 1.0 Hz, 3H), 0.96 (d, J= 7.2 Hz, 3H)
19F NMR (376 MHz, CDC13) δ
-169.17
l NMR (400 MHz, CDC13) δ 12.11 (s, IH), 8.35 (d, J= 8.0 Hz, IH), 7.97 (d, J= 5.2 Hz, IH), 7.22 - 7.12 (m, 4H), 6.90 -
HRMS-ESI 6.73 (m, 5H), 5.73 (dq, J= 9.8, 6.1 Hz,
(m/z) IH), 4.64 - 4.44 (m, IH), 3.96 (d, J= 9.9 ([M+H]+) Hz, IH), 3.93 (s, 3H), 3.75 (s, 3H), 3.73 calcd (s, 3H), 1.24 (d, J= 6.2 Hz, 3H), 1.05 (d,
98 — — calcd for J= 7.2 Hz, 3H)
Figure imgf000226_0001
495.2131; 13C NMR (101 MHz, CDC13) δ 171.65, found, 168.54, 158.36, 158.20, 155.34, 148.70, 495.2124 140.40, 133.83, 133.69, 130.45, 128.97,
128.92, 114.11, 113.81, 109.39, 73.77, 56.11, 56.04, 55.20, 55.19, 47.90, 19.20, 17.75
Figure imgf000227_0001
Figure imgf000228_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 12.09 (s, lH), 8.35 (d, J= 8.0 Hz, lH), 7.97 (d, J=
HRMS-ESI
5.2 Hz, lH), 7.54 (d, J= 8.1 Hz, 2H),
(m/z)
7.42 (d, J= 8.1 Hz, 2H), 7.34 - 7.21 (m, ([M+H]+)
4H), 7.21 - 7.13 (m, 1H), 6.86 (d, J= 5.2 calcd
Hz, 1H), 5.85 (dq, J= 9.8, 6.1 Hz, 1H),
106 — — calcd for
4.61 - 4.46 (m, 1H), 4.15 (d, J= 9.9 Hz,
Figure imgf000229_0001
lH), 3.93 (s, 3H), 1.27 (d, J= 6.2 Hz, 503.1794;
3H), 1.00 (d, J= 7.2 Hz, 3H) found,
503.1794
19F NMR (376 MHz, CDC13) δ
-62.53
l NMR (400 MHz, CDC13) δ 12.05 (s, lH), 8.32 (d, J= 8.0 Hz, lH), 7.97 (d, J=
HRMS-ESI 5.2 Hz, lH), 7.38 - 7.10 (m, 8H), 6.87 (d,
(m/z) J= 5.2 Hz, lH), 5.73 (dq, J= 9.9, 6.2 Hz, ([M+H]+) lH), 4.62 - 4.45 (m, 1H), 4.03 (d, J= 9.6 calcd Hz, lH), 3.94 (s, 3H), 1.25 (d, J= 6.1 Hz,
107 — — calcd for 3H), 1.09 (d, J= 7.2 Hz, 3H)
C25H25C12N205,
503.1140; 13C NMR (101 MHz, CDC13) δ 171.52, found, 168.61, 155.41, 148.74, 140.45, 139.26, 503.1139 139.15, 133.04, 132.77, 130.32, 129.41,
129.36, 129.05, 128.73, 109.49, 72.95, 56.35, 56.08, 47.86, 19.08, 17.67 l NMR (400 MHz, CDC13) δ 12.10 (s, lH), 8.36 (d, J= 7.9 Hz, lH), 7.95 (d, J= 5.2 Hz, 1H), 7.57 - 7.46 (m, 8H), 7.43 - 7.38 (m, 7H), 7.34 - 7.29 (m, 2H), 6.81 (d, J= 5.2 Hz, 1H), 5.90 (dq, J= 12.2, 6.1 Hz, lH), 4.56 (p, J= 7.2 Hz, lH), 4.16 (d, J= 10.0 Hz, lH), 3.89 (d, J= 1.9
ESIMS
Hz, 3H), 1.34 (d, J= 6.1 Hz, 3H), 1.02 m/z 587
109 — — (d, J= 7.2 Hz, 3H)
([M+H]+)
13C NMR (101 MHz, CDC13) δ 171.71, 168.59, 155.33, 148.72, 140.65, 140.58, 140.43, 140.1 1, 139.94, 139.66, 130.44, 128.77, 128.73, 128.67, 128.53, 127.58, 127.30, 127.26, 127.21, 127.00, 126.94, 109.40, 73.58, 57.25, 56.04, 47.91, 19.33, 17.66 Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3374,
2984, lH NMR (400 MHz, CDC13) δ 11.80 (s,
1735, lH), 8.30 (d, J= 8.0 Hz, lH), 8.07 (dd, J
1649, = 4.3, 1.5 Hz, 1H), 7.40-7.15 (m, 6H),
1602, 7.05 - 6.85 (m, 4H), 5.73 (dq, J= 9.8, 6.2
1577, Hz, lH), 4.65 - 4.45 (m, lH), 4.05 (d, J=
1530, HRMS-ESI 9.8 Hz, lH), 1.25 (d,J=6.1Hz, 3H),
1507, (m/z) 1.07 (d,J=7.2 Hz, 3H)
1449, ([M+H]+)
1380, calcd 13CNMR(101 MHz, CDC13) δ 171.60,
110 — 1329, calcd for 168.26, 161.76 (d, J= 246.1 Hz), 161.64
1296, C24H23F2N2O4, (d,J= 245.7 Hz), 157.79, 139.65, 136.82
1222, 441.1620; (d, J= 3.3 Hz), 136.71 (d, J= 3.5 Hz),
1188, found, 131.04, 129.50 (d,J= 7.9 Hz), 128.80,
1159, 441.1620 126.08, 115.74 (d,J=21.3 Hz), 115.41
1130, (d, J= 21.3 Hz), 73.34, 56.14, 47.84,
1105, 19.12, 17.69
1049,
1015,906, 19F NMR (376 MHz, CDC13) δ
826, 809, -115.44,-115.76
792, 778,
731,704,
666
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3370, lH NMR (400 MHz, CDC13) δ 12.06 (d, J
2984, = 0.6 Hz, 1H), 8.33 (d, J= 8.0 Hz, 1H),
2936, 7.95 (d,J=5.2Hz, lH), 7.35 - 7.14 (m,
2256, 4H), 7.04 - 6.87 (m, 4H), 6.84 (d, J= 5.2
1735, Hz, 1H),5.73 (dq,J=9.7,6.1Hz, 1H),
1647, 4.60- 4.48 (m, lH), 4.16 (q,J= 7.0 Hz,
1604, 2H), 4.05 (d, J= 9.7 Hz, lH), 1.51 (t, J=
HRMS-ESI
1574, 7.0 Hz, 3H), 1.24 (d,J=6.1Hz, 3H),
(m/z)
1529, 1.06 (d,J=7.2 Hz, 3H)
([M+H]+)
1507,
calcd
1483, 13C NMR (101 MHz, CDC13) δ 171.58,
Ill calcd for
1469, 168.66, 161.75 (d, J= 246.1 Hz), 161.64
1452,
Figure imgf000231_0001
(d,J= 245.7 Hz), 154.75, 148.82,
485.1883;
1381, 140.38, 136.82 (d, J= 3.3 Hz), 136.73 (d, found,
1323, J=3.3 Hz), 130.41, 129.51 (d,J=7.6
485.1880
1281, Hz), 115.72 (d,J=21.4Hz), 115.39 (d, J
1262, = 21.2 Hz), 110.13, 73.32, 64.67, 56.12,
1222, 47.84, 19.11, 17.69, 14.37
1158,
1109, 19F NMR (376 MHz, CDC13) δ
1048, -115.47,-115.80
1015,990,
904, 824,
800, 730
Figure imgf000232_0001
Figure imgf000233_0001
Figure imgf000234_0001
Figure imgf000235_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
lH NMR (400 MHz, CDC13) δ 12.06 (d, J film) HRMS-ESI
= 0.6 Hz, 1H), 8.33 (d, J= 8.0 Hz, 1H),
3285, (m/z)
7.98 (d, J= 5.2 Hz, lH), 7.45 - 7.40 (m, 2981, ([M+H]+)
2H), 7.40 - 7.35 (m, 2H), 7.28 - 7.18 (m, 2107, calcd for
123 — 4H), 6.86 (d, J= 5.2 Hz, lH), 5.78 (dq, J
1736, C2 H27N2O5,
= 9.8, 6.1 Hz, 1H), 4.61 - 4.45 (m, 1H), 1648, 483.1914;
4.07 (d, J= 9.8 Hz, lH), 3.94 (s, 3H), 1528, found,
3.05 (s, lH), 3.03 (s, 1H), 1.25 (d, J= 6.2 1263, 483.1919
Hz, 3H), 1.04 (d, J= 7.2 Hz, 3H) 1050
(Thin
film)
lH NMR (400 MHz, CDC13) δ 12.12 (s,
3368,
HRMS-ESI lH), 8.37 (d, J= 8.0 Hz, lH), 7.98 (d, J= 2963,
(m/z) 5.2 Hz, 1H), 7.24 - 7.18 (m, 4H), 7.14 - 1735,
([M+H]+) 7.08 (m, 2H), 7.08 - 7.02 (m, 2H), 6.85 1648,
calcd for (d, J= 5.2 Hz, 1H), 5.80 (dq, J= 10.1,
124 — 1527,
C2 H35N2O5, 6.2 Hz, lH), 4.63 - 4.40 (m, 1H), 3.99 (d, 1480,
491.2540; J= 10.2 Hz, lH), 3.93 (s, 3H), 2.65 - 1450,
found, 2.50 (m, 4H), 1.25 (d, J= 6.1 Hz, 3H), 1280,
491.2551 1.18 (t, J= 7.6 Hz, 3H), 1.14 (t, J= 7.6 1263,
Hz, 3H), 0.94 (d, J= 7.2 Hz, 3H) 1142,
1053
lH NMR (400 MHz, CDC13) δ 12.08 (d, J = 0.6 Hz, 1H), 8.33 (d, J= 8.0 Hz, 1H), 7.98 (d, J= 5.2 Hz, lH), 7.32 - 7.20 (m, 5H), 7.19 - 7.10 (m, 1H), 6.97 (t, J= 8.7 Hz, 2H), 6.86 (d, J= 5.2 Hz, lH), 5.78
HRMS-ESI
(dq, J= 10.0, 6.2 Hz, lH), 4.58 - 4.45
(m/z)
(m, 1H), 4.05 (d, J= 10.0 Hz, lH), 3.94 ([M+H]+)
(s, 3H), 1.26 (d, J= 6.2 Hz, 3H), 0.98 (d, calcd for
125 — — J= 7.2 Hz, 3H)
C25H26FN205,
453.1820;
13C NMR (126 MHz, CDC13) δ 171.63, found,
168.54, 161.72 (d, J= 245.7 Hz), 155.35, 453.1831
148.71, 141.10, 140.41, 136.91 (d, J= 3.5 Hz), 130.42, 129.58 (d, J= 7.8 Hz), 128.59, 127.95, 126.84, 115.64 (d, J= 21.3 Hz), 109.40, 73.39, 57.04, 56.07, 47.83, 19.15, 17.59 Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 1 1.77 (d, J = 0.6 Hz, 1H), 8.25 (d, J= 8.0 Hz, 1H), 7.96 (d, J= 5.2 Hz, 1H), 7.53 (dd, J= 20.0, 2.2 Hz, 2H), 7.35 (dd, J= 8.5, 1.8 Hz, 2H), 7.18 (ddd, J= 10.9, 8.5, 2.3 Hz, 2H), 6.88 (d, J= 5.2 Hz, lH), 5.80 (q, J=
ESIMS 6.3 Hz, 1H), 4.68 - 4.47 (m, lH), 3.95 (s, m/z 589.5 3H), 1.27 (d, J= 7.3 Hz, 3H), 1.20 (d, J=
127 — —
([M+H]+) 6.4 Hz, 3H)
13C NMR (126 MHz, CDC13) δ 170.98, 168.86, 155.52, 148.74, 144.18, 141.99, 140.57, 132.92, 132.87, 132.02, 131.86, 130.48, 130.37, 129.91, 128.15, 127.74, 125.09, 124.82, 109.64, 78.58, 74.60, 56.11, 48.05, 17.56, 14.13
¾ NMR (400 MHz, CDC13) δ 1 1.78 (d, J = 0.6 Hz, 1H), 8.25 (d, J= 8.0 Hz, 1H), 7.96 (d, J= 5.3 Hz, lH), 7.33 - 7.27 (m, 2H), 7.22 (dd, J= 10.4, 2.2 Hz, 1H), 7.08 (dddd, J= 19.0, 8.5, 2.1, 0.8 Hz, 2H), 6.88 (d, J= 5.2 Hz, lH), 5.82 (q, J= 6.3 Hz, lH), 4.65 - 4.51 (m, 1H), 3.95 (s, 3H), 3.00 (s, 1H), 1.26 (d, J= 7.2 Hz,
ESIMS 3H), 1.20 (d, J= 6.3 Hz, 3H) ni z 555.6
128 — —
([M+H]+) 13C NMR (126 MHz, CDC13) δ 170.92,
168.87, 158.04 (d, J= 249.8 Hz), 157.99 (d, J= 249.5 Hz), 155.54, 148.76, 145.02 (d, J= 5.5 Hz), 142.77 (d, J= 6.0 Hz), 140.55, 130.65, 130.55, 129.94, 122.05 (d, J= 3.7 Hz), 121.65 (d, J= 3.6 Hz), 120.45 (d, J= 17.8 Hz), 120.25 (d, J= 17.7 Hz), 1 14.56 (d, J= 22.7 Hz), 114.26 (d, J= 23.0 Hz), 109.62, 78.63, 74.64, 56.12, 48.02, 17.52, 14.30 Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.32 (d, J= 8.0 Hz, lH), 7.98 (d, J= 5.2 Hz, lH), 7.25 (d, J= 9.7 Hz, lH), 7.19 (d, J= 8.2 Hz, 1H), 7.09 (dd, J= 4.0, 2.3 Hz, 2H), 7.02 (td, J= 8.5, 2.3 Hz,
HRMS-ESI
2H), 6.87 (d, J= 5.2 Hz, 1H), 5.71 (dq, J
(m/z)
= 10.0, 6.1 Hz, lH), 4.54 (p, J= 7.3 Hz, ([M+H]+)
lH), 3.99 - 3.92 (m, 4H), 2.33 (s, 3H), calcd for
129 — — 2.29 (s, 3H), 1.24 (d, J= 6.1 Hz, 3H),
C27H2 CI2N2O5,
1.07 (d, J= 7.2 Hz, 3H)
531.1448;
found,
13C NMR (126 MHz, CDC13) δ 171.61, 531.1454
168.57, 155.39, 148.74, 140.44, 139.53, 139.35, 136.56, 136.15, 133.12, 132.77, 130.63, 130.59, 130.34, 129.45, 129.12, 126.59, 126.41, 109.44, 73.05, 56.45, 56.08, 47.85, 20.17, 20.08, 19.15, 17.69
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3376,
2986,
2360, lH NMR (400 MHz, CDC13) δ 12.63 (s,
2107, lH), 8.32 (d, J= 7.9 Hz, lH), 7.88 (d, J=
1736, 4.9 Hz, lH), 7.62 (d, J= 4.9 Hz, lH),
1652, 7.29 - 7.15 (m, 4H), 7.05 - 6.85 (m, 4H),
1604, 5.74 (dq, J= 9.9, 6.2 Hz, 1H), 4.61 -
1558, 4.48 (m, lH), 4.05 (d, J= 9.9 Hz, lH),
1530, 1.25 (d,J=6.1Hz, 3H), 1.06 (d,J=7.2
HRMS-ESI
1508, Hz, 3H)
(m/z)
1452,
([M+H]+)
1427, 13CNMR(101 MHz, CDC13) δ 171.39,
— calcd for
130 1381, 167.69, 161.76 (d, J= 246.1 Hz), 161.65
1329,
Figure imgf000239_0001
(d,J= 246.0 Hz), 155.39, 139.43, 136.82
521.0709;
1287, (d,J=3.4Hz), 136.63 (d,J=3.1Hz), found,
1262, 132.21, 131.44, 129.47 (d, J= 8.0 Hz),
521.0713
1247, 129.44 (d,J= 7.9 Hz), 122.15, 115.76 (d,
1223, J= 21.3 Hz), 115.42 (d,J= 21.3 Hz),
1187, 73.47,56.15,48.05, 19.11, 17.61
1159,
1137, 19F NMR (471 MHz, CDC13) δ -115.26 -
1116, -115.47 (m), -115.64 (ddd, J= 13.7, 8.9,
1049, 5.2 Hz)
1015,911,
826, 792,
779, 729,
680, 668
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3373,
2940,
1739,
1651,
lH NMR (300 MHz, CDC13) δ 12.01 (d,J 1609,
= 0.6 Hz, 1H), 8.31 (d, J= 8.0 Hz, 1H), 1577,
7.98 (d,J=5.2Hz, lH), 7.18 - 6.91 (m, 1518, HRMS-ESI
5H), 6.88 (d, J= 5.2 Hz, lH), 5.66 (dq, J 1481, (m/z)
= 9.4, 6.2 Hz, 1H), 4.64 - 4.49 (m, 1H), 1454, ([M+H]+)
4.01 (d, J= 9.4 Hz, lH), 3.95 (s, 3H), 1436, calcd for
131 — 1.32-1.21 (m, 4H), 1.16 (d,J= 7.2 Hz,
1382, C25H23F4N2O5,
3H)
1324, 507.1538;
1283, found,
19FNMR(471 MHz, CDC13) δ -136.05 - 1243, 507.1543
-136.27 (m), -136.61 (ddd,J=20.1, 11.4, 1210,
8.1Hz), -139.14 --139.32 (m),
1149,
-139.45- -139.68 (m)
1120,
1054, 954,
924, 872,
850, 824,
801,754,
733
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3372,
2983,
1737,
1649,
1601,
lH NMR (300 MHz, CDC13) δ 12.02 (d, J 1576,
= 0.6 Hz, 1H), 8.31 (d, J= 7.9 Hz, 1H), 1529, HRMS-ESI
7.97 (d, J= 5.2 Hz, lH), 7.27 (td, J= 7.3, 1498, (m/z)
2.1 Hz, 2H), 7.19 - 6.98 (m, 4H), 6.88 (d, 1481, ([M+H]+)
J= 5.2 Hz, 1H), 5.66 (dq, J= 9.5, 6.1 Hz, 1453, calcd for
132 — lH), 4.66 - 4.48 (m, 1H), 4.01 (d, J= 9.6
1439, C25H23C12F2N205,
Hz, lH), 3.95 (s, 3H), 1.26 (d, J= 6.2 Hz, 1381, 539.0947;
3H), 1.17 (d, J= 7.2 Hz, 3H)
1323, found,
1245, 539.0954
19F NMR (471 MHz, CDC13) δ -116.83 - 1184,
-1 16.94 (m), -117.22 - -117.34 (m) 1145,
1096,
1060, 953,
909, 864,
849, 824,
800, 730,
689
Figure imgf000242_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (300 MHz, CDC13) δ 12.00 (s, lH), 8.30 (d, J= 7.8 Hz, lH), 7.98 (d, J= 5.1 Hz, 1H), 7.42 - 7.28 (m, 4H), 7.09 (ddd, J= 10.1, 8.3, 2.2 Hz, 2H), 6.87 (d,
HRMS-ESI
J= 5.2 Hz, 1H), 5.65 (dt, J= 12.2, 6.1
(m/z)
Hz, lH), 4.57 (p, J= 7.3 Hz, lH), 4.00 ([M+H]+)
(d, J= 9.6 Hz, 1H), 3.95 (s, 3H), 1.27 (d, calcd for
136 — — J= 5.9 Hz, 3H), 1.17 (d, J= 7.2 Hz, 3H)
C25H23C14N205,
571.0356;
13C NMR (126 MHz, CDC13) δ 171.45, found,
168.64, 155.42, 148.74, 140.51, 140.21, 571.0367
140.16, 133.1 1, 132.76, 131.70, 131.38, 130.97, 130.67, 130.27, 130.20, 130.08, 127.25, 127.17, 109.53, 72.38, 56.09, 55.71, 47.87, 19.03, 17.71
l NMR (300 MHz, CDC13) δ 11.99 (s, lH), 8.30 (d, J= 8.0 Hz, lH), 7.98 (d, J= 5.2 Hz, 1H), 7.42 - 7.19 (m, 2H), 7.08 - 6.94 (m, 4H), 6.90 - 6.84 (m, lH), 5.67 (dq, J= 9.4, 6.2 Hz, lH), 4.65 - 4.48 (m,
HRMS-ESI lH), 4.03 (d, J= 9.4 Hz, lH), 3.95 (s,
(m/z) 3H), 1.27 (d, J= 6.1 Hz, 3H), 1.16 (d, J= ([M+H]+) 7.2 Hz, 3H)
calcd for
137 — —
C25H23 CI2F2N2O5, 13C NMR (126 MHz, CDC13) δ 171.41, 539.0947; 168.64, 158.16 (d, J= 250.2 Hz), 158.01 found, (d, J= 250.1 Hz), 155.42, 148.75, 140.91 539.0953 (d, J= 6.1 Hz), 140.83 (d, J= 6.3 Hz),
140.51, 131.12, 130.81, 130.20, 124.67 - 123.96 (m), 120.11 (d, J= 17.5 Hz), 119.82 (d, J= 17.7 Hz), 116.78 - 1 16.06 (m), 109.52, 72.44, 56.09, 47.85, 18.99, 17.71
Figure imgf000244_0001
Figure imgf000245_0001
Figure imgf000246_0001
Figure imgf000247_0001
Figure imgf000248_0001
Figure imgf000249_0001
Figure imgf000250_0001
Figure imgf000251_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
HRMS-ESI
lH NMR (400 MHz, CDC13) δ 8.52 -
(m/z)
8.37 (m, lH), 8.32 - 8.24 (m, lH), 7.80 - ([M+H]+)
7.63 (m, 3H), 7.61 - 7.47 (m, lH), 7.45 - calcd for
163 — — 7.22 (m, 4H), 7.01 - 6.92 (m, lH), 5.83 - C28H2 N2O7,
5.68 (m, 3H), 4.97 - 4.73 (m, lH), 4.38 - 505.1975;
4.19 (m, lH), 3.92 (s, 3H), 2.07 (s, 3H), found,
1.64 - 1.49 (m, 3H), 0.90 - 0.66 (m, 3H) 505.1961
HRMS-ESI
lH NMR (400 MHz, CDC13) δ 8.39 -
(m/z)
8.25 (m, 2H), 7.39 - 7.20 (m, 4H), 7.15 - ([M+H]+)
7.00 (m, 4H), 6.99 - 6.92 (m, lH), 5.81 - calcd for
164 — — 5.72 (m, 2H), 5.16 - 5.09 (m, 1H), 4.79 -
Figure imgf000252_0001
4.67 (m, lH), 4.37 - 4.17 (m, lH), 3.91 521.1924;
(s, 3H), 2.08 (s, 3H), 1.51 - 1.43 (m, 3H), found,
1.09 - 0.93 (m, 3H)
521.1913
lH NMR (400 MHz, CDC13) δ 8.39 (d, J = 6.8 Hz, 1H), 8.31 (d, J= 5.4 Hz, 1H), 7.45 - 7.31 (m, 4H), 7.18 - 7.06 (m, 4H), 7.00 (d, J= 5.5 Hz, 1H), 5.71 (dq, J=
HRMS-ESI
9.5, 6.2 Hz, 1H), 4.65 - 4.46 (m, lH),
(m/z)
4.00 (d, J= 9.5 Hz, lH), 3.89 (s, 3H), ([M+H]+)
2.38 (s, 3H), 1.22 (d, J= 6.2 Hz, 3H), calcd for
165 — — 1.02 (d, J= 7.2 Hz, 3H)
Figure imgf000252_0002
633.0236;
13C NMR (101 MHz, CDC13) δ 172.05, found,
168.89, 162.33, 159.47, 146.65, 141.39, 633.0230
139.74, 139.71, 137.49, 131.97, 131.68, 129.89, 129.78, 121.06, 120.79, 109.84, 72.56, 56.41, 56.30, 47.83, 20.76, 19.09, 17.98
Figure imgf000253_0001
Figure imgf000254_0001
Figure imgf000255_0001
Figure imgf000256_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3387,
2984,
1737, lH NMR (400 MHz, CDC13) δ 8.35 (dd, J
1673, = 4.5, 1.3 Hz, 1H), 8.15 (d, J= 7.8 Hz,
1603, HRMS-ESI lH), 7.52 (dd, J= 8.4, 1.4 Hz, lH), 7.42
1579, (m/z) (dd, J= 8.4, 4.5 Hz, lH), 7.33 - 7.14 (m,
1506, ([M+H]+) 4H), 7.05 - 6.86 (m, 4H), 5.82 (s, 2H),
1451, calcd for 5.72 (dq, J= 9.7, 6.1 Hz, 1H), 4.59 (p, J
1368, C27H27F2N2O6, = 7.3 Hz, 1H), 4.06 (d, J= 9.7 Hz, 1H),
1304, 513.1832; 2.11 (s, 3H), 1.24 (d, J= 6.2 Hz, 3H),
1268, found, 1.01 (d, J= 7.2 Hz, 3H)
1199, 513.1833
1159, 19F NMR (376 MHz, CDC13) δ
1136, -1 15.57, -115.97
1045,
1007, 969,
825, 779,
730
(Thin
film)
3380,
2985,
1737,
1674,
1603, lH NMR (400 MHz, CDC13) δ 8.23 (d, J 1578, = 5.3 Hz, 1H), 8.18 (d, J= 7.8 Hz, 1H),
HRMS-ESI
1507, 7.23 (ddd, J= 13.9, 6.9, 2.6 Hz, 4H),
(m/z)
1473, 7.05 - 6.84 (m, 5H), 5.78 - 5.66 (m, 3H),
([M+H]+)
1455, 4.56 (p, J= 7.3 Hz, lH), 4.12 (q, J= 7.0 calcd for
179 — 1366, Hz, 2H), 4.05 (d, J= 9.7 Hz, lH), 2.06 (s,
C2 H31F2N2O7,
1312, 3H), 1.47 (t, J= 7.0 Hz, 3H), 1.24 (d, J=
557.2094;
1274, 6.2 Hz, 3H), 1.00 (d, J= 7.2 Hz, 3H) found,
1222,
557.2089
1200, 19F NMR (376 MHz, CDC13) δ
1158, -1 15.60, -115.98
1104,
1043,
1003, 968,
910, 886,
824, 792,
728
Figure imgf000258_0001
Figure imgf000259_0001
Figure imgf000260_0001
Figure imgf000261_0001
Figure imgf000262_0001
Figure imgf000263_0001
Figure imgf000264_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
lH NMR (400 MHz, CDC13) δ 8.26 (d, J film)
HRMS-ESI = 5.4 Hz, IH), 8.13 (d, J= 8.1 Hz, IH),
3379,
(m/z) 7.85 (tt, J= 7.6, 1.9 Hz, IH), 7.47 (tt, J= 2987,
([M+H]+) 7.7, 1.8 Hz, IH), 7.28 - 7.20 (m, IH), 1741,
calcd for 7.22 - 7.1 1 (m, 2H), 7.09 - 6.99 (m, IH),
196 1673,
C28H2 F2N2O8, 7.01 - 6.79 (m, 3H), 6.29 - 6.20 (m, IH), 1507,
559.1884; 5.71 (d, J= 6.4 Hz, IH), 5.67 (d, J= 6.4 1486,
found, Hz, IH), 4.75 - 4.57 (m, IH), 3.91 (s, 1453,
559.1886 3H), 3.48 (d, J= 6.1 Hz, 1H), 2.07 (s, 1203,
3H), 1.34 - 1.21 (m, 6H)
1002
(Thin
film)
3379, HRMS-ESI lH NMR (300 MHz, CDC13) δ 8.27 (d, J
3282, (m/z) = 5.4 Hz, IH), 8.21 (d, J= 7.8 Hz, IH),
2984, ([M+H]+) 7.46 - 7.34 (m, 5H), 7.26 - 7.15 (m, 3H),
2107, calcd for 6.94 (d, J= 5.4 Hz, IH), 5.87 - 5.68 (m,
197
1738, C32H31N2O7, 3H), 4.62 - 4.48 (m, IH), 4.07 (d, J= 9.8
1674, 555.2125; Hz, IH), 3.91 (s, 3H), 3.05 (s, IH), 3.03
1503, found, (s, IH), 2.06 (s, 3H), 1.34 - 1.22 (m, 3H),
1202, 555.2126 0.98 (d, J= 7.2 Hz, 3H)
1043,
1004
(Thin
lH NMR (300 MHz, CDC13) δ 8.27 (d, J film) HRMS-ESI
= 5.4 Hz, IH), 8.23 (d, J= 7.8 Hz, IH),
3379, (m/z)
7.24 - 7.18 (m, 4H), 7.14 - 7.03 (m, 5H), 2964, ([M+H]+)
6.93 (d, J= 5.5 Hz, IH), 5.87 - 5.69 (m, 1736, calcd for
198 — 3H), 4.53 (p, J= 7.3 Hz, IH), 3.99 (d, J=
1675, C32H3 N2O7,
10.1 Hz, 1H), 3.90 (d, J= 1.0 Hz, 3H), 1505, 563.2753;
2.68 - 2.48 (m, 4H), 2.06 (d, J= 1.1 Hz, 1202, found,
3H), 1.24 (d, J= 7.1 Hz, 3H), 1.22 - 1.10 1042, 563.2752
(m, 6H), 0.88 (d, J= 7.2 Hz, 2H) 1003
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 8.27 (d, J = 5.3 Hz, 1H), 8.21 (d, J= 7.9 Hz, 1H), 7.31 - 7.22 (m, 5H), 7.21 - 7.12 (m, lH), 7.00 - 6.81 (m, 3H), 5.81 - 5.74 (m, lH),
HRMS-ESI 5.72 (d, J= 0.8 Hz, 2H), 4.54 (p, J= 7.2
(m/z) Hz, lH), 4.05 (d, J= 9.9 Hz, lH), 3.90 (s, ([M+H]+) 3H), 2.06 (s, 3H), 1.24 (d, J= 6.2 Hz, calcd for 3H), 0.92 (d, J= 7.2 Hz, 3H)
199 — —
C28H30FN2O7,
525.2032; 13C NMR (126 MHz, CDC13) δ 172.31, found, 170.28, 162.87, 161.70 (d, J= 245.6 Hz), 525.2045 160.25, 145.69, 143.97, 142.50, 141.20,
137.03 (d, J= 3.3 Hz), 129.60 (d, J= 7.8 Hz), 128.59, 128.02, 126.80, 115.60 (d, J = 21.3 Hz), 109.52, 89.55, 73.11, 57.04, 56.18, 48.05, 20.87, 19.18, 17.74
¾ NMR (400 MHz, CDC13) δ 8.26 (d, J = 5.4 Hz, 1H), 7.89 (d, J= 8.0 Hz, 1H), 7.56 (d, J= 2.2 Hz, lH), 7.48 (d, J= 2.2 Hz, lH), 7.34 (dd, J= 8.5, 4.2 Hz, 2H), 7.18 (ddd, J= 10.5, 8.4, 2.2 Hz, 2H), 6.97 (d, J= 5.4 Hz, lH), 5.79 (q, J= 6.3 Hz, lH), 5.68 (d, J= 6.3 Hz, lH), 5.61
ESIMS (d, J= 6.4 Hz, 1H), 4.63 - 4.52 (m, lH), m/z 661.1 3.92 (s, 3H), 3.55 (s, lH), 2.07 (s, 3H),
201 — —
([M+H]+) 1.27 (d, J= 7.2 Hz, 3H), 1.18 (d, J= 6.3
Hz, 3H)
13C NMR (126 MHz, acetone- g) δ 166.30, 165.13, 158.33, 155.10, 140.60, 139.16, 138.49, 137.43, 137.10, 127.58, 126.60, 126.48, 125.21, 123.17, 122.62, 119.99, 119.77, 104.55, 84.15, 73.35, 69.04, 51.05, 43.24, 26.40, 15.69, 9.20
Figure imgf000267_0001
Figure imgf000268_0001
Figure imgf000269_0001
Figure imgf000270_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (400 MHz, CDC13) δ 8.25 (t, J = 6.2 Hz, 2H), 7.32 - 7.11 (m, 4H), 7.04 - 6.85 (m, 5H), 5.79 - 5.65 (m, 3H), 4.55 (p, J= 7.3 Hz, 1H), 4.04 (d, J= 9.7 Hz,
HRMS-ESI
lH), 3.87 (s, 3H), 2.53 (hept, J= 7.0 Hz,
(m/z)
lH), 1.23 (d, J= 6.2 Hz, 3H), 1.12 (d, J= ([M+H]+)
7.0 Hz, 6H), 0.99 (d, J= 7.2 Hz, 3H) calcd for
211 — —
C30H33F2N2O7,
13C NMR (126 MHz, CDC13) δ 176.25, 571.2242;
172.25, 162.88, 162.70, 162.60, 160.74, found,
160.65, 160.26, 145.54, 144.21, 142.02, 571.225
136.94, 136.92, 136.86, 136.83, 129.60, 129.56, 129.54, 129.49, 115.77, 115.60, 115.47, 1 15.30, 109.53, 89.88, 73.01, 56.13, 48.05, 33.85, 19.15, 18.66, 17.81 l NMR (400 MHz, CDC13) δ 8.23 (dd, J = 16.1, 6.6 Hz, 2H), 7.25 - 7.18 (m, 4H), 7.02 - 6.89 (m, 5H), 5.82 - 5.66 (m, 3H), 4.54 (p, J= 7.3 Hz, lH), 4.08 (s, 2H),
HRMS-ESI 4.04 (d, J= 9.7 Hz, lH), 3.89 (s, 3H),
(m/z) 3.58 (q, J= 7.0 Hz, 2H), 1.25 - 1.20 (m, ([M+H]+) 6H), 0.99 (d, J= 7.2 Hz, 3H) calcd for
212 — —
C30H33F2N2O8, 13C NMR (126 MHz, CDC13) δ 172.20, 587.2199; 170.05, 162.84, 162.70, 162.61, 160.75, found, 160.65, 160.21, 145.73, 143.95, 142.23, 587.2217 136.95, 136.92, 136.85, 136.83, 129.60,
129.56, 129.54, 129.50, 115.78, 115.61, 115.47, 1 15.30, 109.70, 89.55, 73.04, 67.78, 67.17, 56.23, 56.14, 53.46, 48.04, 19.15, 17.81, 15.00, 14.95
Figure imgf000272_0001
Figure imgf000273_0001
Figure imgf000274_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3383,
2983,
1771,
1736,
1676,
1591, lH NMR (300 MHz, CDC13) δ 8.40 (d, J
1572, = 8.2 Hz, 1H), 8.32 (d, J= 5.4 Hz, 1H),
1503, HRMS-ESI 7.14 - 6.96 (m, 5H), 6.96 - 6.81 (m, 2H),
1451, (m/z) 5.68 (dq, J= 9.9, 6.1 Hz, 1H), 4.53 (dt, J
1437, ([M+H]+) = 8.2, 7.1 Hz, 1H), 3.94 (d, J= 10.0 Hz,
1366, calcd for IH), 3.90 (s, 3H), 2.38 (s, 3H), 2.22 (dd,
217
131 1, C2 H31F2N2O6, J= 6.7, 1.9 Hz, 6H), 1.21 (d, J= 6.1 Hz,
1277, 541.2145; 3H), 0.98 (d, J= 7.1 Hz, 3H)
1237, found,
1201, 541.2156 19F NMR (471 MHz, CDC13) δ
1176, -1 19.90 - -120.14 (m), -120.50 -
1119, -120.65 (m)
1099,
1051,
1009, 949,
907, 825,
805, 790,
733, 668,
657
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3376,
2988,
2363,
1742,
1675, lH NMR (300 MHz, CDC13) δ 8.27 (d, J 1609, = 5.4 Hz, 1H), 8.21 (d, J= 7.8 Hz, 1H), 1580, 7.18 - 6.85 (m, 7H), 5.72 (s, 2H), 5.65
HRMS-ESI
1515, (dq, J= 10.5, 6.2 Hz, lH), 4.58 (p, J=
(m/z)
1454, 7.3 Hz, lH), 4.01 (d, J= 9.4 Hz, lH),
([M+H]+)
1435, 3.91 (s, 3H), 2.07 (s, 3H), 1.25 (d, J= 5.9 calcd for
218 — 1368, Hz, 3H), 1.09 (d, J= 7.2 Hz, 3H)
C28H27F4N2O7,
1310,
579.1749;
1284, 19F NMR (471 MHz, CDC13) δ
found,
1236, -136.29 (ddd, J= 20.1, 11.2, 8.0 Hz), - 579.1762
1203, 136.73 (ddd, J= 20.1, 11.3, 8.0 Hz), - 1181, 139.16 - -139.43 (m), -139.64 - 1149, -139.84 (m)
1120,
1043,
1004, 970,
910, 873,
829, 754,
734
Cmpd. MP IR NMR
MASS
No. (°C) (cm1) (¾ 13C, 19F)
(Thin
film)
3393,
2986,
2364,
1742,
lH NMR (300 MHz, CDC13) δ 8.27 (dd, J 1676,
= 5.4, 1.1 Hz, 1H), 8.21 (d,J=7.8Hz, 1580,
IH), 7.35 - 7.19 (m,2H), 7.20 -7.01 (m, 1499,
HRMS-ESI 4H),6.96 (dd,J=5.5, 1.1 Hz, IH), 5.72 1454,
(m/z) (d,J= 1.1 Hz, 2H), 5.64 (dddd,J= 11.6, 1437,
([M+H]+) 9.1, 5.3, 3.3 Hz, IH), 4.65 - 4.51 (m, 1408,
calcd for IH), 4.01 (d, J= 9.5 Hz, IH), 3.92 (d, J=
219 — 1367,
C28H27CI2F2N2O7, 1.1 Hz, 3H),2.07 (d,J= 1.1 Hz, 3H), 1310,
611.1158; 1.30-1.21 (m, 3H), 1.09 (dd, J= 7.1, 1.1 1250,
found, Hz, 3H)
1202,
611.1169
1180,
19F NMR (471 MHz, CDC13) δ
1148,
-116.92--117.10(m), -117.36- 1101,
-117.53 (m)
1061,
1044,
1004, 972,
911,829,
732, 720,
687
Figure imgf000278_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F) lH NMR (300 MHz, CDC13) δ 8.27 (d, J = 5.4 Hz, 1H), 8.20 (d, J= 7.8 Hz, 1H), 7.32 (td, J= 8.3, 7.6 Hz, 2H), 7.1 1 - 6.93 (m, 4H), 5.72 (d, J= 0.5 Hz, 3H), 5.71 - 5.60 (m, lH), 4.67 - 4.51 (m, lH), 4.03 (d, J= 9.3 Hz, 1H), 3.91 (s, 3H), 2.07 (s,
HRMS-ESI
3H), 1.26 (d, J= 6.2 Hz, 3H), 1.09 (d, J=
(m/z)
7.2 Hz, 3H)
([M+H]+)
calcd for
222 — — 13C NMR (126 MHz, CDC13) δ 172.10,
C28H27CI2F2N2O7,
170.29, 162.95, 160.29, 158.15 (d, J= 61 1.1158;
250.2 Hz), 158.01 (d, J= 249.8 Hz), found,
145.70, 144.03, 142.24, 141.03 (d, J= 61 1.1175
6.5 Hz), 131.08, 130.80, 124.51 (d, J= 3.5 Hz), 124.40 (d, J= 3.6 Hz), 120.03 (d, J= 17.6 Hz), 1 19.73 (d, J= 17.7 Hz), 116.55 (d, J= 21.8 Hz), 109.64, 89.51, 72.15, 56.20, 55.99, 48.05, 20.87, 19.03, 17.84
¾ NMR (300 MHz, CDC13) δ 8.80 (d, J = 6.6 Hz, 1H), 8.49 (d, J= 6.8 Hz, 1H), 7.58 (d, J= 6.6 Hz, lH), 7.40 - 7.27 (m,
HRMS-ESI
4H), 7.14 - 7.01 (m, 2H), 5.67 - 5.52 (m,
(m/z)
lH), 4.61 - 4.46 (m, lH), 4.18 (s, 3H), ([M+H]+)
4.10 (d, J= 9.9 Hz, lH), 2.44 (s, 3H), calcd for
223 — — 1.27 (dd, J= 6.3, 3.1 Hz, 6H)
C27H25C14N206,
613.0461 ;
13C NMR (126 MHz, CDC13) δ 174.00, found,
171.63, 170.13, 140.79, 140.20, 133.07, 613.0468
132.34, 131.62, 130.97, 130.85, 130.55, 130.04, 127.30, 126.71, 108.57, 72.40, 58.02, 55.48, 34.67, 18.65, 16.34
Figure imgf000280_0001
Figure imgf000281_0001
Figure imgf000282_0001
Figure imgf000283_0001
Cmpd. MP IR NMR
MASS
No. (°C) (cm 1) (¾ 13C, 19F)
(Thin
film)
3384,
2987,
1743,
1675,
lH NMR (400 MHz, CDC13) δ 8.27 (d, J 1622,
= 5.4 Hz, 1H), 8.20 (d, J= 7.7 Hz, 1H), 1579,
6.96 (d, J= 5.4 Hz, 1H), 6.90 (dd, J= 1526,
HRMS-ESI 8.2, 6.3 Hz, 2H), 6.84 (dd, J= 8.0, 6.2 1506,
(m/z) Hz, 2H), 5.72 (d, J= 1.0 Hz, 2H), 5.58 1447,
([M+H]+) (dq, J= 8.9, 6.2 Hz, 1H), 4.59 (p, J= 7.3 1366,
calcd for Hz, lH), 3.96 (d, J= 8.8 Hz, lH), 3.92 (s,
230 — 1344,
C28H25F6N2O7, 3H), 2.07 (s, 3H), 1.26 (d, J= 6.2 Hz, 131 1,
615.1560; 3H), 1.17 (d, J= 7.3 Hz, 3H)
1237,
found,
1201,
615.1570 19F NMR (376 MHz, CDC13) δ
1180,
-132.49 (d, J= 20.7 Hz), -132.92 (d, J= 1149,
20.6 Hz), -161.02 (t, J= 20.6 Hz), 1117,
-161.33 (t, J= 20.6 Hz)
1101,
1040,
1003, 971,
911, 830,
803, 728,
679
ESIMS
m/z 320
232 — — —
([M+H]+) lH NMR (400 MHz, CDC13) δ 7.21 (ddd, J= 1 1.8, 8.4, 5.2 Hz, 4H), 6.98 (td, J= 8.6, 5.6 Hz, 4H), 5.67 (dq, J= 9.2, 6.2 Hz, lH), 4.80 (d, J= 7.8 Hz, lH), 4.06
ESIMS (dd, J= 21.8, 8.4 Hz, 2H), 1.43 (s, 9H), m/z 420 1.18 (dd, J= 12.5, 6.7 Hz, 6H)
233 — —
([M+H]+)
13C NMR (126 MHz, CDC13) δ 172.42, 162.70, 162.62, 160.74, 160.67, 136.89, 136.87, 129.74, 129.67, 129.61, 115.76, 115.59, 1 15.47, 115.30, 79.79, 72.77, 55.76, 49.40, 30.93, 28.30, 19.00, 18.30 Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.25- 7.17 (m, 1H), 7.14 (dd,J=8.4, 5.8 Hz, 1H), 6.91-6.76 (m, 4H), 5.60 (dq,J=9.8, 6.2 Hz, 1H),
(Thin film) HRMS-ESI (m/z) 4.94(d,J=8.0Hz, 1H), 4.42 3367, 2979, ([M+Na]+) calcd for (d,J=9.8Hz, 1H), 4.12 (qd,
234 1708, 1495, C25H3iF2NNa04, J= 7.2, 2.5 Hz, 1H), 2.37 (s,
1162, 1049, 470.2113; found, 3H), 2.32 (s, 3H), 1.42 (s, 731 470.2110 9H), 1.29 (d,J=6.1Hz,
3H), 0.88 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.52, -117.01.
1H NMR (400 MHz, CDC13) 57.33- 7.17 (m, 8H), 5.77 (dq,J= 10.3, 6.1Hz, 1H),
4.97(d,J=7.9Hz, 1H), 4.10 (dq,J=14.6, 7.2 Hz, 1H), 3.95 (d,J= 10.3 Hz, 1H),
(Thin film) HRMS-ESI (m/z) 1.41 (s, 9H), 1.26 (s, 9H), 3440, 2963, ([M+Na]+) calcd for 1.25- 1.20 (m, 12H), 0.64
235 1708, 1365, C3iH45NNa04, (d,J=7.2Hz, 3H).
1164, 1051, 518.3241; found,
908, 731 518.3245 13CNMR(101 MHz,
CDC13) 5172.88, 154.92, 149.54, 149.34, 138.80, 138.25, 127.65, 127.61, 125.59, 125.29, 79.54, 73.50, 57.27, 49.13,34.34,34.29, 31.30, 28.31, 19.36, 17.73. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.24- 7.17 (m,4H), 7.16- 7.05 (m, 4H), 5.76 (dq,J = 10.2, 6.1 Hz, IH), 4.97 (d,J = 7.9 Hz, 1H),4.09 (dq,J= 17.8, 7.3 Hz, IH), 3.95 (d,J = 10.3 Hz, 1H),2.82 (dhept, J=9.4, 6.9Hz,2H), 1.41 (s,
HRMS-ESI (m/z) 9H), 1.22 (d,J=6.2Hz,
(Thin film)
([M+Na]+) calcd for 3H), 1.17 (dd, 7= 11.6, 6.9 3373, 2960,
236 C29H4iNNa04, Hz, 12H), 0.67 (d,7=7.2
1711, 1163,
490.2928; found, Hz, 3H).
1050, 731
490.2931
13CNMR(101 MHz, CDC13)5172.87, 154.93, 147.27, 147.10, 139.20, 138.70, 127.91, 127.88, 126.75, 126.44, 79.54, 73.45, 57.42, 49.16,33.64,33.60, 28.31,24.00, 23.97, 23.91, 19.35, 17.79.
1H NMR (400 MHz, CDC13) 57.16- 6.89 (m, 6H), 5.73 (dq,7= 10.2, 6.1Hz, IH),
(Thin film) HRMS-ESI (m/z)
5.04- 4.90 (m, IH), 4.19- 3364, 2976, ([M+Na]+) calcd for
4.02 (m, IH), 3.88 (d,7=
237 1712, 1501, C27H37NNa04,
10.3 Hz, IH), 2.17 (dd, 7 = 1450, 1162, 462.2615; found,
10.4, 9.0 Hz, 12H), 1.41 (s, 1052, 731 462.2623
9H), 1.22 (d, 7= 6.1 Hz, 3H), 0.79 (d, 7= 7.1 Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.23 (ddd,J=16.6, 8.5,5.3 Hz, 4H), 6.97 (td, J =8.7,
2.2 Hz, 4H), 5.69 (dq,J = 9.1,6.2 Hz, 1H),4.93 (d,J =
7.3 Hz, 1H), 4.08 (dd,J = 21.8, 8.3 Hz, 2H), 1.43 (s, 9H), 1.18 (dd,J= 13.2, 6.7
Hz, 6H).
ESIMS m/z 442
([M+H]+)
238 13CNMR(101 MHz,
CDC13)5172.40, 162.91, 162.84, 160.46, 160.40, 154.90, 136.97, 136.94, 136.66, 129.81, 129.73, 129.69, 129.61, 129.53, 115.76, 115.71, 115.55, 115.50, 115.43, 115.22, 79.65,77.45,77.13,76.81, 72.71, 55.71,49.44, 28.25, 18.92, 18.10.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13)
57.23 (ddd,J=15.9, 8.7,5.4 Hz, 4H), 6.97 (dtd,J=8.7, 6.4, 2.1 Hz, 4H), 5.71 (dq,J
= 9.8, 6.1Hz, 1H),4.98 (d, J = 7.8 Hz, lH),4.14(dq,J= 14.9, 7.6 Hz, 1H), 4.03 (d, J = 9.8 Hz, 1H), 1.42 (s, 9H),
ESIMS m/z 420 1.22(d,J=6.1Hz, 3H), 0.84 ([M+H]+) (d,J=7.2Hz, 3H).
239
13CNMR(101 MHz, CDC13)5172.75, 162.96, 162.88, 160.51, 160.43, 154.94, 137.01, 136.97, 136.86, 136.82, 129.58, 129.53, 129.51, 129.45, 115.80, 115.59, 115.49, 115.28, 79.71,72.86, 56.20, 49.18, 28.28, 19.17, 18.02.
1H NMR (400 MHz, CDC13) δ 7.34 (dd,J= 8.6, 6.7 Hz, 1H), 7.12 (dd,J= 8.7, 6.7 Hz, 1H), 6.64 - 6.44 (m, 4H), 5.85 (dq,J= 9.5, 6.1
(Thin film) HRMS-ESI (m/z) Hz, 1H), 4.96 (d,J=7.8Hz, 3355,2978, ([M+Na]+) calcd for 1H), 4.81 (d,J=9.8Hz,
240 1711, 1599, C25H3iF2NNa06, 1H), 4.23 - 4.02 (m, 1H),
1500, 1162, 502.2012; found, 3.82 (s, 3H), 3.74 (s, 3H), 954 502.2021 1.42 (s, 9H), 1.20 (d,J=6.2
Hz, 3H), 0.88(d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.46, -113.83. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.30-7.13 (m, 10H), 5.83 (q,J=6.4Hz, 1H), 5.00 (d, J=5.4Hz, 1H), 4.26-4.12 (m, 1H), 1.73 (s, 3H), 1.41 (s, 9H), 1.15(d,J=6.3Hz,
ESIMS m/z 398 3H), 0.98 (d,J=7.2Hz, ([M+H]+) 3H).
241
13CNMR(101 MHz, CDC13)5172.77, 154.93, 146.56, 145.15, 128.16, 128.10, 127.92, 127.40, 126.28, 126.14, 79.69, 75.78, 50.38, 49.39, 28.31,23.89, 18.37, 15.98.
1H NMR (400 MHz, CDC13) δ 7.65 - 7.56 (m, 4H), 7.43 -
(Thin film) 7.33 (m, 4H), 5.85 - 5.73 (m,
ESIMS m/z 434
3375, 2980, 1H), 4.87 (d,J=7.9Hz,
([M+H]+)
242 2934, 2229, 1H), 4.19 (dd,J= 9.3, 2.7
1739, 1708, Hz, 1H), 4.17-4.01 (m, 1605, 1504 1H), 1.42 (s, 9H), 1.25 (d,J
= 6.2 Hz, 3H), 0.85 (d,J= 7.2 Hz, 3H).
1H NMR (400 MHz, CDC13) 57.56(t,J=8.1Hz, 4H), 7.44 - 7.36 (m,4H), 5.89-
(Thin film) ESIMS m/z 520
5.76 (m, 1H), 4.89 (d,J=7.8 3357, 2982, ([M+H]+)
243 Hz, 1H), 4.19(d,J=9.8Hz,
1709, 1617,
lH),4.12(t,J=7.5Hz, 1H), 1455
1.41 (s, 9H), 1.26 (d,J=6.2 Hz, 3H), 0.79 (d,J=7.2Hz,
3H).
Figure imgf000290_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.30 (dd,J= 8.5, 6.8 Hz, 1H), 7.14 (dd,J= 8.5, 6.8 Hz, 1H), 6.61-6.43 (m, 4H), 5.87 (dq,J=12.6, 6.3
(Thin film)
HRMS-ESI (m/z) Hz, 1H), 4.97 (d,J=6.9Hz, 3360, 2980,
([M+Na]+) calcd for 1H), 4.80 (d,J=10.1Hz, 1710, 1598,
246 C27H35F2NNa06, 1H), 4.21-4.07 (m, 1H),
1500, 1274,
530.2325; found, 4.06 - 3.78 (m,4H), 1.56 - 1160, 1040,
530.2336 1.34 (m, 15H), 1.21 (d,J= 990, 821
6.1Hz, 3H), 0.90 (d,J=7.2
Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.72, -114.20.
1H NMR (400 MHz, CDC13) 57.27 (d,J=8.1Hz, 1H), 7.10(d,J=8.2Hz, 1H), 6.84 (dd,J=5.6,2.6Hz, 1H), 6.81 (dd,J=8.2, 2.0 Hz,
(Thin film) HRMS-ESI (m/z)
1H),6.75 (dd,J=14.9, 2.0 3358, 2979, ([M+Na]+) calcd for
Hz, 2H), 5.86 (dq,J= 12.2,
247 1711, 1592, C27H35Cl2NNa06,
6.1Hz, 1H), 4.98 (d,J=6.9 1491, 1247, 562.1734; found,
Hz, 1H), 4.80 (d,J= 10.0 1162, 1042 562.1737
Hz, 1H), 4.23 - 4.07 (m, 1H), 4.07-3.75 (m, 4H), 1.52- 1.34 (m, 15H), 1.21 (d,J=6.2Hz, 3H), 0.91 (d, J=7.2Hz, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.25 (d,J=7.7Hz, 1H), 7.12(d,J=7.8Hz, 1H), 6.69 -6.52(m, 4H), 5.89 (dq,J =
(Thin film) HRMS-ESI (m/z) 12.3, 6.1 Hz, 1H), 5.03 (d,J 3360, 2977, ([M+Na]+) calcd for = 6.7 Hz, 1H), 4.88 (d,J=
248 1712, 1504, C29H4iNNa06, 10.2 Hz, 1H), 4.10 (q,J =
1259, 1161, 522.2826; found, 12.8, 9.8 Hz, 1H), 4.05 - 1044 522.2819 3.78 (m,4H), 2.26 (s, 3H),
2.24 (s, 3H), 1.53 - 1.33 (m, 15H), 1.22 (d,J=6.2Hz, 3H), 0.86 (d,J=7.1Hz,
3H).
1H NMR (400 MHz, CDC13) δ 8.02- 7.89 (m,4H), 7.40- 7.29 (m, 4H), 5.89 - 5.75 (m, 1H), 4.91 (d,J=8.0Hz, 1H), 4.35(q,J=7.1Hz, 2H), 4.34 (q,J=7.1Hz, 2H), 4.18(d,J=9.9Hz, 1H), 4.16-4.03 (m, 1H), 1.41 (s, 9H), 1.37 (t,J= 7.1
ESIMS m/z 528
Hz, 6H), 1.24 (d,J=6.2Hz, ([M+H]+)
249 3H), 0.81 (d,J=7.2Hz,
3H).
13CNMR(101 MHz, CDC13)5172.71, 172.69, 166.18, 166.10, 145.69, 145.36, 130.18, 129.91, 129.56, 129.31, 128.25, 128.12, 72.36, 60.98, 60.95, 57.67, 28.29, 19.18, 18.09, 14.29, 14.28. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 56.65-6.51 (m, 4H), 6.46 (tt,J= 10.3,2.3 Hz,2H), 5.67 (dq,J= 10.0,6.1 Hz, 1H), 4.98 (d,J=7.9Hz,
(Thin film) HRMS-ESI (m/z)
lH),4.14(dd,J= 10.5, 4.8 3378, 2979, ([M+Na]+) calcd for
Hz, 1H), 3.92 (d,J=9.9Hz,
250 1707, 1592, C25H3iF2NNa06,
1H), 3.76 (s, 3H), 3.75 (s, 1453, 1134, 502.2012; found,
3H), 1.42 (s, 9H), 1.24 (d,J 1050, 731 502.2022
= 6.2 Hz, 3H), 0.88 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ-110.64, -111.21.
1H NMR (400 MHz, CDC13) 56.45 (dd,J=4.5, 2.2 Hz, 4H), 6.28 (dt,J=13.7, 2.2 Hz, 2H), 5.73 (dq,J= 10.3, 6.1Hz, 1H), 5.00 (d,J=7.9 Hz, 1H), 4.12 (tt, 7= 7.1, 3.3 Hz, 1H), 3.87 (d, 7= 10.4
(Thin film) HRMS-ESI (m/z) Hz, 1H), 3.75 (s, 6H), 3.73 3375, 2978, ([M+Na]+) calcd for (s, 6H), 1.42 (s, 9H), 1.24 (d,
251 1708, 1593, C27H37NNa08, 7= 6.1 Hz, 3H),0.84 (d,7=
1456, 1149, 526.2411; found, 7.2 Hz, 3H).
1059, 729 526.2409
13CNMR(101 MHz, CDC13)5172.84, 160.97, 160.78, 154.94, 143.51, 143.22, 106.45, 106.20, 98.58, 98.44, 79.63, 72.69, 58.27, 55.28, 55.26, 49.25, 28.31, 19.27, 18.07. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 6.69 (s, 2H), 6.66 - 6.62 (m, 2H), 6.54 (s, 1H), 6.50 (s, 1H), 5.72 (dq, J= 10.4, 6.1 Hz, 1H), 5.00 (d, J= 7.9 Hz, 1H), 4.22 - 4.00 (m, 1H), 3.86 (d, J = 10.4 Hz, 1H), 3.74 (s, 3H), 3.73 (s,
(Thin film) 3H), 2.28 (s, 3H), 2.25 (s,
HRMS-ESI (m/z)
3370, 2978, 3H), 1.41 (s, 9H), 1.22 (d, J
([M+Na]+) calcd for
1708, 1594, = 6.2 Hz, 3H), 0.80 (d, J=
252 C27H37NNa06,
1454, 1292, 7.1 Hz, 3H).
494.2513; found,
1153, 1051,
494.2510
729 13C NMR (101 MHz,
CDC13) 5 172.85, 159.78, 159.65, 154.93, 142.79, 142.49, 139.72, 139.28, 121.29, 112.72, 112.69, 111.34, 110.84, 79.59, 72.99, 57.93, 55.12, 55.11, 49.24, 28.32, 21.65, 21.58, 19.31,
18.02.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.00 (ddd,J= 13.3, 7.6,0.9
Hz, 2H), 6.85- 6.68 (m, 4H), 5.78 (dq,J= 10.3,6.1 Hz, 1H), 5.11 -4.82 (m, 1H), 4.12 (qd,J= 7.1, 2.3 Hz, 1H), 3.94 (d,J=10.2 Hz, 1H), 3.79 (s, 3H), 3.78 (s, 3H),2.14(s, 3H),2.12(s,
(Thin film) HRMS-ESI (m/z)
3H), 1.41 (s, 9H), 1.24 (d,J 3377, 2978, ([M+Na]+) calcd for
= 6.1 Hz, 3H), 0.80 (d,J=
253 1711, 1508, C27H37NNa06,
7.2 Hz, 3H).
1252, 1163, 494.2513; found,
1041,732 494.2493
13CNMR(101 MHz, CDC13)5172.87, 157.86, 157.65, 154.93, 140.45, 140.25, 130.75, 130.47, 125.22, 124.79, 119.74, 119.69, 109.82, 109.77, 79.64, 73.09, 57.95, 55.27, 55.25,49.29, 28.32, 19.35, 18.06, 15.80, 15.75.
1H NMR (400 MHz, CDC13) δ 7.06 - 6.92 (m, 4H), 6.88 (td,J=8.7,4.6Hz,2H), 5.63 (dq,J=9.6, 6.2 Hz, 1H), 4.99 (d,J=7.9Hz,
(Thin film) HRMS-ESI (m/z)
1H), 4.13 (p,J=6.9Hz, 3377, 2979, ([M+Na]+) calcd for
1H), 3.91 (d,J=9.6Hz,
254 1706, 1513, C25H31F2NNa06,
1H), 3.84 (s, 3H), 3.83 (s, 1274, 1161, 502.2012; found,
3H), 1.42 (s, 9H), 1.22 (d,J 1025, 729 502.2008
= 6.2 Hz, 3H), 0.90 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -134.14, -134.59. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.05 (ddd,J=7.8,4.8, 2.3 Hz, 2H), 7.01 (d,J=2.2Hz, 2H), 6.70 (t, J= 8.8 Hz, 2H),
5.68 (dq,J= 10.1,6.1 Hz, 1H), 4.98 (d,J=7.9Hz, 1H), 4.12 (ddp,J= 11.8, 7.9, 4.3 Hz, 1H), 3.85 (d,J=10.2
Hz, 1H), 3.76 (s, 3H), 3.74
(Thin film) HRMS-ESI (m/z) (s, 3H),2.16(s, 3H),2.14(s, 3376, 2978, ([M+Na]+) calcd for 3H), 1.41 (s, 9H), 1.21 (d,J
255 1711, 1502, C27H37NNa06, = 6.1 Hz, 3H), 0.82 (d,J=
1247, 1163, 494.2513; found, 7.2 Hz, 3H).
1052, 730 494.2515
13CNMR(101 MHz, CDC13) 5172.87, 156.53, 156.36, 154.94, 133.77, 133.55, 130.40, 130.30, 126.81, 126.38, 126.06, 125.86, 110.05, 109.91, 79.58, 73.47,56.31,55.32, 55.27, 49.28, 28.32, 19.34, 18.15, 16.32, 16.24.
1H NMR (400 MHz, CDC13) 57.04 (d,J=3.0Hz, 1H), 6.86(d,J=3.0Hz, 1H), 6.74 (dd,J= 19.1, 8.9Hz,2H),
(Thin film) HRMS-ESI (m/z) 6.66 (ddd,J=9.1,6.3, 3.0 3355,2978, ([M+Na]+) calcd for Hz, 2H), 5.88 (dq,J=10.0,
256 1712, 1497, C27H37NNa08, 6.2 Hz, 1H), 5.03 (d,J=7.8
1223, 1161, 526.2411; found, Hz, 1H), 4.91 (d,J= 10.1 1047, 730 526.2405 Hz, 1H), 4.12 (m, 1H), 3.80
(s, 3H),3.73 (s, 3H), 3.71 (s, 3H), 3.70 (s, 3H), 1.41 (s, 9H), 1.30- 1.19 (m, 3H), 0.86 (d,J=7.2Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13)
57.05 (d,J=8.4Hz, 1H), 6.99(d,J=8.3Hz, 1H), 6.88
(d,J=2.7Hz, 1H), 6.81 (d, J=2.7Hz, 1H),6.63 (ddd,J
(Thin film) HRMS-ESI (m/z)
= 15.9, 8.3, 2.7 Hz, 2H), 5.63
SN 3364, 2978, ([M+Na]+) calcd for
(dq,J= 10.0, 6.1Hz, 1H),
257 S8 1710, 1497, C27H37NNa06,
< 4.99(d,J=7.9Hz, 1H), 4.43
1245, 1160, 494.2513; found,
(d,J= 10.1 Hz, 1H), 3.72 (s, 1045, 730 494.2507
3H), 3.72 (s, 3H),2.32 (s, 3H),2.26 (s, 3H), 1.46-
1.39 (m, 10H), 1.30 (d,J= 6.2 Hz, 3H), 0.86 (d,J=7.2
Hz, 3H).
1H NMR (400 MHz, CDC13) 57.08-6.91 (m, 3H), 6.89- 6.82 (m, 1H),6.76 (ddd,J = 8.0, 3.8, 1.7 Hz, 2H), 5.76- 5.53 (m, 1H), 5.15- 5.07 (m, 1H), 5.07-4.93 (m, 1H), 4.21-4.03 (m, 1H), 3.90- 3.80 (m, 9H), 3.76 -3.72 (m,
3H), 1.47- 1.37 (m, 9H),
HRMS-ESI (m/z)
1.24(t,J=6.0Hz, 3H), 1.14 ([M+H]+)
(d,J=6.9Hz, 1H), 0.86 (d, calcd for J=7.0Hz, 2H).
258
C27H37N08Na,
526.2411; found, 13CNMR(101 MHz, 526.2405 CDC13) 5172.73, 172.19,
152.83, 152.74, 147.49, 147.21, 135.15, 135.02, 134.77, 134.64, 123.63, 123.58, 123.52, 120.98, 120.94, 120.51, 120.38, 110.86, 110.74, 110.67, 73.58, 60.35, 60.29, 60.20, 55.65,42.03,41.98, 28.31, 18.90, 18.77, 18.52, 18.19. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.09 - 7.02 (m, 1H), 6.88- 6.74 (m, 3H), 5.70 - 5.59 (m, 1H), 4.95 (d,J=7.9Hz, 1H), 4.85 (d,J=9.7Hz, 1H), 4.22 - 4.07 (m, 1H), 3.97(d,J=2.4Hz, 3H), 3.86 (d,J=2.1Hz, 3H), 1.42 (s, 9H), 1.23 (d,J=6.2Hz,
(Thin film)
3H), 0.96 (d,J=7.2Hz, 3362, 2981,
HRMS-ESI (m/z) 3H).
1713, 1618,
([M+Na]+) calcd for
1501, 1475,
259 C25H29F4N06Na, 13CNMR(126 MHz,
1430, 1293,
538.1823; found, CDCI3) δ 172.67, 154.91, 1252, 1165,
538.1826 151.50, 151.26 (d,J= 11.3 1102, 1058,
Hz), 149.47 (d,J= 11.3 Hz), 951, 748
149.28 (d,J= 11.5 Hz), 147.24, 147.18, 147.03, 146.97, 145.35, 145.24, 143.36, 143.25, 129.90 (d, J = 3.5 Hz), 129.59, 123.09- 122.78 (m), 122.38, 110.96 - 110.60 (m), 79.81, 72.19, 61.23, 61.17, 49.21, 42.46, 28.29, 18.87, 18.29.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.07- 6.84 (m, 6H), 5.64 (dq,J= 11.9, 5.9 Hz, 1H),
4.96(d,J=8.1Hz, 1H), 4.44 (d,J= 10.3 Hz, 1H), 4.18 - 4.02 (m, lH),2.35(s, 3H), 2.29 (s, 3H), 2.27 (s, 3H),
(Thin film)
2.25 (s, 3H), 1.42 (s, 9H), 3382, 2977, HRMS-ESI (m/z)
1.27(d,J=6.1Hz, 3H), 0.82 2930, 1715, ([M+Na]+) calcd for
(d,J=7.2Hz, 3H).
260 se 1501, 1453, C27H37N04Na,
1365, 1249, 462.2615; found,
13CNMR(126 MHz, 1167, 1049, 462.2615
CDCI3) δ 172.97, 154.93, 811, 734
139.18, 138.55, 135.43, 135.04, 133.58, 133.35, 130.57, 130.28, 128.58, 127.87, 127.22, 126.90, 79.67, 74.72, 49.26, 47.36, 34.67, 28.32, 21.26, 21.22, 19.77, 19.73, 18.86.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.15(d,J=8.5Hz, 1H), 7.11 (d,J=8.5Hz, 1H), 6.96 -6.88(m, 4H), 5.64 (dq,J = 9.9, 6.1Hz, 1H),4.94 (d,J = 7.9 Hz, 1H), 4.42 (d,J= 10.0 Hz, 1H), 4.17- 4.05 (m, 1H), 2.34 (s, 3H), 2.30 (s,
(Thin film) 3H), 2.25 (s, 3H), 2.22 (s,
HRMS-ESI (m/z)
3364, 2977, 3H), 1.42 (s, 9H), 1.28 (d,J
& ([M+Na]+) calcd for
1713, 1499, = 6.2 Hz, 3H), 0.84 (d,J=
261 C27H37N04Na,
1452, 1365, 7.1Hz, 3H).
462.2615; found,
1209, 1164,
462.2614
1049, 731 13CNMR(126 MHz,
CDCI3) δ 172.88, 154.95, 136.54, 136.39, 136.19, 136.07, 135.85, 135.52, 131.49, 131.16, 127.74, 127.12, 126.82, 126.56, 79.63, 74.68, 49.24, 46.84, 34.67, 31.59, 28.32, 20.84, 20.10, 20.06, 18.94.
Figure imgf000301_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.01 - 6.86 (m, 3H), 6.82 (dd,J= 5.8, 3.1Hz, 1H), 6.74-6.64 (m, 2H), 5.82 (dq,J=12.0, 6.2 Hz, 1H), 4.97(d,J=7.8Hz, 1H), 4.67 (d,J= 10.5 Hz, 1H), 4.21- 4.09 (m, 1H),3.74 (s, 6H), 1.42 (s, 9H), 1.29 (d,J=6.2
(Thin film) Hz, 3H), 0.89 (d,J=7.3Hz, 2978, 1710, HRMS-ESI (m/z) 3H).
1497, 1454, ([M+Na]+) calcd for
263 1366, 1249, C25H3iF2N06, 13CNMR(126 MHz,
1209, 1160, 502.2012; found, CDC13) δ 172.70, 156.13, 1036, 814, 502.2011 155.90, 155.74, 155.57, 728 154.90, 154.24, 154.00,
127.94 (d,J= 15.8 Hz), 127.63 (d,J= 16.2 Hz), 116.24 (d,J=24.9Hz), 115.97 (d,J=24.8Hz), 115.14, 114.12, 113.16 (d,J = 8.3 Hz), 113.03 (d,J=8.2 Hz), 79.69, 71.79, 55.70, 49.15, 43.38, 34.66, 28.30, 19.00, 18.12.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13)
57.27(t,J=8.6Hz, 1H), 7.16(t,J=8.5Hz, 1H), 6.65 -6.50 (m, 4H), 5.82-5.72 (m, 1H), 4.96 (d,J=7.9Hz, 1H), 4.60 (d,J= 10.2 Hz, 1H), 4.21-4.09 (m, 1H), 3.75 (s, 3H), 3.74 (s, 3H),
I.42 (s, 9H), 1.26 (d,J=6.1
(Thin film)
Hz, 3H), 0.92 (d,J=7.3Hz, 2978, 2936,
HRMS-ESI (m/z) 3H).
1712, 1623,
([M+Na]+) calcd for
1585, 1506,
264 C25H3iF2N06Na, 13CNMR(126 MHz,
1445, 1366,
502.2012; found, CDC13)5172.73, 161.24 (d, 1288, 1159,
502.2016 J= 245.7 Hz), 161.01 (d,J= 1031, 950,
246.0 Hz), 159.73 (d,J= 834, 731
II.1 Hz), 159.50 (d,J= 11.3 Hz), 154.93, 129.86 (d,J = 5.8 Hz), 129.31, 119.70 (d, J
= 14.6 Hz), 119.41 (d,J = 15.1 Hz), 110.15 (d,J=2.9 Hz), 109.77 (d,J=3.0Hz),
101.81 (d,J=26.8Hz), 79.67, 72.07, 55.51, 49.19, 41.73, 28.31, 19.01, 18.24.
Figure imgf000304_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.39 (dd,J= 8.7, 5.6 Hz, 1H), 7.27 - 7.22 (m, 1H), 7.16 - 7.05 (m,2H), 6.98- 6.89 (m, 2H), 5.58(dq,J = 8.8, 6.2 Hz, 1H),4.95 (d,J = 7.4 Hz, 1H), 4.68 (d,J=9.1
(Thin film) HRMS-ESI (m/z)
Hz, 1H), 4.61 (d,J= 12.4 3355,2961, ([M+Na]+) calcd for
Hz, 1H), 4.53 (d,J= 12.5
266 1712, 1493, C27H35F2N06Na,
Hz, 1H), 4.42 (d,J= 12.3 1366, 1266, 530.2325; found,
Hz, 2H), 4.18 -4.06 (m, 1160, 1095 530.2331
1H), 3.42 (s, 3H), 3.41 (s, 3H), 1.42 (s, 9H), 1.27 (d,J = 6.2 Hz, 3H), 0.90 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.52, -115.88.
1H NMR (400 MHz, CDC13) 57.40 (dd,J=8.7, 5.6 Hz, 1H),7.24 (dd,J=8.7, 5.6 Hz, 1H), 7.13 (t,J=3.2Hz, lH),7.10(t,J=3.2Hz, 1H), 6.96-6.88 (m, 2H), 5.59 (dq,J=8.7, 6.2 Hz, 1H), 4.98 (d,J=7.5Hz, 1H), 4.69
(Thin film) HRMS-ESI (m/z)
(d,J=8.9Hz, 1H), 4.65 (d, 3356, 2977, ([M+Na]+) calcd for
J= 12.5 Hz, 1H),4.59 (d,J=
267 1712, 1494, C29H39F2N06Na,
12.6 Hz, 1H), 4.46 (d,J = 1366, 1160, 558.2638; found,
12.5 Hz, 1H), 4.45 (d,J = 1116, 1096 558.2638
12.6 Hz, 1H), 4.20 -4.06 (m, 1H), 3.62 -3.44 (m, 4H), 1.42 (s, 9H), 1.32-
1.18 (m,9H), 0.91 (d,J=7.2
Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.64, -115.97. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.07 (q,J=8.0Hz, 4H), 6.93 (dd,J=7.7, 3.2 Hz,
(Thin film) 2H), 6.85 (t,J=7.5Hz, 2H), 3372, 2978, 6.74-6.62 (m, 4H), 5.65
HRMS-ESI (m/z)
2936, 2835, (dqd,J=9.3, 6.1, 3.1Hz,
([M+H]+)
1713, 1582, 2H), 4.96 (d,J=7.4Hz, 1500, 1457, calcd for 1H), 4.81 (s, 1H), 4.60 (dd, J
268
1366, 1306, C27H37N06Na, = 9.9, 6.0 Hz, 2H), 4.09 (dt, 1257, 1211, 494.2513; found, J= 15.3, 6.9 Hz, 2H), 3.79 1166, 1098, 494.2490 (s, 6H),3.77 (s, 3H), 3.76 (s, 1048, 910, 3H), 2.27 (d,J=7.5Hz, 752, 734 6H), 2.20 (s,6H), 1.43 (s,
9H), 1.42- 1.38 (m, 12H),
1.26(t,J=6.0Hz, 6H), 0.83 (d,J=7.2Hz, 3H).
1H NMR (400 MHz, CDC13) δ 7.30 (dd,J= 7.6, 1.4 Hz, 2H), 7.14(d,J=7.7Hz,
(Thin film)
2H), 7.11-6.99 (m, 4H), 3357, 2978,
HRMS-ESI (m/z) 6.99 - 6.87 (m, 4H), 5.73- 1712, 1500,
([M+H]+) 5.49 (m,2H), 5.20 (d,J=7.3 1467, 1452,
Hz, 1H), 5.14 -4.98 (m, 1420, 1365, calcd for
269 3H), 4.11 (s,2H), 3.81 (s,
1250, 1207, C27H37N06Na,
3H), 3.76 (s, 3H), 3.74 (s, 1162, 1091, 494.2513; found,
3H),3.71 (s, 3H),2.35- 1053, 1006, 494.2509
2.23 (m, 12H), 1.43 (d,J= 909, 866,
12.5 Hz, 18H), 1.26 (dd,J= 765, 730
6.2,2.1 Hz, 6H), 1.09 (d,J = 6.8 Hz, 3H), 0.82 (d,J=7.1
Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.31 (d,J=8.5Hz, 1H), 7.11 (d,J=8.4Hz, 1H), 6.41 (dt,J=5.2,2.6Hz,2H),
(Thin film)
6.37 (dt, J =5.6, 2.7 Hz, 3364, 2976,
2H), 5.84 (dq,J=9.8,6.2 2935, 2836, ESIMS m/z 521
270 Hz, 1H), 5.01 (d,J=7.9Hz,
1711, 1608, ([M+NH4]+)
1H), 4.79 (d,J=9.9Hz, 1585, 1504,
1H), 4.18-4.06 (m, 1H), 1453
3.81 (s, 3H), 3.74 (s, 6H), 3.73 (s, 3H), 1.42 (s, 9H), 1.20(d,J=6.2Hz, 3H), 0.88 (d,J=7.2Hz, 3H).
1H NMR (300 MHz, CDC13) 57.28 (d,J=7.8Hz, 1H), 7.13- 7.03 (m, 1H), 6.69- 6.56 (m, 4H), 5.86 (dq,J =
(Thin film)
9.8, 6.2 Hz, 1H), 5.01 (d,J = 3365, 2977,
ESIMS m/z 489 7.8 Hz, 1H), 4.88 (d,J=9.9
271 2934, 1712,
([M+NH4]+) Hz, 1H), 4.20- 3.98 (m, 1611, 1504,
1H), 3.81 (s, 3H), 3.73 (s, 1452
3H), 2.27 (s, 3H), 2.26 (s,
3H), 1.41 (s, 9H), 1.21 (d,J = 6.1 Hz, 3H), 0.85 (d,J= 7.1Hz, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) 57.18(d,J=2.1Hz, 1H), 7.03 (d,J=2.2Hz, 1H), 6.95 -6.88 (m, 2H), 6.73 (d,J= 8.3 Hz, 1H), 6.68 (d,J=8.3
(Thin film) Hz, 1H), 5.83 (dq,J= 12.2, 3366, 2978, 6.1 Hz, 1H), 5.03 (d,J=7.9
ESIMS m/z 489
272 2933,2835, Hz, 1H), 4.93 (d,J= 10.3
([M+NH4]+)
1714, 1501, Hz, 1H), 4.19- 4.05 (m, 1453 1H), 3.81 (s, 3H), 3.72 (s,
3H), 2.24 (s, 3H), 2.21 (s, 3H), 1.42 (d,J=0.6Hz, 9H), 1.21 (d,J=6.1Hz, 3H), 0.84 (d,J=7.2Hz,
3H).
1H NMR (400 MHz, CDC13) δ 7.05 - 6.93 (m, 2H), 6.91- 6.75 (m, 4H), 5.71 (dq,J = 10.1, 6.2 Hz, 1H), 4.91 (d,J = 7.9 Hz, 1H), 4.20 - 4.07
ESIMS m/z 480
(m, 1H), 3.96 (d,J= 10.0 ([M+H]+)
273 Hz, 1H), 3.86 (s, 3H), 3.85
(s, 3H), 1.42 (s, 9H), 1.23 (d, J=6.1Hz, 3H), 0.86 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -137.12, -137.69.
1H NMR (400 MHz, CDC13) δ 7.22 - 7.04 (m, 2H), 6.77 - 6.56 (m, 4H), 5.60 (dq,J = 9.8, 6.1 Hz, 1H),4.95 (d,J =
ESIMS m/z 472
7.9 Hz, 1H), 4.36 (d,J= 10.0 ([M+H]+)
274 Hz, 1H), 4.20 - 4.03 (m, 1H),
3.75 (s, 3H), 3.73 (s, 3H), 2.35 (s, 3H), 2.31 (s, 3H), 1.42 (s, 9H), 1.27 (d,J=6.2 Hz, 3H), 0.87 (d,J=7.2Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
ESIMS m/z 432
([M+H]+)
275
1H NMR (400 MHz, CDC13) δ 7.35 - 7.28 (m, 2H), 7.25 - 7.20 (m, 2H), 7.20 - 7.09 (m, 2H), 6.65-6.51 (m, 2H), 5.81 (dq,J= 10.0,6.2 Hz,
ESIMS m/z 432 1H), 4.92 (d,J=8.0Hz, ([M+H]+) 1H), 4.53 (d,J=10.1Hz,
276
1H), 4.19- 4.04 (m, 1H), 3.83 (s, 3H), 1.42 (s, 9H), 1.23 (d,J=6.2Hz, 3H), 0.78 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.26.
1H NMR (400 MHz, CDC13) δ 7.33 - 7.20 (m, 5H), 7.19- 7.10 (m, 1H), 6.92-6.81 (m, 2H), 5.75 (dq,J= 10.3,6.1 Hz, 1H), 4.91 (d,J=8.0Hz,
ESIMS m/z 416
1H), 4.26 (d,J= 10.3 Hz, ([M+H]+)
277 1H), 4.18- 4.02 (m, 1H),
2.38 (s, 3H), 1.42 (s, 9H), 1.25 (d,J=6.1 Hz, 3H), 0.79 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -116.70. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.32- 7.12 (m, 6H), 6.59 (td,J=8.3,2.6Hz, 1H), 6.52 (dd,J= 10.9, 2.5 Hz, 1H), 5.79 (dq,J= 10.1,6.1
ESIMS m/z 432 Hz, 1H), 5.00 (d,J=8.2Hz, ([M+H]+) 1H), 4.51 (d, J = 10.2 Hz,
278
1H), 4.19- 4.04 (m, 1H), 3.75 (s, 3H), 1.41 (s, 9H), 1.21 (d, J =6.1 Hz, 3H), 0.86 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.59.
1H NMR (400 MHz, CDC13) 57.38- 7.15 (m, 6H), 6.90- 6.77 (m, 2H), 5.72 (dq,J = 10.1, 6.1 Hz, 1H), 4.97 (d,J = 8.4 Hz, 1H), 4.23 (d,J=
ESIMS m/z 416
10.1 Hz, 1H), 4.19 -4.03 (m, ([M+H]+)
279 1H), 2.31 (s, 3H), 1.42 (s,
9H), 1.23 (d,J=6.1Hz, 3H), 0.82 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -117.14.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.19(d,J=8.0Hz, 2H), 7.13 (dt,J=8.1, 6.5 Hz, 1H), 7.04 (d,J=7.9Hz, 2H), 6.61 -6.50 (m, 2H), 5.78 (dq,J=9.7, 6.1Hz,
ESIMS m/z 446
1H), 4.94 (d,J=7.8Hz, ([M+H]+)
280 1H), 4.49 (d,J=9.8Hz,
1H), 3.82 (s, 3H), 2.26 (s, 3H), 1.42 (s, 9H), 1.21 (d,J = 6.2 Hz, 3H), 0.82 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.47.
1H NMR (400 MHz, CDC13) 57.31 -7.25 (m, 1H), 7.16- 7.09 (m,2H), 7.04 (d,J=7.8 Hz, 2H), 6.91 -6.80 (m,2H), 5.72 (dq,J= 10.2,6.2 Hz, 1H), 4.92 (d,J=8.0Hz,
ESIMS m/z 430
1H), 4.22 (d,J= 10.2 Hz, ([M+H]+)
281 1H), 4.18- 4.02 (m, 1H),
2.37 (s, 3H), 2.25 (s, 3H), 1.42 (s, 9H), 1.24 (d,J=6.1 Hz, 3H), 0.83 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.91.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.26 (dd,J=8.5, 6.5 Hz, 1H), 7.16(d,J=8.1Hz, 2H), 7.06 (d, 7= 8.0 Hz, 2H), 6.58 (td,J= 8.3, 2.6 Hz, 1H), 6.52 (dd,J=10.9, 2.5 Hz, 1H), 5.77 (dq,J =
ESIMS m/z 446
10.1, 6.1 Hz, 1H), 5.01 (d,J ([M+H]+)
282 = 8.4 Hz, 1H), 4.48 (d,J=
¾ 10.3 Hz, 1H), 4.19- 4.04 (m,
1H), 3.76 (s, 3H), 2.27 (s, 3H), 1.41 (s, 9H), 1.21 (d,J = 6.1 Hz, 3H), 0.85 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.81.
1H NMR (400 MHz, CDC13) 57.31 (dd, 7=8.6, 5.8 Hz, 1H), 7.14- 7.04 (m, 4H), 6.87 - 6.77 (m, 2H), 5.70 (dq,7= 10.1, 6.1Hz, 1H),
¾\ ESIMS m/z 430 4.97 (d, 7= 7.8 Hz, 1H), 4.19
([M+H]+) (d,7= 10.3 Hz, 1H),4.17-
283
4.02 (m, 1H),2.31 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.22 (d, 7= 6.2 Hz, 3H), 0.81 (d, 7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13)
5-117.35. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.35 -7.22 (m, 2H), 7.12 (dd,J=8.4, 6.5 Hz, 1H), 6.98 - 6.84 (m, 2H), 6.71 - 6.48 (m, 2H), 5.78 (dq,J = 12.1, 6.3 Hz, 1H), 4.91 (d,J
¾, ESIMS m/z 450
= 8.0 Hz, 1H), 4.49 (d,J= ([M+H]+)
284 9.9 Hz, 1H), 4.25 - 4.02 (m,
1H), 3.82 (s, 3H), 1.42 (s, 9H), 1.22 (d,J=6.2Hz, 3H), 0.84 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -112.92, -116.53.
1H NMR (400 MHz, CDC13) 57.31 -7.16 (m, 3H), 7.00- 6.79 (m, 4H), 5.70 (dq,J = 10.3, 6.1Hz, 1H), 4.89 (s,
ESIMS m/z 434 1H), 4.25 (d,J= 10.2 Hz, ([M+H]+) 1H), 4.18- 4.04 (m, 1H),
285
2.36 (s, 3H), 1.42 (s, 9H), 1.25 (d,J=6.1 Hz, 3H), 0.87 (d,J=7.0Hz, 3H).
19F NMR (376 MHz, CDC13) δ -116.06, -116.38.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.25 -7.19 (m, 3H), 6.99- 6.90 (m,2H), 6.60 (td, J = 8.3, 2.5 Hz, 1H),6.54 (dd,J = 10.9, 2.5 Hz, 1H), 5.74 (dq,J= 11.9, 6.1Hz, 1H),
ESIMS m/z 450
4.94(d,J=7.8Hz, 1H), 4.48 ([M+H]+)
286 (d,J= 10.2 Hz, 1H),4.19- 4.05 (m, 1H),3.77 (s, 3H), 1.42 (s, 9H), 1.20 (d,J=6.2 Hz, 3H), 0.86 (d,J=7.3Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.32, -116.11.
1H NMR (400 MHz, CDC13) δ 7.30 (dd,J= 8.6, 5.7 Hz, 1H), 7.24-7.11 (m, 2H), 7.01 - 6.93 (m, 2H), 6.92 - 6.69 (m, 2H), 5.67 (dq,J = 10.0, 6.2 Hz, 1H), 4.92 (d,J
ESIMS m/z 434
= 6.4 Hz, 1H), 4.22 (d,J= ([M+H]+)
287 10.0 Hz, 1H), 4.18 -4.01 (m,
1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.22 (d,J=6.2Hz, 3H), 0.83 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -115.53, -116.86.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.21 (dd,J=8.5, 6.6 Hz, IH), 7.16 (dd,J= 8.5, 5.9 Hz, IH), 6.82 (tt,J= 8.4, 4.1 Hz, 2H), 6.59 (td,J= 8.2, 2.5 Hz, IH), 6.53 (dd,J =
HRMS-ESI (m/z) 10.8,2.4 Hz, IH), 5.67 (dq,J
(Thin film)
([M+Na]+) calcd for = 12.3, 6.1Hz, 1H),4.97 (d, 3364, 2978,
288 C25H3iF2NNa05, J=6.5Hz, 1H),4.73 (d,J=
1709, 1600,
486.2063; found, 10.2 Hz, IH), 4.25 -4.04 1496, 1161
486.2063 (m, IH), 3.78 (s, 3H), 2.42
(s, 3H), 1.42 (s, 9H), 1.21 (d, J=6.1Hz, 3H),0.92 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.52, -116.98.
1H NMR (400 MHz, CDC13) δ 7.32 - 7.27 (m, IH), 7.23 - 7.14 (m, IH), 6.81-6.71 (m, 2H),6.61 (td,J=8.3,2.5 Hz, IH), 6.54 (dd,J=10.8, 2.5 Hz, IH), 5.79 (dq,J = 11.8, 6.1 Hz, IH), 4.95 (d,J
HRMS-ESI (m/z)
(Thin film) = 7.1 Hz, IH), 4.76 (d,J=
([M+Na]+) calcd for
3364, 2979, 10.1 Hz, IH), 4.21 -4.05
289 C24H28F3NNa05,
1710, 1601, (m, IH), 3.76 (s, 3H), 1.42
490.1812; found,
1501, 1162 (s, 9H), 1.23 (d,J=6.3Hz,
490.1809
3H), 0.90 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) 5-112.15(d,J=44.2Hz), - 112.17(d,J=44.3 Hz), - 112.91.
Figure imgf000316_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) for both diastereomers of a 1 : 1 mixture d 7.18 - 7.09 (m, 2H), 7.01 - 6.87 (m, 10H), 5.76 - 5.58 (m, 2H), 5.03 (d, J= 5.4 Hz, 1H), 5.01 (d, J=
(Thin film) 4.9 Hz, 1H), 5.01 - 4.90 (m,
3363, 2979, 2H), 4.20 - 4.06 (m, 2H),
292 2939, 2838, 3.92 (d, 7= 2.1 Hz, 3H), 3.89
¾ 1712, 1586, (d, 7= 2.0 Hz, 3H), 3.81 (d,
1477 7= 1.9 Hz, 3H), 3.80 (d, 7=
1.9 Hz, 3H), 1.44 (s, 9H), 1.42 (s, 9H), 1.25 (d, 7= 6.6 Hz, 3H), 1.23 (d, 7= 6.3 Hz,
3H), 1.17 (d, 7= 7.1 Hz,
3H), 0.90 (d, 7= 7.2 Hz,
3H).
1H NMR (400 MHz, CDC13) major diastereomer of a 2: 1 mixture d 7.15 (dt, 7= 9.6, 3.0 Hz, 1H), 6.93 (td, 7= 8.8, 8.2, 3.1 Hz, 1H), 6.89 -
(Thin film)
6.81 (m, 2H), 6.80 - 6.68 (m, 3364, 2980,
293 2H), 5.84 (dd, 7= 9.6, 6.2
2839, 1712,
Hz, 1H), 4.98 (s, 1H), 4.86 1495, 1455
(d, 7= 9.2 Hz, 1H), 4.24 - 4.07 (m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H),
1.23 (d, 7= 6.3 Hz, 3H), 0.90 (d, 7= 7.2 Hz, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.19- 7.10 (m,2H), 7.10- 7.07 (m, 4H), 7.03 - 6.98 (m, 1H), 6.98 - 6.92 (m, 1H), 5.76 (dq,J= 10.3,6.1 Hz, 1H), 4.94 (d,J=7.9Hz, 1H), 4.18-4.03 (m, 1H), 3.94 (d,J= 10.3 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.22 (d,J=6.1
ESIMSw/ 412
Hz, 3H), 0.76 (d,J=7.2Hz, ([M+H]+)
294 f ^ 3H).
13CNMR(101 MHz, CDCI3) missing one aromatic C signal due to overlap d 172.84, 141.56, 141.27, 138.32, 137.91, 128.87, 128.87, 128.60, 128.34, 127.62, 127.30, 125.06, 124.89, 73.20, 57.91, 53.39, 49.25,28.31,21.46, 21.42, 19.32, 18.01.
1H NMR (400 MHz, CDC13) 57.32-7.21 (m, 5H), 7.21 - 7.15 (m, 1H), 6.86 (dd,J = 8.0, 1.7 Hz, 1H),6.79 (dd,J = 11.3, 1.6 Hz, 1H), 5.85-
ESIMSw/ 416 5.72 (m, 1H), 5.04- 4.94 (m, ([M+H]+) 1H), 4.39 (d,J= 10.1 Hz,
295
1H), 4.14 (p,J= 7.4, 6.8 Hz, 1H), 2.26 (s, 3H), 1.42 (s, 9H), 1.24 (d,J=6.1Hz, 3H), 0.90-0.81 (m, 3H).
19F NMR (376 MHz, CDC13) δ -118.88. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.28- 7.17 (m, 3H), 6.99- 6.93 (m, 2H), 6.88 (dd,J = 8.0, 1.7 Hz, 1H),6.80 (dd,J = 11.2, 1.6 Hz, 1H), 5.74 (dq,J=9.9, 6.2 Hz, 1H),
½ ESIMS m/z 434
4.98 (d,J=7.9Hz, 1H), 4.37 ([M+H]+)
296 (d,J= 10.0 Hz, 1H), 4.22- 4.07 (m, 1H), 2.27 (s, 3H), 1.42 (s, 9H), 1.23 (d,J=6.2 Hz, 3H), 0.88(d,J=7.5Hz,
3H).
19F NMR (376 MHz, CDC13) δ -115.62, -118.85.
1H NMR (400 MHz, CDC13)
57.22(t,J=8.0Hz, 1H), 7.19-7.13 (m, 2H), 7.07 (d, J=7.9Hz,2H), 6.85(dd,J= 8.0, 1.8 Hz, 1H),6.77 (dd,J = 11.2, 1.6 Hz, 1H), 5.83-
ESIMS m/z 430 5.69 (m, 1H), 5.03 (d,J=8.0 ([M+H]+) Hz, 1H), 4.35 (d,J= 10.3
297
Hz, 1H), 4.19-4.05 (m, 1H), 2.27 (s, 3H), 2.24 (s, 3H), 1.41 (s,9H), 1.23 (d,J = 6.1 Hz, 3H), 0.86 (d,J= 8.4 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -118.95. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.31 -7.22 (m, 4H), 7.22- 7.11 (m, 1H), 7.12 -7.02 (m,
2H),6.91 (dd,J=9.4, 8.2 Hz, 1H), 5.74 (dq,J= 10.1, 6.2 Hz, 1H), 4.92 (d,J=7.9
ESIMSw/ 416
«\ Hz, 1H), 4.17- 4.04 (m, 1H),
([M+H]+)
298 3.97 (d,J= 10.2 Hz, 1H),
2.23 (d,J= 1.9 Hz, 3H), 1.41 (s, 9H), 1.23 (d,J=6.2Hz,
3H), 0.76 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -120.18.
1H NMR (400 MHz, CDC13) 57.23 (dd,J=8.6, 6.6 Hz, 1H), 7.07 - 7.01 (m, 2H), 6.88 (t,J= 9.3 Hz, 1H), 6.60 (td,J=8.3,2.6Hz, 1H), 6.54 (dd,J= 10.9, 2.5 Hz, 1H), 5.72 (dq,J=11.8, 6.0
ESIMS m/z 464
Hz, 1H), 4.95 (d,J=8.0Hz, ([M+H]+)
299 1H), 4.44 (d,J= 10.3 Hz,
1H), 4.19- 4.07 (m, 1H), 3.78 (s, 3H), 2.22 (d,J= 1.9 Hz, 3H), 1.42 (s, 9H), 1.20 (d,J=6.1Hz, 3H), 0.86 (d, J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.49, -120.41. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.24 (dd,J=9.6, 5.6 Hz, lH),7.16(t,J=7.9Hz, 1H), 6.85 (dt,J= 10.4, 2.4 Hz, 3H), 6.79 (dt,J=11.3, 1.1
Hz, 1H), 5.70 (dq,J= 10.2,
ESIMS m/z 448 6.2 Hz, 1H), 4.99 (d,J=8.0 ([M+H]+) Hz, 1H), 4.61 (d,J= 10.1
300 OS
Hz, 1H), 4.22 - 4.09 (m, 1H), 2.39 (s, 3H), 2.26 (s,
3H), 1.42 (s, 9H), 1.25 (d,J = 6.1 Hz, 3H), 0.92 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -116.47, -118.10.
1H NMR (400 MHz, CDC13) 57.30-7.21 (m, 2H), 6.92- 6.85 (m, 1H), 6.85 - 6.74 (m,
3H), 5.84-5.73 (m, 1H), 4.97(d,J=7.9Hz, 1H), 4.68 (d,J= 10.0 Hz, 1H), 4.22-
ESIMS m/z 452
4.07 (m, 1H), 2.28 (s, 3H), ([M+H]+)
301 1.42 (s, 9H), 1.26 (d,J=6.2
Hz, 3H), 0.90 (d,J=7.3Hz,
3H).
19F NMR (376 MHz, CDC13) δ -111.63 (d,J=7.5Hz),- 112.07 (d,J=7.0Hz), - 118.16. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.29-7.21 (m, 4H), 7.19- 7.13 (m, 3H), 7.09 (d,J=7.9 Hz, 2H), 5.77 (dq,J= 10.3, 6.1Hz, 1H), 4.92 (d,J=7.9 Hz, 1H), 4.17- 4.04 (m,
(Thin film) 1H), 3.99 (d,J=10.3Hz,
HRMS-ESI (m/z)
3366, 2979, 1H), 2.28 (s, 3H), 1.41 (s,
([M+H]+)
2932, 1713, 9H), 1.23 (d,J=6.1Hz, 1496, 1452, calcd for 3H), 0.75 (d,J=7.2Hz,
302
1365, 1306, C24H32N04, 3H).
1248, 1211, 398.2326; found,
1165, 1053, 398.2328 13CNMR(126 MHz, 699 CDC13) δ 172.83, 154.94,
141.81, 138.26, 136.50, 129.98, 129.46, 128.47, 127.93 (d,J=3.6Hz), 126.56, 120.94, 79.63, 73.17, 57.62, 49.18, 34.67, 28.31, 20.97, 19.30, 18.00.
1H NMR (400 MHz, CDC13) 57.26 (d,J=4.5Hz, 5H), 7.18 (d,J=7.9Hz, 2H), 7.05 (d,J=7.9Hz, 2H), 5.77 (dq, J= 10.0, 6.2 Hz, 1H), 4.94 (d,J=7.9Hz, 1H), 4.18 - 4.05 (m, 1H), 3.99 (d,J=
HRMS-ESI (m/z)
(Thin film) 10.0 Hz, 1H), 2.26 (s, 3H),
([M+H]+)
3371,2978, 1.42 (s, 9H), 1.22 (d,J=6.2 2931, 1712, calcd for Hz, 3H), 0.80 (d,J=7.2Hz,
303 ¾ 1495, 1451, C24H32N04, 3H).
1365, 1165, 398.2326; found,
1051,699 398.2324 13CNMR(126 MHz,
CDC13) δ 172.83, 154.94, 141.52, 138.41, 136.15, 129.12, 128.73, 128.21, 128.05, 127.95, 126.79,
124.35, 79.63, 73.17, 57.47, 49.21, 34.67, 28.31,
20.94, 19.30, 18.08. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.25 - 7.20 (m, 2H), 7.15 (d,J=8.1Hz, 2H), 7.07 (d, J=7.9Hz, 2H), 6.96 (t,J= 8.7 Hz, 2H), 5.72 (dq,J = 9.7, 6.2 Hz, 1H),4.93 (d,J = 7.9 Hz, 1H), 4.17- 4.06 (m, 1H), 3.99 (d,J=9.8Hz, 1H), 2.27 (s, 3H), 1.42 (s,
(Thin film)
9H), 1.21 (d,J=6.2Hz, 3371,2979, HRMS-ESI (m/z)
3H), 0.81 (d,J=7.2Hz, 2932, 1712, ([M+Na]+) calcd for
3H).
304 1508, 1452, C24H3oFN04Na,
1366, 1222, 438.2051; found,
13CNMR(126 MHz, 1160, 1053, 438.2052
CDC13)5172.80, 161.65 (d, 816
J= 245.5 Hz), 154.94, 138.13, 137.32 (d,J= 3.2 Hz), 136.35, 129.52 (d,J = 7.9 Hz), 129.22, 127.89, 126.12 (d,J= 7.8 Hz), 115.56 (d,J=21.3Hz), 79.68, 73.01, 56.60, 49.19, 34.67, 31.59, 28.31, 20.95, 19.22, 18.07.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.31 -7.23 (m, 7H), 6.98- 6.92 (m, 2H), 5.75 (dq,J = 10.0, 6.2 Hz, 1H), 4.91 (d,J = 7.8 Hz, 1H), 4.18-4.07 (m, 1H), 4.02 (d,J= 10.0
(Thin film) Hz, 1H), 1.42 (s, 9H), 1.23 3371,2979, (d,J=6.2Hz, 3H), 0.83 (d,
ESIMS m/z 402.2
as 2933, 1710, J=7.2Hz, 3H).
([M+H]+)
305 1509, 1452,
1366, 1222, 13CNMR(126 MHz, 1160, 1051, CDC13)5172.80, 161.61 (d, 699 J= 245.2 Hz), 154.93,
141.02, 137.26 (d,J= 3.4 Hz), 129.55 (d,J= 7.9 Hz), 128.86, 127.99, 127.05, 115.29 (d,J=21.2Hz), 79.74, 73.05, 57.10, 49.18, 34.67, 28.31, 19.29, 18.12.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.26-7.21 (m, 2H), 7.14 (d,J=8.2Hz, 2H), 7.09 (d, J=8.1Hz,2H), 6.98-6.90 (m,2H), 5.73 (dq,J=10.2, 6.1Hz, 1H), 4.91 (d,J=8.0 Hz, 1H), 4.17- 4.06 (m, 1H), 3.98 (d,J= 10.2 Hz,
(Thin film) 1H), 2.29 (s, 3H), 1.42 (s, 3371,2979, 9H), 1.22 (d,J=6.1Hz, be 2932, 1712, 3H), 0.82 (d,J=7.2Hz,
ESIMSw/z 438.2
306 1509, 1452, 3H).
([M+Na]+)
1366, 1222,
1161, 1052, 13CNMR(126 MHz, 815 CDC13)5172.80, 161.56 (d,
J= 245.0 Hz), 154.93, 138.04, 137.58 (d,J= 3.3 Hz), 136.69, 129.54, 129.43 (d,J=7.8Hz), 127.82, 115.25 (d,J=21.2Hz), 79.72, 73.11, 56.76, 49.18, 34.67, 28.31, 20.97, 19.28,
18.12.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.33 - 7.24 (m, 5H), 7.22 - 7.14 (m, 1H), 6.86-6.73 (m,
2H), 5.84-5.72 (m, 1H), 4.90(d,J=8.0Hz, 1H), 4.40 (d,J= 10.2 Hz, 1H), 4.18 - 4.05 (m, 1H), 1.42 (s, 9H),
(Thin film) HRMS-ESI (m/z) 1.26(d,J=6.1Hz, 3H), 0.78 3370, 2980, ([M+H]+) (d,J=7.2Hz, 3H). 2936, 1712,
calcd for
307 f¾ 1503, 1453, 13CNMR(126 MHz,
C23H28F2NO4,
1366, 1164, CDC13)5172.74, 162.98- 420.1981; found,
1053, 966, 161.09 (m), 160.06 (dd,J =
420.1995
851, 698 169.5, 12.1 Hz), 154.93,
140.15, 129.79, 128.61, 128.22, 127.00, 124.39 (d, J = 18.6 Hz), 111.62 (d,J = 19.5 Hz), 104.70- 103.41 (m), 79.71, 72.30, 49.40, 49.15, 34.67, 28.31, 18.97,
17.99.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 7.25 - 7.20 (m, 1H), 7.18 (d,J=8.1Hz, 2H), 7.07 (d, J=7.6Hz,2H), 6.85-6.72 (m,2H), 5.76 (dtd,J=9.5, 6.8, 5.5 Hz, 1H),4.92 (d,J = 7.8 Hz, 1H), 4.36 (d,J= 10.0 Hz, 1H), 4.19-4.01 (m, 1H), 2.27 (s, 3H), 1.42 (s,
(Thin film)
9H), 1.25 (d,J=6.2Hz, 3364, 2980, HRMS-ESI (m/z)
3H), 0.82 (d,J=7.2Hz, 2933, 1713, ([M+Na]+) calcd for
3H).
308 1502, 1453, C24H29F2N04Na,
1366, 1164, 456.1957; found,
13CNMR(126 MHz, 1053, 966, 456.1953
CDC13)5172.74, 161.98 850
(dd,J= 167.8, 11.9 Hz), 160.01 (dd,J= 167.8, 11.9
Hz), 154.93, 137.05, 136.57, 129.90, 129.24, 128.11, 124.66 (d,J= 11.5 Hz), 111.57 (d,J=20.4Hz), 104.69- 102.95 (m), 79.70, 72.38, 49.18, 48.94, 28.31, 20.97, 18.97, 18.07.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 57.29- 7.19 (m, 3H), 6.99- 6.93 (m,2H), 6.86- 6.75 (m,
2H), 5.81-5.70 (m, 1H), 4.90(d,J=7.9Hz, 1H), 4.37 (d,J=10.1Hz, 1H), 4.21- 4.06 (m, 1H), 1.42 (s, 9H),
(Thin film)
1.26(d,J=6.2Hz, 3H), 0.85 3364, 2981,
HRMS-ESI (m/z) (dd,J=7.8, 1.1 Hz, 3H). 1711, 1604,
([M+Na]+) calcd for
1502, 1454,
309 C23H26F3N04Na, 13CNMR(126 MHz,
1380, 1366,
460.1706; found, CDC13) δ 172.71, 162.85, 1224, 1161,
460.1712 162.71, 161.37, 161.28, 1053, 966,
160.87, 160.75, 159.39, 851,
159.30, 154.93, 135.92, 129.76 (d,J=7.7Hz), 115.44 (d,J=21.3Hz), 111.71 (d,J= 18.0 Hz), 104.71 - 103.96 (m), 79.80, 72.20, 49.16, 48.78, 34.67, 28.30, 18.99, 18.09.
HRMS-ESI (m/z)
([M+H]+)
calcd for
310 v?
C26H38N02,
396.2897; found,
396.2896
1H NMR (400 MHz, Acetone-d6) 57.31 -7.21 (m,4H), 7.15 (ddd,J= 10.9,
HRMS-ESI (m/z)
8.5, 2.5 Hz, 4H), 5.87 (dq,J ([M+H]+)
= 10.0, 6.0 Hz, 1H),4.05 (d, calcd for J= 10.5 Hz, 1H), 3.85 (q,J=
311
C24H34N02, 7.2 Hz, 1H),3.31 (dt,J= 368.2584; found, 3.3, 1.7 Hz, 3H), 2.91-2.73 368.2584 (m,2H), 1.26 (d,J=6.1Hz,
3H), 1.19(t,J=6.7Hz, 12H), 0.81 (dd,J=7.3,2.8 Hz, 3H).
Figure imgf000329_0001
Figure imgf000330_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
ESIMS m/z 404
([M+H]+)
327
¾ ESIMS m/z 372
([M+H]+)
328
ESIMS m/z 372
([M+H]+)
329
ESIMS m/z 380
([M+H]+)
330
ESIMS m/z 380
([M+H]+)
331
1H NMR (500 MHz, Methanol-d4) δ 6.74 (dddd, J = 17.6, 8.0,3.7, 1.8 Hz, 4H), 6.58(ddt,J= 12.2, 10.0, 2.3 Hz, 2H), 5.83 (dq,J= 10.2,
HRMS-ESI (m/z)
6.1Hz, 1H), 4.13 (d,J= 10.3 ([M+H]+)
Hz, 1H), 3.93 (q,J=7.2Hz,
* calcd for 1H), 3.78 (s, 3H), 3.77 (s,
332 ¾¾
C20H24F2NO4, 3H), 1.28 (d,J=6.2Hz, 380.1668; found, 3H), 1.00 (d,J=7.3Hz, 3H) 380.1649 (NH protons not observed).
19FNMR(471 MHz, Methanol-d4) δ -112.85 (t, J = 10.0 Hz), -113.22 (t,J = 10.3 Hz). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) 13C, 19F)
1H NMR (500 MHz, Methanol-d4) δ 6.51 (dd, J=
HRMS-ESI (m/z) 5.2,2.3 Hz, 4H), 6.35 (dt, J ([M+H]+) = 13.0, 2.2 Hz, 2H), 5.82
(dq,J= 10.4, 6.1Hz, 1H), calcd for
333 3.99 (d,J= 10.4 Hz, 1H),
C22H3oN06,
3.89(q,J=7.2Hz, 1H), 3.75 404.2068; found,
(s, 6H), 3.74 (s, 6H), 1.27 (d, 404.2038
J=6.2Hz, 3H),0.96 (d,J= 7.3 Hz, 3H) (NH protons not observed).
1H NMR (500 MHz, Methanol-d4) δ 6.75 (d,J= 4.0 Hz, 2H), 6.69 (dt,J=
HRMS-ESI (m/z) 6.6, 1.9 Hz, 2H), 6.61 (s, ([M+H]+) 1H), 6.58(d,J=2.3Hz,
?¾ 1H), 5.82 (dq,J=10.4, 6.1 calcd for
334 Hz, 1H), 3.97 (d,J=10.5
C22H30NO4,
Hz, 1H), 3.85(q,J=7.3Hz, 372.2169; found,
1H), 3.75 (s, 3H), 3.74 (s, 372.2146
3H), 2.29 (s, 3H), 2.27 (s, 3H), 1.25 (d,J=6.2Hz, 3H), 0.92 (d,J=7.2Hz, 3H) (NH protons not observed).
1H NMR (500 MHz, Methanol-d4) δ 6.75 (d,J= 4.0 Hz, 2H), 6.69 (dt,J=
HRMS-ESI (m/z) 6.6, 1.9 Hz, 2H), 6.61 (s, ([M+H]+) 1H), 6.58(d,J=2.3Hz,
1H), 5.82 (dq,J=10.4, 6.1 calcd for
335 Hz, 1H), 3.97 (d,J=10.5
C22H30NO4,
Hz, 1H), 3.85(q,J=7.3Hz, 372.2169; found,
1H), 3.75 (s, 3H), 3.74 (s, 372.2146
3H), 2.29 (s, 3H), 2.27 (s, 3H), 1.25 (d,J=6.2Hz, 3H), 0.92 (d,J=7.2Hz, 3H) (NH protons not observed). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, Methanol-d4) δ 7.03 (dd, J= 11.9, 7.5 Hz, 2H), 6.92- 6.80 (m, 4H), 5.88 (dq,J =
ESIMSw/z 372.1
;·"-« 10.5, 6.1Hz, IH), 4.05 (d,J «S ([M+H]+)
336 = 10.4 Hz, IH), 3.88 (q,J=
7.2 Hz, IH), 3.80 (d,J= 1.0 Hz, 6H), 2.12 (s, 3H),2.11 (s, 3H), 1.26 (d,J=6.1Hz, 3H), 0.90 (d,J=7.2Hz, 3H) (NH protons not observed).
1H NMR (500 MHz, Methanol-d4) 57.15 -7.06 (m,4H), 7.03 (q,J=8.5Hz, 2H), 5.77 (dq,J= 10.1,6.2
HRMS-ESI (m/z) Hz, IH), 4.06 (d,J= 10.0 ([M+H]+) Hz, IH), 3.93 (q,J=7.3Hz,
IH), 3.83 (s, 3H), 3.82 (s, calcd for
337 3H), 1.25 (d,J=6.1Hz,
C20H24F2NO4,
3H), 1.00 (d,J=7.3Hz, 3H) 380.1668; found,
(NH protons not observed). 380.1667
19FNMR(471 MHz, Methanol-d4) δ -136.28 (dd, J=12.6, 8.5 Hz), -136.53 (dd,J= 12.6, 8.9 Hz).
1H NMR (500 MHz, Methanol-d4)57.14-7.03 (m,4H),6.80 (dd,J= 12.7, 8.4 Hz, 2H), 5.77 (dq,J =
ESIMSw/z 372.1 10.3, 6.2 Hz, IH), 3.92 (d,J ([M+H]+) = 10.4 Hz, IH), 3.86 (q,J=
338
7.2 Hz, 1H),3.78 (s, 3H), 3.76 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.23 (d,J=6.1 Hz, 3H), 0.92 (d,J=7.3Hz, 3H) (NH protons not observed). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, Methanol-d4) δ 7.03 (d,J= 3.0 Hz, 1H), 6.90- 6.80 (m,
HRMS-ESI (m/z) 3H),6.75 (ddd,J=8.9, 4.5, ([M+H]+) 3.1Hz, 2H), 5.99 (dq,J =
10.2, 6.2 Hz, 1H), 4.91 (d,J calcd for
339 = 10.2 Hz, 1H), 3.89 (q,J=
C22H30NO6,
7.2 Hz, 1H),3.81 (s, 3H), 404.2068; found,
3.73 (s, 3H), 3.73 (s, 3H), 404.2059
3.70 (s, 3H), 1.24 (d,J=6.2 Hz, 3H), 0.97 (d,J=7.2Hz, 3H) (NH protons not observed).
(Thin film)
HRMS-ESI (m/z)
2938, 1742,
([M+H]+)
1617, 1501,
4¾ 1473, 1429, calcd for
340
1293, 1233, C20H22F4NO4,
1189, 1119, 416.1479; found,
1050, 950, 416.1479
785
(Thin film) HRMS-ESI (m/z)
2866, 1742, ([M+H]+)
1500, 1454,
calcd for
341 1378, 1226,
C22H3oN02,
1113, 1048,
340.2271; found,
808, 792,
340.2269
737
(Thin film)
HRMS-ESI (m/z)
2863, 1748,
([M+H]+)
1736, 1526,
1500, 1456, calcd for
342 «s
1376, 1238, C22H3oN02,
1187, 1116, 340.2271; found,
1048, 810, 340.2274
791, 751
Figure imgf000335_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (¾ 13C, 19F)
ESIMS m/z 436.2
([M+H]+)
348
ESIMS m/z 404.1
([M+H]+)
349
ESIMS m/z 372 A
([M+H]+)
350
ESIMS m/z 372 A
([M+H]+)
351
ESIMS m/z 380
([M+H]+)
352
ESIMS m/z 372
«$
([M+H]+)
353
ESIMS m/z 332
([M+H]+)
354
ESIMS w/z 316
([M+H]+)
355
ESIMS m/z 332
([M+H]+)
356
ESIMS w/z 316
([M+H]+)
357 Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (¾ 13C, 19F)
ESIMS m/z 346
([M+H]+)
358
ESIMS m/z 330
([M+H]+)
359
ESIMS m/z 346
([M+H]+)
360
ESIMS m/z 350
([M+H]+)
361
ESIMS m/z 334
([M+H]+)
362
ESIMS m/z 350
½;
([M+H]+)
363
ESIMS m/z 334
([M+H]+)
364
ESIMS m/z
312([M+H]+)
365
ESIMS m/z 364.2
([M+H]+)
366
ESIMS m/z 368.2
([M+H]+)
367 Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (¾ 13C, 19F)
ESIMS m/z 364.2
([M+H]+)
368 f ^
ESIMS m/z 352.2
([M+H]+)
369
ESIMS m/z
316([M+H]+)
370
ESIMS m/z
334([M+H]+)
371
ESIMS m/z 330
([M+H]+)
372
ESIMS m/z
348([M+H]+)
373
ESIMS m/z 352
([M+H]+)
374
ESIMS w/ 316
([M+H]+)
375
ESIMS m/z 364
([M+H]+)
376
Figure imgf000339_0001
Figure imgf000340_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.05 (d,J=0.6Hz, 1H), 8.31 (d,J=8.0Hz, 1H), 7.97
(d,J=5.2 Hz, 1H), 7.22 (dddd,J= 11.7, 8.5, 5.3,2.6 Hz, 4H), 7.02- 6.89 (m, 4H), 6.86 (d,J=5.2Hz, 1H), 5.72 (dq,J = 9.7, 6.2 Hz, 1H), 4.60 - 4.46 (m,
HRMS-ESI (m/z)
1H), 4.05 (d,J=9.8Hz, ([M+H]+)
1H),3.94 (s, 3H), 1.24 (d,J calcd for = 6.2 Hz, 3H), 1.06 (d,J=
386
C25H25F2N2O5, 7.2 Hz, 3H).
471.1728; found,
471.1726. 13CNMR(101 MHz,
CDC13)5171.56, 168.60, 162.98, 162.87, 160.54,
160.42, 155.41, 148.75,
140.43, 136.83, 136.80, 136.73, 136.70, 130.36, 129.54, 129.46, 115.83, 115.62, 115.50, 115.29,
109.46, 73.32, 56.14, 56.08, 47.87,30.92, 19.12, 17.67.
Figure imgf000342_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 512.05 (s, 1H), 8.32 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2
Hz, 1H), 7.24 (dd,J=8.7,
5.8 Hz, 1H), 7.14(dd,J = 8.6, 5.8 Hz, 1H), 6.92-6.72
HRMS-ESI (m/z)
(Thin film) (m, 5H), 5.64 (dq,J=9.8,
([M+H]+)
3371,2981, 6.2 Hz, 1H), 4.53 (p,J=7.3 1735, 1649, calcd for Hz, 1H), 4.44 (d,J=9.7Hz,
388
1495, 1261, C27H29F2N2O5 , 1H), 3.94 (s, 3H), 2.38 (s, 954, 800, 499.2039; found, 3H),2.31 (s, 3H), 1.31 (d,J 728 499.2044 = 6.1 Hz, 3H), 1.10 (d,J=
7.2 Hz, 3H).
19F NMR (471 MHz, CDC13) δ-116.46 (td,J= 8.8, 5.7 Hz), -116.87 (td,J= 9.0, 5.9
Hz).
1H NMR (500 MHz, CDC13) δ 12.12 (s, 1H), 8.38 (d,J= 7.9 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.29 (d,J=8.3Hz, 2H),7.25 (s, 6H),6.86 (d,J = 5.2 Hz, 1H), 5.80 (dq,J= 10.3, 6.2 Hz, 1H), 4.48 (p, J = 7.3 Hz, 1H), 3.98 (d,J=
HRMS-ESI (m/z)
(Thin film) 10.3 Hz, 1H), 3.93 (s, 3H),
([M+H]+)
3370, 2962, 1.28- 1.25 (m, 12H), 1.24 1735, 1649, calcd for (s, 9H), 0.83 (d,J=7.2Hz,
389
1527, 1264, C33H43N2O5, 3H).
1145, 801, 547.3166; found,
729 547.3163 13CNMR(126 MHz,
CDC13)5171.76, 168.50, 155.32, 149.63, 149.44, 148.70, 140.42, 138.71, 138.13, 130.51, 127.66, 127.63, 125.64, 125.36, 109.37, 74.03, 57.25, 56.05, 47.78,34.37,34.32,31.31, 31.30, 19.33, 17.40. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.12 (s, 1H), 7.98 (d,J=
5.2 Hz, 1H), 7.23 (dd,J = 8.3, 2.6 Hz, 5H), 7.13 (d,J = 7.9 Hz, 2H), 7.09 (d,J=7.9 Hz, 2H), 6.86 (d,J=5.2Hz,
1H), 5.80 (dq,J=10.4, 6.1 Hz, 1H), 4.49(p,J=7.3Hz,
1H), 3.98 (d,J= 10.2 Hz,
(Thin film) HRMS-ESI (m/z) 1H), 3.93 (s, 3H),2.82(tp,J 3370, 2959, ([M+H]+) = 13.9, 6.9Hz,2H), 1.25 (d, 1734, 1649, J=6.1Hz, 3H), 1.20 (d,J= calcd for
390 1527, 1450, 6.9 Hz, 6H), 1.16 (d,J= 6.9
C31H39N2O5,
1280, 1145, Hz, 6H), 0.86 (d,J=7.2Hz,
519.2853; found,
1045, 801, 3H).
519.2848
729
13CNMR(126 MHz, CDC13)5171.75, 168.50, 155.32, 148.70, 147.36, 147.20, 140.41, 139.09, 138.58, 130.51, 127.91, 126.79, 126.50, 109.37, 73.97, 57.39, 56.05,47.80, 33.64,33.62, 23.98, 23.97, 23.93, 19.31, 17.45.
Figure imgf000345_0001
Figure imgf000346_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1 : 1 mixture of diastereomers. 1H NMR (500 MHz, CDC13) δ 12.14 (s, 1H), 12.09 (s, 1H), 8.34 (d,J=8.0Hz, 1H), 8.24 (d,J=7.9Hz,
(Thin film)
1H), 8.00 (d,J=5.2Hz, 3370, 2981,
HRMS-ESI (m/z) 1H), 7.98 (d,J=5.2Hz, 1734, 1648,
([M+H]+) 1H), 7.32- 7.17 (m, 9H), 1575, 1527,
7.16- 7.10 (m, 1H), 6.88 (d, 1494, 1480, calcd for
395 J=5.2Hz, 1H),6.86 (d,J=
1450, 1279, C25H27N2O5,
5.2 Hz, 1H), 5.88-5.75 (m, 1262, 1242, 435.1914; found,
1H), 4.56-4.44 (m, 1H), 1144, 1047, 435.1924
4.07(d,J=5.6Hz, 1H), 4.05 909, 729,
(d,J=6.1Hz, 1H), 3.95 (s, 702
3H),3.94 (s, 1H), 1.29 (d,J = 7.2 Hz, 3H), 1.26 (d,J= 6.2 Hz, 3H), 1.24 (d,J=6.2 Hz, 3H), 0.97 (d,J=7.2Hz,
3H).
1H NMR (400 MHz, CDC13) δ 11.96 (s, 1H), 8.24 (d,J= 7.9 Hz, 1H), 7.98 (t,J=5.4
HRMS-ESI (m/z)
(Thin film) Hz, 1H), 7.63 -7.59 (m,
([M+H]+)
3372, 2985, 2H), 7.57-7.50 (m, 2H), 2228, 1738, calcd for 7.40 - 7.37 (m,2H), 7.37-
396
1649, 1576, C27H25N4O5, 7.33 (m,2H), 6.93 - 6.84 (m, 1529, 1504, 485.1819; found, 1H), 5.83 - 5.71 (m, 1H), 1452 485.1824 4.61- 4.46 (m, 1H), 4.21 (d,
J=9.3Hz, 1H), 3.96 (s, 3H), 1.28 (d,J=6.1 Hz, 3H), 1.13 (d,J=7.2Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.01 (s, IH), 8.31 (d,J= 8.0 Hz, IH), 7.98 (d,J=5.2 Hz, IH), 7.57(d,J=8.1Hz, 2H), 7.52 (d,J=8.3Hz,
HRMS-ESI (m/z)
2H), 7.42 (d,J=8.3Hz,
(Thin film) ([M+H]+)
2H), 7.39(d,J=8.3Hz, 2984, 1739,
calcd for 2H), 6.87 (d,J=5.3Hz,
397 1681, 1617,
C27H25F6N2O5, IH), 5.90-5.82 (m, IH), 1577, 1530,
571.1662; found, 4.59 - 4.48 (m, IH), 4.22 (d, 1482
571.1671 J=9.6Hz, IH), 3.94 (s, 3H),
1.29(d,J=6.2Hz, 3H), 1.03 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -62.66, -62.69.
1H NMR (400 MHz, CDC13) δ 12.03 (s, IH), 8.33 (d,J= 8.0 Hz, IH), 8.00 - 7.95 (m, 3H), 7.93 (d,J=8.4Hz, 2H), 7.38(d,J=8.4Hz,
HRMS-ESI (m/z)
2H), 7.35 (d,J=8.3Hz,
(Thin film) ([M+H]+)
2H), 6.86 (d,J=5.2Hz, 3364, 2981,
calcd for IH), 5.86 (dp, J= 9.1, 7.1,
398 1713, 1650,
C31H35N2O9, 6.6 Hz, IH), 4.60- 4.50 (m, 1607, 1529,
579.2337; found, IH), 4.35 (qd,J= 7.1, 2.8 1481, 1418
579.2349 Hz, 4H), 4.22 (d,J=9.7Hz,
1H),3.93 (s, 3H), 1.37 (t, J = 7.2 Hz, 3H), 1.37 (t, J =7.1 Hz, 3H), 1.28 (d,J=6.2Hz, 3H), 1.05 (d,J=7.2Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.10 (s, 1H), 8.34 (d,J= 7.9 Hz, 1H), 7.96 (d,J=5.2 Hz, 1H), 7.32(d,J=8.3Hz,
HRMS-ESI (m/z) 1H), 7.09 (d,J=8.7Hz,
(Thin film) ([M+H]+) 1H), 6.86 (d,J=5.3Hz,
3364, 2939, 1H), 6.85 - 6.80 (m, 3H), calcd for
399 1734, 1649, 6.74(d,J=2.0Hz, 1H), 5.88
1488, 1449,
Figure imgf000349_0001
(dq,J=9.6, 6.2 Hz, 1H),
563.1346; found,
1243 4.83 (d,J=9.7Hz, 1H), 4.54
563.1354
(p,J=7.2Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 1.23 (d,J=6.2Hz, 3H), 1.11 (d,J=7.2Hz,
3H).
1H NMR (400 MHz, CDC13) δ 12.12 (s, 1H), 8.36 (d,J= 7.9 Hz, 1H), 7.96 (d,J=5.2 Hz, 1H), 7.32 (dd,J= 8.5, 6.8 Hz, 1H), 7.15(dd,J = 9.0,6.9 Hz, 1H), 6.85 (d,J =
HRMS-ESI (m/z)
(Thin film) 5.2 Hz, 1H), 6.62- 6.39 (m,
([M+H]+)
3373, 2980, 4H), 5.99-5.89 (m, 1H), 1734, 1649, calcd for 4.82 (d,J= 10.1 Hz, 1H),
400
1598, 1480, C29H33F2N2O7, 4.55 (p,J=7.2Hz, 1H), 4.03 1263, 1161, 559.225; found, -3.81 (m, 7H), 1.47 (t,J = 1040 559.2258 7.0 Hz, 3H), 1.40 (t, J =7.0
Hz, 3H), 1.24 (d,J=6.1Hz, 3H), 1.10(d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.62, -114.03. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.10 (s, 1H), 8.36 (d,J= 7.9 Hz, 1H), 7.96 (d,J=5.2 Hz, 1H), 7.29 (d,J=8.3Hz, 1H), 7.11 (d,J=8.2Hz,
HRMS-ESI (m/z) 1H), 6.85 (d,J=5.3Hz,
(Thin film)
([M+H]+) 1H),6.80 (dd,J=8.2,2.0 3367, 2980,
«s Hz, 2H), 6.77 (d,J=2.0Hz,
1735, 1650, calcd for
401 1H), 6.70 (d,J=2.1Hz,
1576, 1528, C29H33CI2N2O7,
1H), 5.92 (dq,J=10.2, 6.2 1243, 1147, 591.1659; found,
Hz, 1H), 4.82 (d,J= 10.0 1041 591.1662
Hz, 1H), 4.62 - 4.47 (m, 1H), 4.03-3.81 (m, 7H), 1.47(t,J=6.9Hz, 3H), 1.39 (t,J=6.9Hz, 3H), 1.24 (d,J = 6.1 Hz, 3H), 1.12 (d,J= 7.2 Hz, 3H).
1H NMR (400 MHz, CDC13) δ 12.17 (s, 1H), 8.40 (d,J= 7.9 Hz, 1H), 7.96 (d,J=5.2 Hz, 1H), 7.28 (d,J=7.8Hz, 1H), 7.13 (d,J=7.6Hz,
HRMS-ESI (m/z)
(Thin film) 1H), 6.84 (d,J=5.3Hz,
([M+H]+)
3374, 2976, 1H), 6.70-6.50 (m, 4H), 1733, 1649, calcd for 5.96 (dq,J= 10.4,6.1 Hz,
402
1527, 1450, C31H39N2O7, 1H), 4.90 (d,J= 10.2 Hz, 1261, 1142, 551.2752; found, 1H), 4.53 (p,J=7.2Hz, 1044 551.2716 1H), 4.05-3.80 (m, 7H),
2.26 (s, 3H), 2.22 (s, 3H), 1.47(t,J=7.0Hz, 3H), 1.39 (t,J=6.9Hz, 3H), 1.24 (d,J = 6.1 Hz, 3H), 1.04 (d,J= 7.2 Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.04 (d,J=0.7Hz, 1H), 8.31 (d,J=7.9Hz, 1H), 7.97
(d,J=5.2Hz, 1H), 7.05-
HRMS-ESI (m/z) 6.90 (m, 2H), 6.90 - 6.77 (m, ([M+H]+) 5H), 5.73 (dq,J=10.0, 6.1
Hz, 1H), 4.63 - 4.47 (m, 1H), calcd for
403 3.99(d,J=9.9Hz, 1H), 3.94
Figure imgf000351_0001
(s, 3H),3.86 (s, 3H), 3.85 (s, 531.1944; found,
3H), 1.26 (d,J=6.1Hz, 531.1937
3H), 1.08 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -137.02, -137.51.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,J=
8.0 Hz, 1H), 7.97 (d,J=5.2
Hz, 1H), 7.20 (d,J=8.6Hz, 1H), 7.16-7.08 (m, 1H),
6.86(d,J=5.3Hz, 1H), 6.71 -6.63(m, 3H), 6.59 (d,J= 2.8 Hz, 1H), 5.65 (dq,J =
9.9, 6.1Hz, 1H), 4.61 - 4.46 (m, 1H), 4.39 (d,J= 10.0
HRMS-ESI (m/z)
Hz, 1H), 3.94 (s, 3H), 3.75 ([M+H]+)
(s, 3H),3.72 (s, 3H),2.37(s, calcd for 3H),2.30(s, 3H), 1.30 (d, J
404
C29H35N2O7, = 6.2 Hz, 3H), 1.09 (d,J= 523.2432; found, 7.2 Hz, 3H).
523.2426
13CNMR(101 MHz, CDC13)5171.70, 168.56, 157.82, 157.67, 155.37, 148.74, 140.37, 137.93, 137.69, 131.88, 131.34, 130.50, 128.88, 128.13, 116.26, 116.08, 111.28, 110.86, 109.41, 75.02, 56.04, 55.08, 47.93, 46.22, 20.36, 20.30, 18.82, 17.78.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) δ 12.16 (s, 1H), 8.37 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.32(d,J=8.4Hz,
HRMS-ESI (m/z) 1H), 7.11 (d,J=8.4Hz,
(Thin film)
([M+H]+) 1H), 6.85 (d,J=5.3Hz, 3368, 2937,
1H), 6.42 - 6.34 (m, 3H), 2837, 1732, calcd for
405 6.32(d,J=2.5Hz, 1H), 5.88
1650, 1609, C29H35N2O9,
(dq,J=9.8, 6.2 Hz, 1H), 1578, 1529, 555.2337; found,
4.82(d,J=9.9Hz, 1H), 4.61 1504 555.2327
-4.46(m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 1.23 (d,J=6.2Hz, 3H), 1.07 (d,J=7.2Hz, 3H).
1H NMR (300 MHz, CDC13) δ 12.16 (d,J= 0.6 Hz, 1H), 8.38(d,J=8.0Hz, 1H), 7.97 (d,J=5.2Hz, 1H), 7.30 (d, J=7.8Hz, lH),7.10(d,J=
HRMS-ESI (m/z)
8.1Hz, 1H), 6.85 (dd,J =
(Thin film) ([M+H]+)
5.3, 0.6 Hz, 1H), 6.70-6.59 * 3373, 2936,
calcd for (m, 3H), 6.57-6.53 (m,
406 1734, 1650,
C29H35N2O7, 1H), 5.92 (dq,J=9.9,6.2 1611, 1577,
523.2439; found, Hz, 1H), 4.90 (d,J=9.9Hz, 1529, 1505
523.2437 1H), 4.60 - 4.43 (m, 1H),
3.94 (s, 3H), 3.83 (s, 3H), 3.72 (s, 3H), 2.27 (s, 3H), 2.24 (s, 3H), 1.23 (d,J=6.2 Hz, 3H), 1.03 (d,J=7.2Hz,
3H).
Figure imgf000354_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) for the major isomer of a 2: 1 mixture of diastereomers d 12.09 (d,J=0.6Hz, 1H), 8.37(d,J=8.0Hz, 1H), 7.98
HRMS-ESI (m/z)
(d,J=5.2Hz, 1H), 7.16 (dd,
(Thin film) ([M+H]+)
J= 9.6, 2.9 Hz, 1H), 6.96 3368, 2940,
calcd for (dd,J=9.3, 3.2 Hz, 1H),
409 2839, 1736,
C27H29F2N2O7, 6.90 - 6.75 (m, 4H), 6.72 (d, 1650, 1528,
531.1937; found, J=4.7Hz, 1H), 5.98-5.79 1495, 1482
531.1937 (m, 1H), 4.91-4.83 (m,
1H), 4.62 - 4.46 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.73 (s, 3H), 1.25 (d,J=6.2 Hz, 3H), 1.11 (d,J=7.2Hz,
3H).
Figure imgf000356_0001
Figure imgf000357_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) for 1 : 1 mixture of diastereomers δ 12.18 (s,
1H), 12.11 (s, 1H), 8.36 (d, J = 7.9 Hz, 1H), 8.28 (d,J=
7.7 Hz, 1H), 8.06-7.91 (m, 2H), 7.11-7.00 (m, 4H),
6.95(t,J=8.6Hz, 2H), 6.89
-6.82 (m, 4H), 6.70 (d,J= 8.2 Hz, 2H), 6.65 (dd,J =
8.0, 4.5 Hz, 2H), 5.70 (ddq,J
= 12.3, 6.1, 3.3, 2.6 Hz, 2H), 4.62 (dd,J= 12.2, 9.9 Hz, 2H),4.49 (dp, J =22.0, 7.2 Hz, 2H), 3.94 (s, 3H), 3.93
(s, 3H),3.79 (s, 3H), 3.79 (s, 3H), 3.75 (s, 3H), 3.74 (s,
4
3H), 2.29 (s, 3H), 2.26 (s,
412
3H), 2.19 (s, 3H), 2.18 (s, 3H), 1.35- 1.25 (m, 9H), 1.05 (d,J=7.2Hz, 3H).
13CNMR(101 MHz, CDCl3)for 1:1 mixture of diastereomers δ 171.69, 171.27, 168.52, 157.74, 157.55, 155.32, 148.73, 140.69, 140.38, 140.12, 139.96, 130.52, 126.17, 126.11, 125.90, 125.55, 125.38, 120.47, 120.38, 119.87, 119.66, 109.38, 108.32, 74.97, 74.87, 56.03, 55.46, 55.43, 47.92, 47.89, 47.53, 18.74, 18.72, 17.98, 17.69, 11.84, 11.74, 11.42. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 512.03 (s, 1H), 8.28 (d,J= 8.0 Hz, 1H), 7.96 (d,J=5.3 Hz, 1H), 7.05 (ddd,J=8.4, 5.6, 2.2 Hz, 1H), 6.89-6.72
(m, 4H), 5.67 (dq,J=9.6, 6.2 Hz, 1H), 4.86 (d,J=9.6
Hz, 1H), 4.56 (dt,J=8.1, 7.0 Hz, 1H), 3.97 (d,J=2.4
Hz, 3H), 3.95 (s, 3H), 3.83
(Thin film)
(d,J=2.1Hz, 3H), 1.25 (d, 3374, 2941, HRMS-ESI (m/z)
J=6.2Hz, 3H), 1.20 (d,J= 1737, 1650, ([M+H]+)
7.2 Hz, 3H).
1529, 1501,
calcd for
413 1476, 1453,
C27H27F4N2O7, 13CNMR(126 MHz, 1431, 1281,
567.1749; found, CDC13)5171.48, 168.61, 1263, 1243,
567.1750 155.43, 148.73, 147.12 (d, J 1058, 952,
= 7.3 Hz), 146.96 (d,J=7.6 801
Hz), 145.26 (d,J= 13.9 Hz), 143.28 (d,J= 13.8 Hz), 140.44, 130.25, 129.70, 129.47, 123.09 (dd,J= 8.2,
3.8 Hz), 122.45- 122.20 (m), 110.82 (d,J= 17.3 Hz),
110.57, 109.47, 72.53, 61.22 (d,J=4.1 Hz), 61.16
(d,J=3.6Hz), 56.11, 47.96, 42.46, 18.74, 17.75.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.11 -7.00 (m, 3H), 6.94-6.84 (m, 4H), 5.73- 5.64 (m, 1H), 4.55- 4.44(m,2H),3.94 (s, 3H),
(Thin film)
2.36 (s, 3H), 2.28 (s, 3H), 3369, 2925,
HRMS-ESI (m/z) 2.26 (s, 6H), 1.30 (d,J= 6.1 1735, 1650,
([M+H]+) Hz, 3H), 1.03 (d,J=7.2Hz, 1576, 1528,
½ 3H).
1501, 1481, calcd for
414
1451, 1331, C29H35N2O5,
13CNMR(126 MHz, 1280, 1263, 491.2540; found,
CDC13)5171.84, 168.52, 1212, 1145, 491.2536
155.34, 148.73, 140.40, 1045, 801,
139.09, 138.45, 135.47, 733
135.11, 133.53, 133.33, 130.60, 130.49, 130.27, 128.60, 127.81, 127.27, 126.95, 109.39, 75.10, 56.07, 47.89, 47.34, 21.29, 21.22, 19.79, 19.75, 18.78,
17.66.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.18(d,J=7.9Hz, 1H), 7.12(d,J=7.7Hz, 1H), 6.98 - 6.89 (m, 3H), 6.87-6.81 (m, 2H), 5.69 (dq,J=10.0, 6.2 Hz, 1H), 4.58- 4.48 (m, 1H), 4.45 (d,
(Thin film)
J= 10.0 Hz, 1H), 3.94 (s,
3369, 2937,
HRMS-ESI (m/z) 3H), 2.35 (s, 3H), 2.29 (s, 1734, 1649,
([M+H]+) 3H), 2.25 (s, 3H), 2.21 (s, 1576, 1527,
3H), 1.30(d,J=6.2Hz,
Ss 1500, 1480, calcd for
415 3H), 1.05 (d,J=7.2Hz,
1450, 1329, C29H35N2O5,
3H).
1280, 1262, 491.2540; found,
1242, 1139, 491.2536
13CNMR(126 MHz, 1043, 908,
CDC13)5171.71, 168.51, 799, 728
155.32, 148.69, 140.38, 136.43, 136.33, 136.15, 135.95, 135.90, 135.58, 131.50, 131.15, 130.49, 127.77, 127.05, 126.85, 126.58, 109.37, 75.04, 56.06, 47.89, 46.81, 20.84, 20.80, 20.12, 20.07, 18.85,
17.71.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 512.05 (s, 1H), 8.36 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.12 (dd,J= 8.4, 6.0 Hz, 1H), 7.06 - 7.00 (m, 2H), 6.93 - 6.77 (m, 4H), 5.60 (dq,J=9.6, 6.2 Hz, 1H), 4.61-4.50 (m, 1H), 4.48 (d,J=9.6Hz, 1H), 3.94 (s, 3H), 2.35 (s, 3H), 2.28 (s,
(Thin film)
3H), 1.34 (d,J=6.2Hz, 3369, 2938,
3H), 1.10(d,J=7.2Hz, 1736, 1649, HRMS-ESI (m/z)
3H).
1576, 1528, ([M+H]+)
1494, 1480,
calcd for 13CNMR(126 MHz,
416 1452, 1326,
C27H29F2N2O5 , CDC13)5171.60, 168.60, 1279, 1263,
499.2039; found, 161.36 (d,J= 244.0 Hz), 1240, 1184,
499.2035 155.35, 148.72, 140.57 (d, J 1145, 1044,
= 6.5 Hz), 140.48, 139.99 910, 803,
(d,J=6.6Hz), 132.34 (d,J 728
= 3.2 Hz), 132.07 (d,J=7.8 Hz), 132.00 (d,J=3.3Hz),
131.72 (d,J=7.9Hz), 130.39, 114.85 (d,J=22.3 Hz), 114.32 (d,J=22.3Hz), 113.72 (d,J=20.7Hz), 113.42 (d,J=20.5Hz), 109.44, 74.21, 56.08, 47.79, 47.70, 19.41, 19.36, 18.76, 17.68.
Figure imgf000363_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.09 (s, 1H), 8.34 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.27(t,J=8.6Hz, 1H), 7.16(t,J=8.5Hz, 1H), 6.86(d,J=5.2Hz, 1H), 6.64 -6.54(m, 3H), 6.47 (dd,J = 12.1, 2.6 Hz, 1H), 5.79 (dq,J = 12.0, 6.1 Hz, 1H),4.66- 4.52(m,2H),3.94 (s, 3H),
(Thin film) 3.75 (s, 3H), 3.72 (s, 3H), 3369, 2938, 1.28 (d,J=6.1 Hz, 3H), 1.14 1737, 1650, (d,J=7.2Hz, 3H).
HRMS-ESI (m/z)
1623, 1577,
([M+H]+)
1529, 1507, 13CNMR(126 MHz, 1481, 1443, calcd for CDC13)5171.55, 168.55,
418 5s
1320, 1282, C27H29F2N2O7, 161.19 (d,J= 245.6 Hz), 1264, 1242, 531.1937; found, 161.00 (d,J= 245.8 Hz), 1195, 1154, 531.1933 159.75 (d,J= 11.3 Hz), 1031, 951, 159.47 (d,J= 11.3 Hz), 849, 834, 155.35, 148.69, 140.39, 800, 731 130.42, 129.87 (d,J= 6.2
Hz), 129.23 (d,J=5.9Hz), 119.53 (d,J= 14.6 Hz), 119.33 (d,J= 15.0 Hz), 110.16 (d,J= 3.0 Hz), 109.66 (d,J=3.0Hz), 109.38, 101.82 (d,J= 26.7 Hz), 101.59 (d,J=26.6Hz), 72.49, 56.05, 55.48 (d,J= 6.8 Hz), 47.90, 41.70, 18.91, 17.79. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.34 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.54 (d,J=7.8Hz, 1H), 7.30(d,J=8.0Hz, 1H), 7.12 (dd,J= 7.9, 1.6 Hz, 2H), 7.04 (d,J= 1.8 Hz, 1H), 6.98 (d,J= 1.7 Hz, 1H), 6.86 (d,J=5.2Hz,
(Thin film)
1H), 5.99 (dq,J=9.5,6.2 3370, 2941,
HRMS-ESI (m/z) Hz, 1H), 5.00 (d,J=9.4Hz, 1737, 1651,
([M+H]+) 1H), 4.59-4.48 (m, 1H), 1616, 1577,
3.94 (s, 3H), 3.89 (s, 3H), 1529, 1454, calcd for
419 3.81 (s, 3H), 1.26 (d,J=6.2
1417, 1326, C29H29F6N2O7,
Hz, 3H), 1.05 (d,J=7.2Hz, 1241, 1119, 631.1873; found,
3H).
1080, 1032, 631.1876
905, 860,
13CNMR(126 MHz, 801, 738
CDC13)5171.62, 168.58, 157.53, 155.38, 148.73, 140.44, 132.32 (d,J= 8.6
Hz), 130.37, 130.18, 130.04, 129.47, 125.02, 122.83, 117.30, 116.98, 109.43, 107.83- 106.97 (m), 72.18, 56.07, 55.75, 55.69, 47.82, 18.89, 17.66.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.04 (d,J=0.6Hz, 1H), 8.34(d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 6.86 (d, J=5.2Hz, 1H), 6.65-6.52
HRMS-ESI (m/z)
(Thin film) (m,4H), 6.45 (ddt,J=24.3,
([M+H]+)
3369, 2940, 10.5,2.2 Hz, 2H), 5.69 (dq,J 1737, 1592, calcd for = 10.1, 6.1 Hz, 1H),4.61 -
420
1453, 1135, C27H29F2N2O7, 4.50 (m, 1H), 3.97-3.91 (m, 1057, 849, 531.1937; found, 4H), 3.77 (s, 3H), 3.75 (s, 730 531.1924 3H), 1.29- 1.24 (m, 3H),
1.11 (d,J=7.2Hz, 3H).
19F NMR (471 MHz, CDC13) δ -110.48 - -110.65 (m), - 111.08 (t,J= 10.0 Hz).
1H NMR (500 MHz, CDC13) δ 12.10 (s, 1H), 8.35 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 6.86 (d,J=5.2Hz, 1H), 6.46 - 6.43 (m, 4H), 6.27 (dt,J=26.6, 2.2 Hz, 2H), 5.75 (dq,J= 10.3,6.1 Hz, 1H), 4.58- 4.47 (m,
HRMS-ESI (m/z)
(Thin film) 1H),3.94 (s, 3H),3.89 (d,J
([M+H]+)
3371,2938, = 10.5 Hz, 1H), 3.76 (s, 6H), 1735, 1593, calcd for 3.74 (s, 6H), 1.30- 1.23 (m,
421
1454, 1204, C29H35N2O9, 3H), 1.05 (d,J=7.2Hz, 1150, 1063, 555.2337; found, 3H).
730 555.2329
13CNMR(126 MHz, CDC13)5171.70, 168.53, 160.93, 160.75, 155.32, 148.71, 143.38, 143.10, 140.39, 130.45, 109.36, 106.42, 106.08, 98.42, 98.35, 73.11, 58.22, 56.06, 55.30, 55.26, 47.87, 19.21, 17.70. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.11 (s, 1H), 8.36 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 6.86 (d,J=5.2Hz,
1H),6.69 (dd,J=3.8, 1.8 Hz, 2H), 6.64 (t, J = 1.9 Hz, 2H), 6.55 (t,J=2.0Hz, 1H), 6.49 (t,J= 1.9 Hz, 1H), 5.75 (dq,J=10.5, 6.2 Hz, 1H), 4.58- 4.48 (m, 1H), 3.94 (s,
HRMS-ESI (m/z) 3H), 3.89 (d,J= 10.5 Hz,
(Thin film)
([M+H]+) 1H), 3.76 (s, 3H), 3.73 (s, 3372, 2937,
3H), 2.29 (s, 3H), 2.25 (s, 1735, 1594, calcd for
422 3H), 1.25 (d,J=6.2Hz,
1528, 1452, C29H35N2O7,
3H), 1.00 (d,J=7.1Hz, 1151, 1065, 523.2439; found,
3H).
730 523.2434
13CNMR(126 MHz, CDC13)5171.74, 168.51, 159.74, 159.61, 155.32, 148.70, 142.68, 142.37, 140.40, 139.79, 139.36, 130.47, 121.27, 121.12, 112.62, 112.61, 111.34, 110.82, 109.36, 73.43, 57.89, 56.06, 55.15, 55.11,47.86, 21.69,21.61, 19.25, 17.66.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.10 (s, 1H), 8.33 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.02 (dd,J=7.5, 0.9 Hz, 1H), 6.97 (dd,J =
HRMS-ESI (m/z) 7.6, 0.8 Hz, 1H), 6.86 (d,J =
(Thin film)
([M+H]+) 5.2 Hz, 1H),6.80 (dt,J= 3370, 2937,
7.5, 2.1 Hz, 2H), 6.74 (d,J = 1734, 1649, calcd for
423 1.6 Hz, 1H), 6.71 (d,J= 1.6
1528, 1452, C29H35N2O7,
Hz, 1H), 5.80 (dq,J= 10.3, 1260, 1137, 523.2439; found,
6.1Hz, 1H), 4.58- 4.47 (m, 1039, 729 523.2434
1H), 3.96 (d,J=10.3Hz, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 3.78 (s, 3H), 2.14 (s, 3H),2.11 (s, 3H), 1.27 (d,J = 6.1 Hz, 3H), 1.00 (d,J= 7.2 Hz, 3H).
1H NMR (500 MHz, CDC13) 512.05 (s, 1H), 8.33 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.01-6.91 (m, 4H), 6.91 - 6.79 (m, 3H),
HRMS-ESI (m/z) 5.65 (dq,J=9.6, 6.2 Hz,
(Thin film) ([M+H]+) 1H), 4.61-4.51 (m, 1H), 3370, 2938, 3.94 (s, 3H), 3.92 (d,J=9.7 calcd for
424 1736, 1515, Hz, 1H), 3.85 (s, 3H), 3.83
1442, 1275,
Figure imgf000368_0001
(s, 3H), 1.24 (d,J=6.1Hz,
531.1937; found,
1216, 731 3H), 1.13 (d,J=7.2Hz,
531.1935
3H).
19F NMR (471 MHz, CDC13) δ -134.12 (dd,J= 12.1,8.5 Hz), -134.58 (dd,J= 12.1,
8.7 Hz). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.13 (d,J=0.6Hz, 1H), 8.36(d,J=8.1Hz, 1H), 7.98 (d,J=5.1Hz, 1H), 7.06 (ddd,J=9.0, 7.1,2.4 Hz,
HRMS-ESI (m/z) 2H), 7.01 (d,J=2.0Hz,
(Thin film)
([M+H]+) 2H), 6.86 (d,J=5.2Hz, 3370, 2941,
1H), 6.72 (d,J=8.4Hz, 1734, 1649, calcd for
425 1H), 6.68 (d,J=8.4Hz,
1503, 1243, C29H35N2O7,
1H), 5.71 (dq,J= 10.1,6.1 1135, 1033, 523.2439; found,
Hz, 1H), 4.58- 4.48 (m, 801, 729 523.2428
1H),3.94 (s, 3H),3.88 (d,J = 10.1 Hz, 1H), 3.77 (s, 3H),
3.74 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H), 1.24 (d,J=6.2 Hz, 3H), 1.03 (d,J=7.1Hz,
3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.14 (s, 1H), 8.38 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.05 (d,J=3.0Hz, 1H), 6.88 (d,J=3.1Hz, 1H), 6.85 (d,J=5.2Hz, 1H), 6.77 (d,J=8.9Hz, 1H), 6.72- 6.55 (m, 3H), 5.94 (dq,J= 10.1,6.1 Hz, 1H), 4.93 (d,J=10.1Hz,
HRMS-ESI (m/z)
(Thin film) 1H), 4.60 - 4.49 (m, 1H),
([M+H]+)
3372, 2940, 3.94 (s, 3H), 3.82 (s, 3H), 1735, 1650, calcd for 3.74 (s, 3H), 3.71 (s, 6H),
426
1498, 1223, C29H35N2O9, 1.28- 1.22 (m, 3H), 1.04 (d, 1047, 804, 555.2337; found, J=7.2Hz, 3H).
730 555.2304
13CNMR(126 MHz, CDC13)5171.72, 168.47, 155.28, 153.41, 153.37, 151.78, 151.70, 148.67, 140.35, 130.55, 130.51, 116.43, 115.36, 112.05, 112.00, 111.68, 111.46, 109.31, 73.26, 56.27, 56.05, 55.62, 55.57, 47.90, 18.87,
17.81.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) δ 12.10 (s, 1H), 8.36 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.06 (d,J=8.4Hz, 1H), 6.95 (d,J=8.4Hz, 1H), 6.90 (d,J=2.7Hz,
HRMS-ESI (m/z)
(Thin film) 1H), 6.86 (d,J=5.2Hz,
([M+H]+)
3370, 2939, 1H), 6.82 (d,J=2.7Hz, 1736, 1529, calcd for 1H),6.66 (dd,J=8.4,2.7
427 «S
1452, 1243, C29H35N2O7, Hz, 1H), 6.60 (dd,J=8.3, 1143, 1043, 523.2439; found, 2.7 Hz, 1H), 5.67 (dq,J = 801, 730 523.2420 10.0, 6.2 Hz, 1H), 4.58- 4.49 (m, 1H), 4.46 (d,J= 10.1 Hz, 1H), 3.94 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.34 (s, 3H), 2.26 (s, 3H), 1.32(d,J=6.2Hz, 3H), 1.05 (d,J=7.2Hz, 3H).
1H NMR (400 MHz, CDC13) 512.05 (s, 1H), 8.32 (d,J= 7.9 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.43 (dd,J=8.7, 5.6 Hz, 1H), 7.23 (dd,J = 8.7, 5.6 Hz, 1H),7.11 (dd,J = 9.6, 2.8 Hz, 1H), 7.04 (dd,
HRMS-ESI (m/z)
(Thin film) J= 9.6, 2.8 Hz, 1H), 6.96- ([M+H]+)
3368, 2933, 6.89 (m,2H), 6.87 (d,J=5.2 1736, 1648, calcd for Hz, 1H), 5.63 (dq,J=8.7,
428
1528, 1492, C29H33F2N2O7, 6.2 Hz, 1H), 4.71 (d,J=8.8 1481, 1263, 560.2283; found, Hz, 1H), 4.63 (d,J= 12.4 1094 560.2285 Hz, 1H), 4.58- 4.36 (m,
4H), 3.94 (s, 3H), 3.43 (s, 3H),3.38(s, 3H), 1.30 (d, J = 6.2 Hz, 3H), 1.12 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.46, -115.76. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.33 (d,J= 7.9 Hz, 1H), 7.98 (d,J=5.2
Hz, 1H), 7.45 (dd,J=8.7,
5.6 Hz, 1H), 7.21 (dd,J = 8.7, 5.6 Hz, lH),7.12(dd,J
HRMS-ESI (m/z)
= 9.6, 2.8 Hz, 1H), 7.07 (dd,
(Thin film) ([M+H]+)
J= 9.7, 2.8 Hz, 1H), 6.94- 3369, 2975,
calcd for 6.84 (m, 3H), 5.73 - 5.56 (m,
429 1736, 1649,
C31H37F2N2O7, 1H), 4.78 - 4.63 (m, 2H), 1527, 1481,
587.2563; found, 4.60- 4.38 (m, 4H), 3.94 (s, 1262, 1093
587.2559 3H), 3.62-3.42 (m, 4H),
1.33 - 1.25 (m, 6H), 1.23 (t, J=7.0Hz, 3H), 1.12 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.57, -115.85.
1H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.3 Hz, 1H), 7.48 - 7.07 (m, 6H),
HRMS-ESI (m/z)
6.85 (d,J=5.3Hz, 1H), 6.58 ([M+H]+)
(t,J=8.3 Hz, 2H), 5.85 (dd, calcd for J= 10.1, 6.0 Hz, 1H), 4.72-
430
C26H28FN2O6, 4.38 (m,2H), 3.93 (s, 3H), 483.1931; found, 3.83 (s, 3H), 1.25 (d,J=6.2 483.1928 Hz, 3H), 0.99 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.13. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.09 (s, IH), 8.33 (d,J= 7.9 Hz, IH), 7.97 (d,J=5.2 Hz, IH), 7.36 - 7.07 (m, 6H),
HRMS-ESI (m/z)
6.94 - 6.78 (m, 3H), 5.78 ([M+H]+)
(dq,J= 10.4, 6.1Hz, IH), calcd for 4.52 (p,J=7.3Hz, IH), 4.29
431
C26H28FN2O5, (d,J= 10.3 Hz, IH), 3.93 (s, 467.1982; found, 3H),2.39(s, 3H), 1.28 (d,J 467.1976 = 6.1 Hz, 3H), 1.00 (d,J=
7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -116.60.
1H NMR (400 MHz, CDC13) δ 12.09 (s, IH), 8.34 (d,J= 8.0 Hz, IH), 7.97 (d,J=5.2 Hz, IH), 7.47 - 7.20 (m, 5H), 7.20- 7.10 (m, IH), 6.86 (d,
HRMS-ESI (m/z)
J=5.2Hz, IH), 6.57(td,J= ([M+H]+)
8.3, 2.6 Hz, IH), 6.49 (dd, J calcd for = 10.9, 2.5 Hz, IH), 5.83
432
C26H28FN2O6, (dq,J= 10.2, 6.1Hz, IH), 483.1931; found, 4.61 -4.49 (m,2H), 3.94 (s, 483.1931 3H),3.76 (s, 3H), 1.24 (d,J
= 6.1 Hz, 3H), 1.07 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.49.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.07 (s, 1H), 8.34 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.35 (dd,J= 8.7, 5.7 Hz, 1H), 7.31-7.13 (m,
HRMS-ESI (m/z) 5H), 6.92 - 6.80 (m, 2H), ([M+H]+) 6.76 (dd,J=9.7, 2.8 Hz,
1H), 5.75 (dq,J= 10.1,6.1 calcd for
433 Hz, 1H), 4.53 (p,J=7.3Hz,
¾ C26H28FN2O5,
1H), 4.26 (d,J=10.1Hz, 467.1982; found,
1H), 3.93 (s, 3H), 2.30 (s, 467.1974
3H), 1.26 (d,J=6.1Hz, 3H), 1.05 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.99.
1H NMR (400 MHz, CDC13) δ 12.12 (s, 1H), 8.35 (d,J=
8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.19(d,J=8.0Hz,
2H), 7.17-7.08 (m, 1H),
HRMS-ESI (m/z)
7.01 (d,J=8.0Hz, 2H), 6.86 ([M+H]+)
(d,J=5.2Hz, 1H), 6.64- calcd for 6.51 (m, 2H), 5.82 (dq,J =
434
C27H30FN2O6, 9.9, 6.2 Hz, 1H), 4.63 -4.41 497.2088; found, (m,2H), 3.94 (s, 3H), 3.83 497.2077 (s, 3H), 2.25 (s, 3H), 1.24 (d,
J=6.2Hz, 3H), 1.03 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.38. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.11 (s, IH), 8.34 (d,J= 8.0 Hz, IH), 7.98 (d,J=5.2 Hz, IH), 7.38- 7.26 (m, IH), 7.13 (d,J=8.1Hz, 2H), 7.00
HRMS-ESI (m/z)
(d,J=8.0Hz,2H), 6.95- ([M+H]+)
6.80 (m, 3H), 5.76 (dq,J = calcd for 10.2, 6.2 Hz, IH), 4.53 (p,J
435
C27H30FN2O5, = 7.3 Hz, IH), 4.25 (d,J= 481.2139; found, 10.2 Hz, IH), 3.93 (s, 3H), 481.2133 2.38 (s, 3H), 2.24 (s, 3H),
1.27(d,J=6.1Hz, 3H), 1.04 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -116.80.
1H NMR (400 MHz, CDC13) δ 12.10 (s, IH), 8.34 (d,J= 8.0 Hz, IH), 7.97 (d,J=5.2 Hz, IH), 7.33 - 7.22 (m, IH), 7.19-7.13 (m,2H), 7.06 (d, J= 7.8 Hz, 2H), 6.85 (d,J=
HRMS-ESI (m/z)
5.2 Hz, IH), 6.56 (td, J = ([M+H]+)
8.3, 2.6 Hz, IH), 6.48 (dd, J calcd for = 10.9, 2.5 Hz, IH), 5.80
436
C27H30FN2O6, (dq,J= 10.4, 6.1Hz, IH), 497.2088; found, 4.62 - 4.44 (m, 2H), 3.94 (s, 497.2076 3H), 3.76 (s, 3H), 2.28 (s,
3H), 1.23 (d,J=6.1Hz, 3H), 1.06 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.69. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.07 (s, 1H), 8.33 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.33 (dd,J= 8.7, 5.8 Hz, 1H), 7.18 -7.00 (m,
HRMS-ESI (m/z) 4H), 6.94-6.81 (m, 2H), ([M+H]+) 6.74 (dd,J=9.7, 2.8 Hz,
1H), 5.73 (dq,J= 10.1,6.1 calcd for
437 Hz, 1H), 4.52(p,J=7.3Hz,
C27H30FN2O5,
1H), 4.22 (d,J= 10.3 Hz, 481.2139; found,
1H), 3.94 (s, 3H), 2.29 (s, 481.2121
3H),2.28 (s, 3H), 1.25 (d,J = 6.1 Hz, 3H), 1.04 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -117.22.
1H NMR (400 MHz, CDC13) δ 12.09 (s, 1H), 8.33 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.31 -7.23 (m,2H),
HRMS-ESI (m/z) 7.12 (dd,J= 8.2, 6.5 Hz, ([M+H]+) 1H), 6.94 - 6.80 (m, 3H),
¾: 6.64 - 6.52 (m, 2H), 5.81 calcd for
438 (dq,J=10.0, 6.2 Hz, 1H),
Figure imgf000376_0001
4.61 -4.38 (m,2H), 3.94 (s, 501.1837; found,
3H),3.83 (s, 3H), 1.25 (d,J 501.1829
= 6.2 Hz, 3H), 1.06 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -112.82, -116.36. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.08 (s, IH), 8.33 (d,J= 7.9 Hz, IH), 7.97 (d,J=5.2 Hz, IH), 7.33 -7.12 (m, 3H),
HRMS-ESI (m/z)
6.97 - 6.83 (m, 5H), 5.73 ([M+H]+)
(dq,J= 9.9, 6.1Hz, IH), calcd for 4.68 - 4.46 (m, IH), 4.28 (d,
439
C26H27F2N2O5, J= 10.1 Hz, IH), 3.94 (s, 485.1888; found, 3H),2.36(s, 3H), 1.28 (d,J 485.1874 = 6.1 Hz, 3H), 1.09 (d,J=
7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.88, -116.28.
1H NMR (400 MHz, CDC13) δ 12.08 (s, IH), 8.33 (d,J= 8.0 Hz, IH), 7.97 (d,J=5.2 Hz, IH), 7.30- 7.19 (m, 3H), 6.99 - 6.90 (m, 2H), 6.86 (d,
HRMS-ESI (m/z)
J=5.3Hz, IH), 6.57(td,J= ([M+H]+)
8.3, 2.5 Hz, 1H),6.50 (dd,J calcd for = 10.9, 2.5 Hz, IH), 5.92-
440
C26H27F2N2O6, 5.68 (m, IH), 4.64 - 4.40 (m, 501.1837; found, 2H), 3.94 (s, 3H), 3.76 (s, 501.1824 3H), 1.23 (d,J=6.2Hz,
3H), 1.09 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.15, -116.03.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.34 (d,J= 8.0 Hz, 1H), 7.96 (d,J=5.2 Hz, 1H), 7.33 (dd,J= 8.7, 5.7 Hz, 1H), 7.19(dd,J = 8.5, 5.4 Hz, 2H), 7.02-6.90
HRMS-ESI (m/z)
(m, 2H), 6.91 - 6.82 (m, 2H), ([M+H]+)
6.77 (dd,J=9.7, 2.8 Hz, calcd for 1H), 5.71 (dq,J=9.8,6.1
441
C26H27F2N2O5, Hz, 1H), 4.53 (p,J=7.3Hz, 485.1888; found, 1H), 4.26 (d,J=9.9Hz, 485.1876 1H), 3.93 (s, 3H), 2.27 (s,
3H), 1.25 (d,J=6.2Hz, 3H), 1.07 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -115.42, -116.65.
1H NMR (400 MHz, CDC13) δ 12.11 (s, 1H), 8.35 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.20-7.13 (m,
HRMS-ESI (m/z)
1H), 7.12-7.06 (m, 5H),
(Thin film) ([M+H]+)
7.03 - 6.97 (m, 1H), 6.96 - 3376, 2929,
calcd for 6.92 (m, 1H), 6.85 (d,J=5.2
442 1736, 1650,
C27H3iN205, Hz, 1H), 5.79 (dq,J= 10.3, 1576, 1529,
463.2224; found, 6.1Hz, 1H), 4.57- 4.44 (m, 1481, 1452
463.2227 1H), 3.97 (d,J= 10.4 Hz,
1H), 3.93 (s, 3H), 2.31 (s, 3H),2.27 (s, 3H), 1.25 (d,J = 6.1 Hz, 3H), 0.97 (d,J= 7.2 Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.09 (s, 1H), 8.35 (d,J= 7.7 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.23 (dd,J=8.5, 6.6 Hz, 1H), 7.17(dd,J = 8.6, 5.8 Hz, 1H), 6.90-6.73
HRMS-ESI (m/z)
(m,2H), 6.57 (td,J= 8.3, 2.5 ([M+H]+)
Hz, 1H), 6.49 (dd,J=10.8, calcd for 2.5 Hz, 1H), 5.70 (dq,J =
443 f
C27H29F2N2O6, 10.1, 6.1 Hz, 2H), 4.75 (d,J 516.2021; found, = 10.2 Hz, 1H), 4.55 (p,J= 516.2018 7.3 Hz, 1H),3.94 (s, 3H),
3.76 (s, 3H), 2.43 (s, 3H), 1.24(d,J=6.2Hz, 3H), 1.12 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.36, -116.89.
1H NMR (400 MHz, CDC13) δ 12.07 (s, 1H), 8.33 (d,J= 7.9 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.29 (dd,J=8.4, 6.7 Hz, 1H), 7.25- 7.14 (m, 1H), 6.86 (d,J=5.2Hz, 1H), 6.81-6.70 (m, 2H),
HRMS-ESI (m/z) 6.56 (td,J= 8.3, 2.5 Hz, ([M+H]+) lH),6.50(dd,J= 10.8, 2.5
Hz, 1H), 5.82 (dq,J= 11.5, calcd for
444 6.2 Hz, 1H), 4.78 (d,J= 10.1
Figure imgf000379_0001
Hz, 1H), 4.55(p,J=7.2Hz, 519.1737; found,
1H), 3.94 (s, 3H), 3.75 (s, 519.1734
3H), 1.26 (d,J=6.1Hz, 3H), 1.12(d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -112.12 (d, J = 7.5Hz),- 112.18 (d, J = 7.5Hz), - 112.75 Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.08 (s, 1H), 8.33 (d,J=
7.9 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.32 (dd,J= 8.6, 5.8 Hz, 1H), 7.03 (dd,J =
8.3, 6.7 Hz, 1H), 6.86 (d,J =
HRMS-ESI (m/z) 5.2 Hz, 1H), 6.81 (td,J= ([M+H]+) 8.5, 2.8 Hz, 1H),6.75 (dd,J
= 9.7, 2.7 Hz, 1H), 6.62 - calcd for
445 6.51 (m, 2H), 5.69 (dq,J =
Figure imgf000380_0001
10.0, 6.2 Hz, 1H), 4.76 (d,J 516.2021; found,
= 9.8 Hz, 1H), 4.53 (p,J= 516.2021
7.2 Hz, 1H),3.94 (s, 3H), 3.84 (s, 3H), 2.26 (s, 3H),
1.27(d,J=6.2Hz, 3H), 1.07 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -112.84, -117.29.
1H NMR (400 MHz, CDC13) δ 12.04 (s, 1H), 8.31 (d,J= 7.8 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.32 (dd,J= 8.6, 5.7 Hz, 1H), 7.18- 7.07 (m, 1H), 6.90 - 6.72 (m, 5H),
HRMS-ESI (m/z)
5.70 (dq,J= 11.7,6.4 Hz, ([M+H]+)
1H), 4.64 (d,J= 10.0 Hz, calcd for 1H), 4.54(p,J=7.2Hz,
446
C26H26F3N2O5, 1H), 3.94 (s, 3H), 2.27 (s, 504.1821; found, 3H), 1.29 (d,J=6.1Hz, 504.1818 3H), 1.09 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -111.40 (d,J=7.6Hz),- 112.58 (d,J= 7.6 Hz), - 116.32. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.30- 12.00 (m, 1H), 8.36(d,J=8.0Hz, 1H), 7.96 (dd,J=5.2, 1.5 Hz, 1H), 7.39- 7.12 (m, 6H), 6.89-
HRMS-ESI (m/z)
(Thin film) 6.82 (m, 2H), 6.72 (dd,J =
([M+H]+)
3373, 2980, 11.3, 1.6 Hz, 1H), 5.82 (dq,J 2938, 1737, calcd for = 9.8, 6.0 Hz, lH),4.56(p,J
447
1650, 1576, C26H28FN2O5, = 7.3 Hz, 1H), 4.41 (d,J= 1530, 1481, 467.1977; found, 10.1 Hz, 1H), 3.92 (s, 3H), 1452 467.1974 2.23 (s, 3H), 1.26 (d,J=6.1
Hz, 3H), 1.09 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -118.95.
1H NMR (400 MHz, CDC13) δ 12.07 (d,J=0.6Hz, 1H), 8.34(d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.29- 7.23 (m,2H), 7.21 (t,J= 7.9
HRMS-ESI (m/z) Hz, 1H), 7.00 - 6.93 (m,
(Thin film)
([M+H]+) 2H), 6.89-6.84 (m, 2H), 3377, 2983,
6.75-6.71 (m, 1H), 5.81 - 1737, 1650, calcd for
448 5.68 (m, 1H), 4.60- 4.49 (m,
1577, 1530, C26H27F2N2O5,
1H), 4.39 (d,J= 10.1 Hz, 1510, 1481, 485.1883; found,
1H), 3.94 (s, 3H), 2.24 (s, 1453, 1440 485.1877
3H), 1.26 (d,J=6.1Hz, 3H), 1.10(d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -115.56, -118.95. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.10 (s, 1H), 8.36 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.1 Hz, 1H), 7.28- 7.12 (m, 3H), 7.08 (d,J=7.8Hz,
HRMS-ESI (m/z) 2H), 6.88-6.81 (m, 2H),
(Thin film)
([M+H]+) 6.71 (d,J= 11.2 Hz, 1H), 3378, 2982,
5.80 (dq,J= 12.1,6.2 Hz, 2932, 1738, calcd for
449 1H), 4.55 (p,J=7.3Hz,
1650, 1576, C27H30FN2O5,
1H), 4.38 (d,J= 10.1 Hz, 1530, 1481, 481.2133; found,
1H), 3.92 (s, 3H), 2.28 (s, 1452 481.2133
3H),2.22 (s, 3H), 1.26 (d,J = 6.1 Hz, 3H), 1.09 (d,J= 7.0 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -119.09.
1H NMR (400 MHz, CDC13) δ 12.09 (d,J=0.6Hz, 1H), 8.34(d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.24 (dd, J=9.4, 5.5 Hz, 1H), 7.15 (t,
HRMS-ESI (m/z) J=7.9Hz, 1H), 6.90-6.78
(Thin film) ([M+H]+) (m, 4H), 6.75 - 6.67 (m,
¾\ 3373, 2982, 1H), 5.79-5.68 (m, 1H), calcd for
450 1737, 1651, 4.64 (d,J= 10.2 Hz, 1H),
C27H29F2N2O5,
1577, 1530, 4.61 -4.52 (m, 1H), 3.94 (s,
499.2039; found,
1482, 1453 3H), 2.39 (s, 3H), 2.24 (s,
499.2033
3H), 1.27 (d,J=6.2Hz, 3H), 1.13 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.44, -118.17. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.06 (s, 1H), 8.33 (d,J=
HRMS-ESI (m/z) 8.0 Hz, 1H), 7.98 (d,J=5.2
(Thin film)
([M+H]+) Hz, 1H), 7.32 - 7.20 (m, 3375, 2982,
2H), 6.91 - 6.70 (m, 5H), 2939, 1739, calcd for
451 5.86- 5.76 (m, 1H), 4.70 (d,
1651, 1577, C26H26F3N2O5,
J= 10.0 Hz, 1H), 4.62-4.51 1530, 1504, 503.1788; found,
(m, 1H), 3.94 (s, 3H), 2.25 1481, 1453 503.1784
(s, 3H), 1.29 (d,J=6.2Hz, 3H), 1.12(d,J=7.3Hz,
3H).
1H NMR (400 MHz, CDC13) δ 12.08 (d,J=0.6Hz, 1H),
8.33 (d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.31 -
7.19 (m, 4H), 7.17 -7.12 (m, 1H), 7.12- 7.02 (m, 2H),
HRMS-ESI (m/z)
6.91 (dd,J=9.3, 8.3 Hz, ([M+H]+)
1H), 6.86 (d,J=5.2Hz, calcd for 1H), 5.77 (dq,J=10.2, 6.1
452 i C26H28FN2O5, Hz, 1H), 4.59 - 4.46 (m, 1H),
467.1982; found, 3.99 (d,J= 10.2 Hz, 1H), 467.1969 3.94 (s, 3H), 2.23 (d,J= 1.9
Hz, 3H), 1.25 (d,J=6.2Hz, 3H), 0.97 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -120.09.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.08 (s, 1H), 8.33 (d,J= 8.0 Hz, 1H), 7.97 (d,J=5.2 Hz, 1H), 7.25 - 7.20 (m, 1H), 7.12-7.01 (m, 2H), 6.93 - 6.82 (m,2H), 6.57(td,J =
HRMS-ESI (m/z)
8.3, 2.5 Hz, 1H),6.50 (dd,J ([M+H]+)
= 10.9, 2.5 Hz, 1H), 5.76 calcd for (dq,J= 10.3, 6.1Hz, 1H),
453
C27H29F2N2O6, 4.61 -4.48 (m, 1H), 4.45 (d, 515.1993; found, J= 10.2 Hz, 1H), 3.94 (s, 515.1980 3H),3.77 (s, 3H),2.22 (d,J
= 1.9 Hz, 3H), 1.22 (d,J= 6.1Hz, 3H), 1.07 (d,J=7.2
Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.33, -120.33.
1H NMR (400 MHz, CDC13) δ 12.10 (d,J= 0.6 Hz, 1H),
8.34(d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.31-
7.27 (m,2H), 7.24- 7.15 (m, 4H), 7.15-7.06 (m, 3H),
(Thin film)
6.86(d,J=5.2Hz, 1H), 5.81 3373, 2980,
(dq,J= 10.2, 6.1Hz, 1H), 2938, 1735, HRMS-ESI (m/z)
4.57 - 4.46 (m, 1H), 4.02 (d, 1649, 1576, ([M+H]+)
J= 10.2 Hz, 1H), 3.94 (s, 1528, 1495,
calcd for 3H),2.28 (s, 3H), 1.26 (d,J
454 1480, 1451,
C26H29N2O5, = 6.1 Hz, 3H), 0.96 (d,J= 1332, 1280,
449.2071; found, 7.2 Hz, 3H).
1263, 1242,
449.2063
1213, 1144,
13CNMR(126 MHz, 1048, 799,
CDC13)5171.68, 168.51, 733, 699
155.33, 148.70, 141.68, 140.40, 138.15, 136.55, 130.48, 129.48, 128.48, 127.93, 126.59, 109.38, 73.63, 57.57, 56.07, 47.85,
20.98, 19.24, 17.61. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.11 (d,J=0.6Hz, 1H), 8.35 (d,J=8.0Hz, 1H), 7.98
(d,J=5.2Hz, 1H), 7.29- 7.24 (m,4H), 7.20- 7.15 (m, 3H), 7.03 (d,J=7.9Hz, 2H), 6.86 (d,J=5.2Hz,
(Thin film) 1H), 5.80 (dq,J= 10.1,6.2 3367, 2981, Hz, 1H), 4.58- 4.47 (m,
HRMS-ESI (m/z)
2938, 1736, 1H), 4.02 (d,J= 10.0 Hz,
([M+H]+)
1649, 1576, 1H), 3.94 (s, 3H), 2.25 (s, 1529, 1480, calcd for 3H), 1.25 (d,J=6.1Hz,
455 i¾ 1451, 1333, C26H29N2O5, 3H), 1.01 (d,J=7.2Hz,
1281, 1263, 449.2071; found, 3H).
1213, 1146, 449.2068
1048, 801, 13CNMR(126 MHz, 734, 700 CDC13)5171.65, 168.50,
155.33, 148.69, 141.41, 140.38, 138.28, 136.20, 130.47, 129.12, 128.74, 128.05, 127.90, 126.82, 109.36, 73.61, 57.44, 56.06, 47.86, 20.92, 19.23,
17.67.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.09 (s, 1H), 8.34 (d,J= 8.0 Hz, 1H), 7.98 (d,J=5.2 Hz, 1H), 7.25-7.21 (m, 2H), 7.18-7.13 (m, 2H), 7.04 (d, 7= 7.9 Hz, 2H), 7.00 -6.92 (m, 2H), 6.86 (d,J= 5.2 Hz, 1H), 5.75 (dq,J =
(Thin film)
9.9, 6.2 Hz, 1H), 4.59-4.47 3369, 2982,
(m, 1H), 4.02 (d,J=9.8Hz, 2937, 1735, HRMS-ESI (m/z)
1H), 3.94 (s, 3H), 2.26 (s, 1649, 1576, ([M+H]+)
3H), 1.24 (d,J=6.2Hz, 1528, 1508,
calcd for 3H), 1.02 (d, 7= 7.2 Hz,
456 1480, 1451,
C26H28FN2O5, 3H).
1329, 1280,
467.1977; found,
1263, 1218,
467.1974 13CNMR(126 MHz, 1157, 1049,
CDC13)5171.61, 168.52, 815, 800,
161.66 (d,J= 245.6 Hz), 729
155.35, 148.71, 140.40, 138.01, 137.20 (d, 7= 3.3 Hz), 136.40, 130.44, 129.53
(d,J=7.9Hz), 129.22, 127.84, 115.57 (d, 7= 21.1 Hz), 109.39, 73.44, 56.56, 56.07, 47.85, 20.92, 19.14,
17.66.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) δ 12.07 (d,J=0.6Hz, 1H), 8.33 (d,J=8.0Hz, 1H), 7.98
(d,J=5.2Hz, 1H), 7.33- 7.19 (m, 7H), 6.96-6.88 (m, 2H), 6.87 (dd,J= 5.3, 0.6
(Thin film)
Hz, 1H), 5.78 (dq,J=9.9, 3373, 2982,
6.1Hz, 1H), 4.61- 4.47 (m, 2938, 1736,
HRMS-ESI (m/z) 1H), 4.05 (d,J=10.0Hz, 1649, 1576,
([M+H]+) 1H),3.94 (s, 3H), 1.26 (d,J 1529, 1509,
= 6.2 Hz, 3H), 1.05 (d,J= 1480, 1452, calcd for
457 7.2 Hz, 3H).
1330, 1280, C25H26FN205,
1263, 1242, 453.1820; found,
13CNMR(126 MHz, 1220, 1159, 453.1810
CDC13)5171.62, 168.57, 1048, 815,
161.59 (d,J= 245.2 Hz), 799, 732,
155.38, 148.73, 140.92, 699
140.43, 137.11 (d,J=3.5 Hz), 130.39, 129.53 (d,J = 7.8 Hz), 128.88, 127.99, 127.08, 115.29 (d,J= 21.2 Hz), 109.43, 73.50, 57.03, 56.08, 47.87, 19.21, 17.69.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) δ 12.08 (d,J=0.6Hz, 1H),
8.33 (d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.30-
7.21 (m,2H), 7.14 (d,J= 8.3
Hz, 2H), 7.09 (d,J=8.2Hz, 2H), 6.95 - 6.84 (m, 3H),
(Thin film) 5.76 (dq,J= 10.1,6.1 Hz,
3366, 2979, 1H), 4.59-4.47 (m, 1H), 2939, 1736, HRMS-ESI (m/z) 4.01 (d,J= 10.1 Hz, 1H), 1649, 1576, ([M+H]+) 3.94 (s, 3H), 2.29 (s, 3H), 1529, 1509, 1.25 (d,J=6.1 Hz, 3H), 1.04 calcd for
458 1481, 1451, (d,J=7.2Hz, 3H).
C26H28FN2O5,
1332, 1264,
467.1977; found,
1242, 1220, 13CNMR(126 MHz,
467.1969
1159, 1049, CDC13)5171.61, 168.55, 815, 800, 161.53 (d,J= 244.9 Hz), 770, 732 155.37, 148.71, 140.41,
137.93, 137.41 (d,J=3.3
Hz), 136.72, 130.39, 129.54, 129.41 (d,J=7.9 Hz), 127.82, 115.24(d,J =
21.3 Hz), 109.41, 73.55, 56.67, 56.07, 47.87, 20.96, 19.20, 17.68.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.07 (d,J=0.6Hz, 1H),
8.32(d,J=8.0Hz, 1H), 7.98 (d,J=5.2Hz, 1H), 7.35-
7.20 (m, 5H), 7.19- 7.10 (m, 1H), 6.88 - 6.75 (m, 3H),
(Thin film) 5.88- 5.77 (m, 1H), 4.58- 3376, 2984, 4.47 (m, 1H), 4.42 (d,J= 2938, 1737, 10.1 Hz, 1H), 3.94 (s, 3H),
HRMS-ESI (m/z)
1649, 1576, 1.29(d,J=6.2Hz, 3H), 1.00
([M+H]+)
1529, 1503, (d,J=7.2Hz, 3H). 1481, 1452, calcd for
459 i¾ 1327, 1281, C25H25F2N2O5, 13CNMR(126 MHz,
1263, 1243, 471.1726; found, CDC13)5171.56, 168.54, 1212, 1146, 471.1726 162.05 (dd,J= 172.5, 11.9 1050, 966, Hz), 161.09- 159.28 (m), 849, 800, 155.35, 148.72, 140.42, 733, 699 140.02, 130.41, 130.23- 129.63 (m), 128.61, 128.18,
127.03, 124.46- 123.89 (m), 111.63 (d,J=21.2Hz),
109.41, 104.54- 103.81 (m), 72.76, 56.08, 49.36, 47.83, 18.90, 17.60.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.08 (d,J=0.6Hz, 1H), 8.33 (d,J=8.0Hz, 1H), 7.98
(d,J=5.2Hz, 1H), 7.26- 7.21 (m, 1H), 7.20-7.15 (m, 2H), 7.07-7.01 (m, 2H), 6.88-6.85 (m, 1H), 6.84- 6.74 (m, 2H), 5.86 - 5.72 (m,
(Thin film)
1H), 4.59-4.48 (m, 1H), 3370, 2983,
4.39(d,J=9.9Hz, 1H), 3.94 2937, 1737,
HRMS-ESI (m/z) (s, 3H), 2.26 (s, 3H), 1.28 (d, 1649, 1576,
([M+H]+) J=6.3Hz, 3H), 1.04 (d,J= 1529, 1502,
«\ 7.2 Hz, 3H).
1481, 1452, calcd for
460
1439, 1329, C26H27F2N2O5,
13CNMR(126 MHz, 1281, 1264, 485.1883; found,
CDC13)5171.55, 168.53, 1243, 1211, 485.1880
161.99 (dd,J= 171.0, 11.9 1147, 1050,
Hz), 160.02 (dd,J= 170.8, 966, 849,
11.7 Hz), 155.36, 148.72, 801, 732
140.41, 136.92, 136.63, 130.43, 129.97- 129.69
(m), 129.24, 128.06, 124.73
- 124.42 (m), 111.58 (d,J= 17.7 Hz), 109.40, 104.83 - 103.37 (m), 72.82, 56.08,
48.91, 47.85, 20.95, 18.90,
17.67.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 12.05 (d,J=0.6Hz, 1H), 8.30(d,J=8.0Hz, 1H), 7.98
(d,J=5.2Hz, 1H), 7.31- 7.17 (m, 3H), 6.97-6.75 (m,
5H), 5.83 - 5.73 (m, 1H),
(Thin film)
4.59 - 4.49 (m, 1H), 4.40 (d, 3371,2984,
J= 10.0 Hz, 1H), 3.95 (s, 2939, 1738,
3H), 1.28 (d,J=6.1Hz, 1649, 1604, HRMS-ESI (m/z)
3H), 1.08 (d,J=7.2Hz, 1577, 1529, ([M+H]+)
3H).
1503, 1481,
calcd for
461 i¾ 1452, 1439,
C25H24F3N2O5, 13CNMR(126 MHz, 1326, 1281,
489.1632; found, CDC13)5171.51, 168.59, 1264, 1242,
489.1624 162.96- 162.09 (m), 161.43 1223, 1160,
- 159.21 (m), 155.41, 1050, 966,
148.74, 140.45, 135.75, 849, 810,
130.33, 129.73 (d,J= 8.0 732
Hz), 124.13 (dd,J= 15.2, 3.7Hz), 115.43 (d,J=21.3 Hz), 111.73 (d,J=25.0Hz), 109.46, 104.30 (t,J= 25.8 Hz), 72.66, 56.10, 48.70, 47.86, 18.91, 17.67.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.28 (d,J=5.4Hz, 1H), 8.14(d,J=7.8Hz, 1H), 7.26 -7.15(m, 4H), 6.94 (dddd,J = 24.3, 8.7,6.9, 2.1Hz, 5H), 5.76-5.63 (m, 3H), 4.55 (p, J=7.3Hz, 1H),4.05 (d,J=
8.9 Hz, 1H),3.92 (s, 3H), 2.06 (s, 3H), 1.32 (d,J=7.1
HRMS-ESI (m/z)
Hz, 3H), 1.22 (d,J=6.2Hz, ([M+H]+)
3H).
calcd for
462
C28H29F2N2O7, 13CNMR(101 MHz, 543.1931; found, CDC13)5171.92, 170.28, 543.1937. 162.91, 162.81, 162.77,
160.46, 160.37, 145.63, 144.13, 142.28, 136.93, 136.90, 136.54, 136.51, 129.82, 129.74, 129.70, 129.62, 115.72, 115.51, 115.43, 115.22, 109.60, 89.60, 73.10,56.20,55.58, 48.04, 20.85,20.81, 18.94,
18.05.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.20(d,J=7.9Hz, 1H), 7.28 -7.17(m, 4H), 7.02-6.89 (m, 5H), 5.76- 5.66 (m, 3H), 4.55 (p,J=7.3Hz, 1H), 4.04 (d,J=9.7Hz, 1H), 3.90 (s, 3H), 2.05 (s, 3H), 1.23 (d,J=6.1Hz,
HRMS-ESI (m/z)
3H), 0.99 (d,J=7.2Hz, ([M+H]+)
3H).
calcd for
463
C28H29F2N2O7, 13CNMR(101 MHz, 543.1931; found, CDC13)5172.24, 170.26, 543.1937. 162.95, 162.90, 162.86,
160.51, 160.42, 160.28, 145.68, 143.98, 142.41, 136.94, 136.91, 136.86, 136.82, 129.62, 129.57, 129.54, 129.49, 115.79, 115.58, 115.49, 115.28, 109.58, 89.51,73.04, 56.18, 56.13,48.05,20.85, 19.14,
17.81.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.3Hz, 1H), 8.21 (d,J=7.9Hz, 1H), 7.26 -7.22(m, 1H), 7.14 (dd, J = 8.6, 5.8 Hz, 1H), 6.94 (d,J = 5.4 Hz, 1H), 6.89- 6.77 (m, 4H), 5.73 (s, 2H), 5.62 (dq, J = 9.7, 6.2 Hz, 1H), 4.56 (p, J = 7.2 Hz, 1H), 4.44 (d,J= 9.8 Hz, 1H),3.91 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H), 2.06 (s, 3H), 1.30 (d,J= 6.2 Hz, 3H), 1.04 (d,J=7.2Hz,
3H).
HRMS-ESI (m/z)
13CNMR(101 MHz,
(Thin film) ([M+H]+)
CDC13)5172.30, 170.26, 3378, 2984,
calcd for 162.91, 161.19 (d,J= 245.6
464 1738, 1676,
C30H33F2N2O7, Hz), 161.10 (d,J= 245.0 1496, 1202,
571.2250; found, Hz), 160.28, 145.70, 143.98, 1003, 729
571.2265 142.43, 139.12 (d,J= 7.4
Hz), 138.81 (d,J=7.5Hz), 134.89 (d,J=3.3Hz), 134.39 (d,J= 3.2 Hz), 129.37 (d,J= 8.2 Hz), 128.75 (d,J=8.3Hz), 117.41 (d,J=20.9Hz), 117.10(d,J=20.9Hz), 112.94 (d,J=20.9Hz), 112.63 (d,J=20.8Hz), 109.59, 89.52, 74.29, 56.19, 48.07, 46.40, 20.86, 20.20, 20.12, 18.82, 17.86.
19F NMR (376 MHz, CDC13) δ -116.57, -117.03.
Figure imgf000395_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.22(d,J=7.8Hz, 1H), 7.28 -7.19(m, 4H), 7.16-7.06 (m,4H), 6.93 (d,J=5.4Hz, 1H), 5.78 (dq,J=10.2, 6.1 Hz, 1H), 5.72 (d,J=0.9Hz, 2H), 4.51 (p,J=7.2Hz, 1H), 3.98 (d,J= 10.2 Hz, 1H), 3.89 (s, 3H), 2.81 (dh, J
HRMS-ESI (m/z)
(Thin film) = 10.6, 6.9 Hz, 2H), 2.05 (s,
([M+H]+)
3378, 2959, 3H), 1.24 (d,J=6.1Hz, 1737, 1676, calcd for 3H), 1.18 (dd,J= 13.6, 6.9
466
1506, 1202, C34H43N2O7, Hz, 12H), 0.81 (d,J=7.2 1044, 1004, 591.3065; found, Hz, 3H).
828, 731 591.3077
13CNMR(101 MHz, CDC13)5172.42, 170.24, 162.85, 160.24, 147.29, 147.13, 145.69, 143.92, 142.63, 139.19, 138.71, 127.95, 127.92, 126.75, 126.48, 109.49, 89.55, 73.66, 57.39,56.16, 48.05,33.65, 33.61,23.99, 23.97, 23.93, 20.86, 19.33, 17.57.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.27 (d,J=5.3Hz, 1H), 8.23 (d,J=7.8Hz, 1H), 7.07 -6.90 (m, 7H), 5.82-5.67 (m, 3H), 4.54 (p,J=7.2Hz, 1H),3.90 (s, 3H), 2.17 (t,J = 11.4 Hz, 12H), 2.06 (s, 3H),
HRMS-ESI (m/z) 1.28- 1.20 (m, 4H), 0.93 (d,
(Thin film)
([M+H]+) J=7.2Hz, 3H).
3388, 2979,
«\ 1756, 1677, calcd for
467 13CNMR(101 MHz,
1503, 1203, C32H39N2O7,
CDC13) 5172.41, 170.25, 1044, 1004, 563.2752; found,
162.84, 160.23, 145.69, 970, 731 563.2764
143.90, 142.67, 139.25, 139.11, 136.78, 136.34, 134.93, 134.51, 129.90, 129.62, 129.39, 129.38, 125.30, 125.08, 109.48, 89.55,73.49,57.11,56.16, 48.12, 20.86, 19.87, 19.80, 19.32, 19.29, 19.24, 17.80.
1H NMR (400 MHz, CDC13) 58.41 (d,J=7.7Hz, 1H), 8.30(d,J=5.4Hz, 1H), 7.32 -7.21 (m, 1H), 7.14(dd,J = 8.5, 5.8 Hz, 1H), 6.99 (d,J = 5.5 Hz, 1H), 6.83 (ddd,J = 15.6, 10.1, 7.6 Hz, 4H), 5.62
ESIMSw/z 541.2
(dq,J= 9.6, 6.1Hz, 1H), ([M+H]+)
468 4.62- 4.50 (m, 1H), 4.43 (d,
J=9.7Hz, 1H), 3.88 (s, 3H),
2.38 (s, 3H), 2.36 (s, 3H), 2.31 (s, 3H), 1.29 (d,J=6.2 Hz, 3H), 1.03 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) 5-116.52, -116.96. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.43 (d,J=7.9Hz, 1H), 8.32(d,J=5.4Hz, 1H), 7.26 (d,J=12.1Hz, 8H), 6.98 (d, J=5.4Hz, 1H), 5.78 (dq,J= 10.1, 6.1Hz, 1H), 4.56- 4.43 (m, 1H), 3.97 (d,J= 10.2 Hz, 1H), 3.88 (s, 3H),
HRMS-ESI (m/z)
2.37 (s, 3H), 1.25 (d,J=
(Thin film) ([M+H]+)
12.6 Hz, 21H), 0.77 (d,J= 3379, 2962,
calcd for 7.2 Hz, 3H).
469 Si 1772, 1677,
C35H45N206,
1508, 1198,
589.3272; found, 13CNMR(101 MHz, 731
589.3289 CDC13)5172.32, 168.88,
162.23, 159.40, 149.55, 149.37, 146.64, 141.60, 138.76, 138.25, 137.43, 127.70, 127.65, 125.60, 125.32, 109.67, 73.75, 57.22, 56.25,47.81,34.35,34.31, 31.31,31.30, 20.73, 19.32,
17.69.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.42 (d,J=7.6Hz, 1H), 8.32(d,J=5.5Hz, 1H), 7.22
(dd,J=8.3,2.5Hz,4H), 7.15- 7.04 (m, 4H), 6.98 (d, J=5.5Hz, 1H), 5.78 (dq,J= 10.1, 6.1Hz, 1H), 4.54- 4.43 (m, 1H), 3.97 (d,J= 10.2 Hz, 1H), 3.89 (s, 3H),
HRMS-ESI (m/z) 2.82 (dp,J= 11.9, 6.9 Hz,
(Thin film)
([M+H]+) 2H),2.37(s, 3H), 1.23 (d,J 3379, 2960,
= 6.2 Hz, 3H), 1.18(dd,J= 1772, 1677, calcd for
470 14.7, 6.9 Hz, 12H), 0.80 (d,J
1509, 1201, C33H4iN206,
= 7.2 Hz, 3H).
1175, 1047, 561.2959; found,
731 561.2977
13CNMR(101 MHz, CDC13)5172.31, 168.89, 162.23, 159.41, 147.28,
147.13, 146.64, 141.61,
139.14, 138.70, 137.43, 127.96, 127.92, 126.75,
126.47, 109.68, 73.70, 57.36, 56.25,47.83,33.64,33.61, 23.97, 23.93,20.74, 19.31,
17.75.
1H NMR (400 MHz, CDC13) δ 8.48 - 8.37 (m, 1H), 8.32
(Thin film) HRMS-ESI (m/z)
(d,J=5.4Hz, 1H), 7.09- 3379, 2978, ([M+H]+)
6.90 (m, 7H), 5.74 (dq,J = 1771, 1676,
calcd for 10.0, 6.1Hz, 1H), 4.58-
471 1505, 1450,
C3iH37N206, 4.46 (m, 1H), 3.98-3.83 (m, 1310, 1199,
533.2646; found, 4H), 2.38 (s, 3H), 2.17 (dd, J 1050, 907,
533.2659 = 12.4, 11.0 Hz, 12H), 1.22 730
(d,J=6.1Hz, 3H), 0.92 (d, 7=7.1 Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H),
8.22(d,J=7.9Hz, 1H), 7.38
HRMS-ESI (m/z) (m, 1H), 7.13(m, 1H), 6.94 ([M+H]+) (d,J=5.4Hz, 1H), 6.61-
(Thin film)
6.47 (m, 4H), 5.87 (dq,J = 3382, 2982, calcd for
472 9.7, 6.2 Hz, 1H), 5.72 (s,
1737, 1677, C30H33F2N2O9,
2H), 4.84 (d,J=9.6Hz, 1501, 1202 603.2149; found,
1H), 4.64 - 4.48 (m, 1H), 603.2163
3.90 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H),
1.22(d,J=6.2Hz, 3H), 1.03 (d,J=7.2Hz, 3H).
1H NMR (400 MHz, CDC13)
HRMS-ESI (m/z) 58.77- 8.42 (m, 1H), 8.42-
(Thin film) ([M+H]+) 8.15 (m, 1H), 7.26-7.15 (m, 3367, 2985, 4H), 7.06-6.86 (m, 5H), calcd for
473 s 1749, 1694, 5.84- 5.66 (m, 3H), 5.37- C28H26F5N2O7,
1506, 1201, 5.19 (m, 1H), 4.13-4.03 (m,
597.1655; found,
1130, 828 1H), 4.04-3.83 (m, 3H),
597.1672
2.09- 1.99 (m, 3H), 1.30- 1.16 (m, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) 58.28(t,J=7.2Hz, 2H), 7.35- 7.12 (m, 10H), 6.94 (d,J=5.4Hz, 1H), 5.86 (q, J=6.3Hz, 1H), 5.75-5.68 (m,2H), 4.62 (p,J=7.2Hz,
1H), 3.90 (s, 3H), 2.06 (s,
HRMS-ESI (m/z)
3H), 1.75 (s, 3H), 1.16 (d, J ([M+H]+)
= 6.3 Hz, 3H), 1.12 (d,J= calcd for 7.2 Hz, 3H).
474
C29H33N2O7,
521.2282; found, 13CNMR(101 MHz, 521.2292. CDC13)5172.27, 170.20,
162.88, 160.26, 146.57, 145.66, 145.11, 143.98, 142.56, 128.18, 128.09, 127.92, 127.40, 126.28, 126.11, 109.53, 89.54, 75.94, 56.17, 50.41,48.23,23.95, 20.84, 18.13, 15.97.
1H NMR (400 MHz, CDC13) 58.41 (d,J=4.6Hz, 1H),
8.31 (d,J=5.4Hz, 1H), 7.37 (dd,J=8.5, 6.7 Hz, 1H), 7.12 (dd,J= 8.3, 6.7 Hz,
(Thin film)
HRMS-ESI (m/z) 1H), 6.99 (d,J=5.5Hz, 3379, 2940,
([M+H]+) 1H), 6.63 - 6.44 (m, 4H), 1769, 1736,
5.86 (dq,J=9.5, 6.2 Hz, 1677, 1598, calcd for
475 1H), 4.83 (d,J=9.5Hz,
1500, 1277, C29H31F2N2O8,
1H), 4.62 - 4.45 (m, 1H), 1192, 1174, 573.2043; found,
3.90 (s, 3H), 3.82 (s, 3H), 1151, 1033, 573.2055
3.73 (s, 3H), 2.38 (s, 3H), 953
1.21 (d,J=6.2Hz, 3H), 1.01 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.49, -113.81. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1 : 1 mixture of diastereomers. 1H NMR (500 MHz, CDC13)
(Thin film)
58.52- 8.46 (m, 1H), 8.20 3382, 3028, HRMS-ESI (m/z)
(d,J=7.6Hz, 1H), 8.16 (d, 2984, 1736, ([M+H]+)
J=7.5Hz, 1H), 7.33-7.10 1677, 1498,
calcd for (m, 11H), 5.86- 5.74 (m,
476 1451, 1436,
C28H31N2O7, 3H), 4.61-4.48 (m, 1H), 1310, 1201,
507.2126; found, 4.10- 4.04 (m, 1H), 4.02 (s, 1043, 967,
507.2141 3H), 2.06 (s, 3H), 2.05 (s, 910, 829,
3H), 1.31 (d,J=7.1Hz, 728, 703
3H), 1.28- 1.20 (m, 3H), 0.91 (d,J=7.2Hz, 3H).
1H NMR (400 MHz, CDC13) 58.30(d,J=5.5Hz, 1H), 7.60(d,J=8.3Hz, 2H), 7.54
HRMS-ESI (m/z)
(d,J=8.3Hz, 2H), 7.41-
(Thin film) ([M+H]+)
7.30 (m,4H), 7.03 (d,J=5.5 * 3376, 2985,
calcd for Hz, 1H), 5.76 (dq,J=8.8,
477 2228, 1769,
C29H27N4O6, 6.1Hz, 1H), 4.60- 4.52 (m, 1738, 1674,
527.1925; found, 1H), 4.20 (d,J=9.0Hz, 1505
527.1931 1H), 3.95 (d,J=9.9Hz,
1H), 3.92 (s, 3H), 2.39 (s, 3H), 1.25 (d,J=6.2Hz, 3H), 1.08 (d,J=7.2Hz, 3H)
1H NMR (400 MHz, CDC13)
58.38 (d,J=7.9Hz, 1H), 8.32- 8.29 (m, 1H), 7.56 (d,
HRMS-ESI (m/z)
J=7.9Hz,2H),7.52 (d,J=
(Thin film) ([M+H]+)
8.5 Hz, 2H), 7.44- 7.36 (m, 3387, 2986,
calcd for 4H),7.01 (dd,J=5.5,3.5
478 1772, 1739,
C29H27F6N2O6, Hz, 1H), 5.88 - 5.79 (m, 1677, 1617,
613.1768; found, 1H), 4.59-4.53 (m, 1H), 1509
613.178 4.22(d,J=9.2Hz, 1H), 3.90
(s, 3H), 2.38 (s, 3H), 1.28- 1.22 (m, 3H), 0.98 (d,J=7.2
Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDCI3) 58.38 (d,J=8.7Hz, 1H), 8.32- 8.29 (m, 1H), 7.97 (d, J= 8.3 Hz, 2H), 7.93 (d,J=
HRMS-ESI (m/z) 8.2 Hz, 2H), 7.38 (d,J= 8.3 ([M+H]+) Hz, 2H), 7.34(d,J=8.4Hz,
(Thin film)
2H), 7.00 (d,J=5.5Hz, 3379, 2980, calcd for
479 1H), 5.85 (dq,J= 9.6, 6.1
1772, 1714, C33H37N2O10,
Hz, 1H), 4.59- 4.50 (m, 1678, 1508 621.2443; found,
1H), 4.38- 4.30 (m, 4H), 621.2451
4.21 (d,J=9.7Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.36 (t, J=7.3Hz, 6H), 1.25 (d,J=
6.3 Hz, 3H), 0.98 (d,J=7.1
Hz, 3H).
1H NMR (400 MHz, CDC13) δ 8.28 - 8.24 (m, 1H), 8.20 (d,J=7.8Hz, 1H), 8.00- 7.92 (m,4H), 7.42-7.31 (m,
HRMS-ESI (m/z)
4H), 6.95 (d,J=5.4Hz, ([M+H]+)
(Thin film) 1H), 5.85 (dp, J= 9.4, 7.2, 3379, 2983, calcd for 6.6 Hz, 1H), 5.73- 5.67 (m,
480
1714, 1676, C34H39N2O11, 2H), 4.56(p,J=6.9Hz, 1607, 1507 651.2548; found, 1H), 4.39 - 4.28 (m, 4H),
651.2560 4.22(d,J=9.7Hz, 1H), 3.91
(d,J= 1.5 Hz, 3H), 2.06 (s, 3H), 1.37(t,J=7.2Hz, 6H), 1.27(d,J=6.2Hz, 3H), 0.98 (d,J=7.1Hz, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.22(d,J=7.9Hz, 1H), 7.34 (d,J=8.3Hz, 1H), 7.09 (d, J=8.0Hz, 1H),6.94 (d,J= 5.4 Hz, 1H), 6.88- 6.82 (m,
(Thin film) HRMS-ESI (m/z)
2H),6.81 (s, 1H),6.76 (d,J
3379, 2939, ([M+Na]+) calcd for
= 2.0 Hz, 1H), 5.86 (dq,J=
481 1737, 1677, C3oH32Cl2N2Na09,
9.7, 6.2 Hz, 1H), 5.72 (s, 1490, 1247, 657.1377; found,
2H), 4.84 (d,J=9.6Hz, 1202, 1033 657.1387
1H), 4.57(p,J=7.2Hz, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H), 1.22 (d,J=6.2Hz, 3H), 1.04 (d,J=7.2Hz,
3H).
1H NMR (400 MHz, CDC13) 58.25 (t,J=6.6Hz, 2H), 7.34 (dd,J=8.5, 6.9 Hz, 1H), 7.13 (td,J= 7.9, 6.7, 4.7 Hz, 1H), 6.93 (d,J=5.4
Hz, 1H), 6.60- 6.36 (m,
HRMS-ESI (m/z)
(Thin film) 4H), 5.90 (dq,J=10.2, 6.2
([M+H]+)
3380, 2981, Hz, 1H), 5.73 (s, 2H), 4.83 1736, 1677, calcd for (d,J= 10.1 Hz, 1H), 4.63-
482
1597, 1500, C32H37F2N209, 4.48 (m, 1H), 4.08- 3.79 (m, 1274, 1202, 631.2462; found, 7H), 2.06 (s, 3H), 1.47 (t, J = 1003 631.2461 6.9 Hz, 3H), 1.40 (t, J =6.9
Hz, 3H), 1.23 (d,J=6.2Hz, 3H), 1.04 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -113.76, -114.20. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.29- 8.19 (m, 2H), 7.31 (d,J=8.3Hz, 1H), 7.11 (d, J=8.2Hz, 1H),6.94 (d,J=
HRMS-ESI (m/z) 5.4 Hz, 1H), 6.86-6.73 (m,
(Thin film)
([M+H]+) 3H), 6.72 (d,J=2.0Hz, 3378, 2980,
1H), 5.89 (dq,J=9.9,6.2 1736, 1677, calcd for
483 Hz, 1H), 5.73 (s, 2H), 4.83
1591, 1491, C32H37CI2N2O9,
(d,J=9.8Hz, 1H), 4.57 (p, 1247, 1201, 663.1871; found,
J=7.2Hz, 1H), 4.05 -3.83 1040 663.1877
(m, 7H),2.06 (s, 3H), 1.47 (t, J=6.9Hz, 3H), 1.39 (t,J= 6.9 Hz, 3H), 1.23 (d,J=6.1 Hz, 3H), 1.06 (d,J=7.2Hz,
3H).
1H NMR (400 MHz, CDC13) 58.29- 8.18 (m, 2H), 7.30 (d,J=7.8Hz, 1H), 7.13 (d, J=7.7Hz, 1H),6.92 (d,J= 5.4 Hz, 1H), 6.67- 6.57 (m,
HRMS-ESI (m/z)
3H), 6.54 (s, 1H), 5.93 (dq, J
(Thin film) ([M+H]+)
= 10.3, 6.1 Hz, 1H), 5.72 (s, 3378, 2978,
calcd for 1H), 5.72 (s, 1H),4.90 (d,J
484 1758, 1734,
C34H43N2O9, = 10.1 Hz, 1H), 4.55 (p,J= 1676, 1504,
623.2963; found, 7.1Hz, 1H), 4.04-3.81 (m, 1200, 1043
623.2962 7H), 2.26 (s, 3H), 2.23 (s,
3H), 2.05 (d,J= 1.8 Hz, 3H), 1.47(t,J=7.0Hz, 3H), 1.39(t,J=7.0Hz, 3H), 1.23 (d,J=6.1Hz, 3H), 0.99 (d, J=7.2Hz, 3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 8.39 (d, 7= 6.9 Hz, 1H), 8.29(d,J=5.4Hz, 1H), 7.05 -6.92(m, 3H), 6.89 (dd,J = 8.1,2.1Hz, 1H), 6.82 (dddd,
HRMS-ESI (m/z)
7=15.8, 8.3, 4.0, 2.1 Hz, ([M+H]+)
3H), 5.72 (dq, 7= 9.7, 6.1 calcd for Hz, 1H), 4.65 - 4.48 (m, 1H),
485
C29H31F2N2O8, 3.99 (d, 7= 9.8 Hz, 1H), 3.88 573.2051; found, (s, 3H),3.85 (s, 6H), 2.38 (s, 573.2044 3H), 1.24 (d, 7= 6.1 Hz,
3H), 1.02 (d, 7= 7.1 Hz,
3H).
19F NMR (376 MHz, CDC13) δ -137.20, -137.68.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.43 (d,J=7.8Hz, 1H), 8.28(d,J=5.4Hz, 1H), 7.21
(d,J=8.5Hz, 1H), 7.17- 7.09 (m, 1H), 6.96 (d,J=5.5 Hz, 1H), 6.79 - 6.57 (m, 4H), 5.63 (dq,J=9.7, 6.1Hz, 1H), 4.64 - 4.50 (m, 1H), 4.38 (d,J=9.9Hz, 1H), 3.86 (s, 3H),3.73 (s, 3H), 3.71 (s,
HRMS-ESI (m/z)
3H), 2.38 (s, 3H), 2.35 (s, ([M+H]+)
3H),2.31 (s, 3H), 1.29 (d,J calcd for = 6.1 Hz, 3H), 1.01 (d,J=
486
C31H37N2O8, 7.1Hz, 3H).
565.2542; found,
565.2535 13CNMR(101 MHz,
CDC13) 5172.25, 168.81, 162.28, 159.43, 157.80, 157.67, 146.63, 141.55, 137.98, 137.71, 137.44, 131.95, 131.46, 128.85, 128.22, 116.24, 116.03, 111.25, 110.94, 109.75, 74.80, 56.24, 55.05, 47.92, 46.23,20.71,20.36, 20.28, 18.88, 18.08.
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.21 (d,J=7.8Hz, 1H), 7.06
- 6.92 (m, 3H), 6.92 - 6.74
HRMS-ESI (m/z)
(m,4H), 5.84-5.61 (m, 3H), ([M+H]+)
4.56 (p,J=7.3Hz, 1H), 4.00 calcd for (d,J=9.8Hz, 1H), 3.91 (s,
487
C30H33F2N2O9, 3H), 3.86 (s,6H), 2.06 (s, 603.2157; found, 3H), 1.25 (d,J=6.2Hz, 603.2150 3H), 1.02 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) 5-137.20, -137.72. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 58.44 (s, 1H), 8.31 (d,J=
5.4 Hz, 1H), 7.33 (d,J=8.5
Hz, 1H), 7.10(d,J=8.4Hz,
HRMS-ESI (m/z)
(Thin film) 1H), 6.98 (d,J=5.5Hz,
([M+H]+)
3383,2938, 1H), 6.42 - 6.34 (m, 4H), 2837, 1770, calcd for 5.85 (dq,J=9.7, 6.2 Hz,
488
1733, 1677, C31H37N2O10, 1H), 4.81 (d,J=9.8Hz, 1609, 1586, 597.2443; found, 1H), 4.59-4.49 (m, 1H), 1505, 1453 597.2438 3.90 (s, 3H), 3.82 (s, 3H),
3.75 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H),
1.21 (d,J=6.2Hz, 3H), 0.99 (d,J=7.2Hz, 3H).
1H NMR (500 MHz, CDC13) 58.44 (s, 1H), 8.31 (d,J= 5.4 Hz, 1H), 7.31 (d,J=7.7 Hz, 1H), 7.10(d,J=8.1Hz, 1H), 6.98 (d,J=5.5Hz,
HRMS-ESI (m/z)
1H), 6.69 - 6.65 (m, 1H),
(Thin film) ([M+H]+)
6.65 - 6.62 (m, 2H), 6.60 - 3382, 2937,
calcd for 6.54 (m, 1H), 5.89 (dq,J =
489 1771, 1733,
C31H37N2O8, 9.8, 6.2 Hz, 1H),4.90 (d,J = 1677, 1572,
565.2544; found, 9.8 Hz, 1H), 4.58- 4.48 (m, 1505, 1452
565.2541 1H), 3.90 (s, 3H), 3.82 (s,
3H), 3.73 (s, 3H), 2.38 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.21 (d,J=6.2Hz, 3H), 0.95 (d,J=7.2Hz,
3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 58.45 (s, IH), 8.32 (d,J = 5.4 Hz, IH), 7.22 (d,J=2.1 Hz, IH), 7.03 (d,J=2.2Hz,
IH), 6.98 (d,J=5.5Hz, 1H),6.93 (ddd,J=8.3,2.3,
HRMS-ESI (m/z)
0.8 Hz, IH), 6.89 (ddd,J =
(Thin film) ([M+H]+)
8.2, 2.2, 0.8 Hz, IH), 6.73 (d, 3383,2937,
calcd for J=8.3Hz, 1H),6.67 (d,J=
490 2836, 1772,
C31H37N2O8, 8.2 Hz, IH), 5.85 (dq,J = 1735, 1678,
565.2544; found, 10.0, 6.2 Hz, IH), 4.95 (d,J 1502, 1453
565.2538 = 10.0 Hz, IH), 4.58-4.46
(m, IH), 3.90 (s, 3H), 3.82 (s, 3H),3.72 (s, 3H),2.38(s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.22 (d,J=6.1Hz, 3H), 0.95 (d,J=7.1Hz,
3H).
1H NMR (500 MHz, CDC13) for both isomers of a 1 : 1 mixture of diastereomers d 8.40 (s, IH), 8.38 (s, IH), 8.32(d,J=5.0Hz, IH), 8.31
(d,J=5.3Hz, IH), 7.21-
HRMS-ESI (m/z) 7.13 (m,2H), 7.03 - 6.83 (m,
(Thin film)
([M+H]+) 12H), 5.76-5.63 (m, 2H), 3382, 2985,
5.04 (d,J= 11.9 Hz, IH), 2941,2840, calcd for
491 5.02 (d,J= 11.2 Hz, IH),
1771, 1736, C29H31F2N2O8,
4.63- 4.47 (m, 2H), 3.93 (d, 1677, 1578, 573.2043; found,
J=2.0Hz, 3H), 3.92 (s, 3H), 1508, 1479 573.2042
3.91- 3.89 (m, 6H), 3.80 (d, J=1.7Hz, 3H),3.76 (d,J=
1.6 Hz, 3H),2.39(s, 3H), 2.38 (s, 3H), 1.31 (d,J=7.2 Hz, 3H), 1.29- 1.22 (m, 6H), 1.03 (d,J=7.2Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) for the major isomer of a 2: 1 mixture of diastereomers d 8.44 (s, 1H), 8.32 (d, 7= 5.5
Hz, 1H), 7.18 (dd, 7= 9.7,
HRMS-ESI (m/z) 3.0 Hz, 1H), 6.99 (d, 7= 5.5
(Thin film) ([M+H]+) Hz, 1H), 6.96 (dd, 7= 9.5,
*vs 3383, 2941, 3.0 Hz, 1H), 6.87 - 6.79 (m, calcd for
492 2839, 1770, 2H), 6.76 (dd, 7= 9.0, 4.6
1736, 1677,
Figure imgf000410_0001
Hz, 1H), 6.72 (d, 7= 4.6 Hz,
573.2043; found,
1592, 1495 1H), 5.87 (dq, 7= 9.6, 6.2
573.2045
Hz, 1H), 4.88 (d, 7= 9.6 Hz,
1H), 4.60 - 4.53 (m, 1H),
3.90 (s, 3H), 3.83 (s, 3H),
3.74 (s, 3H), 2.38 (s, 3H), 1.23 (d, 7= 6.2 Hz, 3H), 1.02 (d, 7= 7.2 Hz, 3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) for 1 : 1 mixture of diastereomers δ 8.26 (t, J = 5.1Hz, 4H), 7.07 (ddd,J = 13.9, 7.9, 1.1 Hz, 2H), 7.00- 6.89 (m,6H), 6.85(td,J = 8.8, 8.0, 1.3 Hz, 2H), 6.78- 6.72 (m, 4H), 5.75 - 5.71 (m, 4H), 5.71 - 5.62 (m, 2H), 5.12(dd,J= 13.7, 9.8 Hz, 2H), 4.63 - 4.47 (m, 2H), 3.91 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.06 (s, 6H), 1.32 (d,J=7.1 Hz, 3H), 1.26 (d,J=6.0Hz,
HRMS-ESI (m/z)
3H), 1.24 (d,J=6.2Hz, ([M+H]+)
3H), 1.00 (d,J=7.2Hz, calcd for 3H).
493 **
C32H39N2O11,
627.2548; found, 13CNMR(126 MHz, 627.2546 CDCl3)for 1:1 mixture of diastereomers δ 172.36, 171.98, 170.28, 162.82, 162.78, 160.26, 160.23, 152.82, 152.78, 152.71, 147.42, 147.31, 147.19, 147.11, 145.68, 143.95, 143.93, 142.70, 142.64, 135.14, 134.87, 134.78, 134.61, 123.66, 123.62, 121.05, 120.97, 120.46, 120.33, 110.74, 110.61, 110.55, 109.44, 99.98, 89.63, 89.59, 73.81,73.75,60.40, 60.36, 60.31,60.25,56.17, 56.16, 55.64, 55.59, 48.18, 48.12,41.96,41.83,29.28, 20.88, 18.86, 18.71, 18.41,
17.91. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) for 1 : 1 mixture of diastereomers δ 8.40 - 8.28 (m, 2H), 8.26 (dd,J=5.3, 3.7 Hz, 2H), 7.07 (ddd,J = 13.1,8.0, 1.2 Hz, 2H), 7.03- 6.89 (m,6H), 6.88- 6.80 (m, 2H), 6.75 (td,J= 5.6, 2.8 Hz, 4H), 5.81 -5.72 (m, 4H), 5.72-5.62 (m, 2H), 5.12(dd,J= 13.4, 9.8 Hz, 2H),4.54 (dp, J= 17.6, 7.2 Hz, 2H), 3.89 (s, 3H), 3.89 (s, 3H),3.88 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.54 (pd,J= 7.0, 4.2 Hz, 2H), 1.32(d,J=7.1Hz, 3H), 1.26 (d,J=6.1Hz,
HRMS-ESI (m/z)
3H), 1.24 (d,J=6.2Hz, ([M+H]+)
3H), 1.14(d,J=3.1Hz, calcd for 6H), 1.13 (d,J=3.1Hz,
494
C34H43N2O11, 6H), 1.00 (d,J=7.2Hz, 655.2861; found, 3H).
655.2858
13CNMR(126 MHz, CDCl3)for 1:1 mixture of diastereomers δ 176.26, 176.24, 172.37, 171.99, 162.79, 162.73, 160.25,
160.21, 152.82, 152.78, 152.70, 147.42, 147.32, 147.19, 147.11, 145.53,
144.22, 144.16, 142.27, 135.14, 134.88, 134.79, 134.62, 123.66, 123.62, 121.06, 120.97, 120.47, 120.33, 110.76, 110.74, 110.61, 110.55, 109.39,
99.98, 90.02, 89.95, 73.79, 73.73,60.40, 60.36, 60.31, 60.26, 56.12, 56.10, 55.64, 55.59, 48.18, 48.12,41.96, 41.82,33.87,33.85, 18.85, 18.68, 18.41, 17.91.
Figure imgf000413_0001
Figure imgf000414_0001
Figure imgf000415_0001
Figure imgf000416_0001
Figure imgf000417_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.42 (s, 1H), 8.31 (d,J=
5.5 Hz, 1H), 7.18 (d,J=7.9
Hz, 1H), 7.12(d,J=8.6Hz, 1H), 6.98 (d,J=5.5Hz, 1H), 6.96-6.85 (m, 4H), 5.66 (dq,J=9.9, 6.2 Hz, 1H), 4.57-4.48 (m, 1H), 4.43 (d,J= 10.0 Hz, 1H),
(Thin film)
3.90 (s, 3H), 2.38 (s, 3H), 3384, 2938, HRMS-ESI (m/z)
2.34 (s, 3H), 2.30 (s, 3H), 1771, 1735, ([M+H]+)
2.25 (s, 3H), 2.21 (s, 3H), 1677, 1505,
calcd for 1.28 (d,J=6.1 Hz, 3H), 0.96
500 S 1451, 1309,
C3iH37N206, (d,J=7.1Hz, 3H). 1198, 1174,
533.2646; found,
1100, 1043,
533.2642 13CNMR(126 MHz, 908, 804,
CDC13) δ 172.30, 168.92, 730
162.24, 159.41, 146.64, 141.59, 137.43, 136.50, 136.40, 136.19, 136.10, 135.84, 135.52, 131.49, 131.15, 127.76, 127.14, 126.81, 126.59, 109.67,
74.83, 56.27, 47.89, 46.82,
20.84, 20.81, 20.76, 20.13, 20.07, 18.92, 18.03.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.43 (d,J=7.9Hz, 1H), 8.32(d,J=5.4Hz, 1H), 7.13 -6.98(m, 4H), 6.91 (dd,J = 10.3, 2.8 Hz, 1H), 6.81 (dtd, J= 12.5, 8.2, 2.7 Hz, 2H), 5.57 (dq,J=9.6, 6.1Hz, 1H), 4.61-4.51 (m, 1H), 4.46(d,J=9.6Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.34 (s, 3H),2.29 (s, 3H), 1.32 (d,J
(Thin film) = 6.2 Hz, 3H), 1.02 (d,J= 3379, 2983, HRMS-ESI (m/z) 7.2 Hz, 3H).
1770, 1738, ([M+H]+)
1677, 1496, 13CNMR(126 MHz,
S calcd for
501 1453, 1310, CDC13)5172.15, 168.90,
1199, 1176,
Figure imgf000419_0001
162.31, 161.35 (d,J= 243.7
541.2145; found,
1148, 1043, Hz), 159.42, 146.68,
541.2146
909, 808, 141.44, 140.63 (d,J= 6.5 729 Hz), 140.14(d,J=6.7Hz),
137.47, 132.40 (d,J= 3.1 Hz), 132.06 (d,J=2.0Hz), 132.01 (d,J=3.1 Hz), 131.69 (d,J=7.8Hz), 114.83 (d,J=22.2Hz), 114.37 (d,J= 22.3 Hz), 113.65 (d,J=20.8Hz), 113.37 (d,J= 20.6 Hz), 109.75, 74.02, 56.28, 47.77, 47.72, 20.75, 19.42, 19.35, 18.83, 18.00.
Figure imgf000420_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.42 (s, 1H), 8.32 (d,J = 5.4 Hz, 1H), 7.29 (t, J =8.7 Hz, 1H), 7.16(t,J=8.5Hz, 1H), 6.99 (d,J=5.5Hz, 1H), 6.65 - 6.55 (m, 3H), 6.51 (dd,J= 12.0, 2.6 Hz, 1H), 5.78 (dq,J= 12.1,6.2 Hz, 1H), 4.66- 4.52 (m, 2H), 3.90 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 2.38 (s,
(Thin film)
3H), 1.27 (d,J=6.2Hz, 3379, 2938,
HRMS-ESI (m/z) 3H), 1.06 (d,J=7.2Hz, 1770, 1736,
([M+H]+) 3H).
1676, 1623,
1585, 1506, calcd for
503 13CNMR(126 MHz,
1444, 1310, C29H31F2N2O8,
«i CDC13)5172.11, 168.91,
1195, 1175, 573.2043; found,
162.24, 161.24 (d,J= 245.7 1154, 1031, 573.2044
Hz), 161.01 (d,J= 245.9 907, 832,
Hz), 159.72 (d,J= 11.2 Hz), 803, 729
159.46 (d,J= 11.3 Hz), 159.44, 146.60, 141.51, 137.44, 129.90 (d,J= 5.4 Hz), 129.34 (d,J= 5.6 Hz), 119.60 (d,J= 14.6 Hz), 119.45 (d,J= 15.0 Hz), 110.13 (d,J=3.0Hz), 109.85- 109.61 (m), 101.99 - 101.44 (m), 72.26, 56.28, 55.50, 55.46, 47.88, 41.64, 20.75, 18.93, 18.13.
Figure imgf000422_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.42 (d,J=7.7Hz, 1H),
8.32(d,J=5.4Hz, 1H), 6.98
(d,J=5.5Hz, 1H), 6.45 (dd, J= 6.5, 2.3 Hz, 4H), 6.28 (dt,J= 17.4, 2.3 Hz, 2H), 5.74 (dq,J= 10.3,6.1 Hz, 1H), 4.59-4.48 (m, 1H),
HRMS-ESI (m/z)
(Thin film) 3.93 - 3.86 (m, 4H), 3.76 (s,
([M+H]+)
3375,2938, 6H), 3.74 (s, 6H), 2.38 (s, 1770, 1677, calcd for 3H), 1.28- 1.22 (m, 3H),
506 *ΐ
1593, 1203, C31H37N2O10, 0.97 (d,J=7.2Hz, 3H). 1152, 1064, 597.2443; found,
731 597.2442 13CNMR(101 MHz,
CDC13)5172.26, 168.86, 162.29, 160.95, 160.78, 159.43, 146.64, 143.47, 143.25, 141.64, 137.47, 109.69, 106.48, 106.26, 98.54, 98.44, 72.91,58.21, 56.26, 55.30, 55.28, 47.92, 20.73, 19.23, 18.01.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.42 (d,J=7.9Hz, 1H), 8.32(d,J=5.4Hz, 1H), 6.98 (d,J=5.5Hz, 1H), 6.69 (d, J= 1.5 Hz, 2H), 6.64 (dt,J= 4.2, 1.9Hz,2H),6.54(t,J= 1.9 Hz, 1H), 6.49 (t, J =1.9 Hz, 1H), 5.73 (dq,J= 10.3, 6.1Hz, 1H), 4.59- 4.47 (m, 1H), 3.89 (s, 4H), 3.75 (s,
HRMS-ESI (m/z) 3H), 3.73 (s, 3H), 2.38 (s,
(Thin film)
([M+H]+) 3H), 2.28 (s, 3H), 2.25 (s, 3384, 2939,
3H), 1.23 (d,J=6.1Hz, 1771, 1677, calcd for
507 3H), 0.93 (d,J=7.1Hz,
1593, 1508, C31H37N2O8,
3H).
1172, 1152, 565.2544; found,
1066, 732 565.2540
13CNMR(101 MHz, CDC13)5172.30, 168.86, 162.27, 159.77, 159.64, 159.43, 146.64, 142.75, 142.51, 141.67, 139.73, 139.31, 137.46, 121.35, 121.29, 112.68, 111.36, 110.95, 109.68, 73.23, 57.88, 56.26, 55.15, 55.13,47.91, 29.30,21.67,21.60, 20.73, 19.27, 17.96.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.40 (d,J=7.9Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.06 -6.94(m, 3H), 6.80 (ddd,J = 7.7,6.1, 1.7 Hz, 2H), 6.73 (dd,J= 14.2, 1.6Hz,2H), 5.79 (dq,J= 10.1,6.1 Hz, 1H), 4.60 - 4.47 (m, 1H), 3.96 (d,J= 10.1 Hz, 1H), 3.89 (s, 3H), 3.79 (s, 3H),
HRMS-ESI (m/z)
3.79 (s, 3H), 2.38 (s, 3H),
(Thin film) ([M+H]+)
2.14 (s, 3H), 2.11 (s, 3H),
¾· 3376, 2939,
calcd for 1.24(d,J=6.4Hz, 3H), 0.93
508 1771, 1678,
C31H37N2O8, (d,J=7.2Hz, 3H). 1508, 1201,
565.2544; found,
1040, 734
565.2538 13CNMR(101 MHz,
CDC13)5172.31, 168.86, 162.28, 159.44, 157.84, 157.65, 146.62, 141.65, 140.39, 140.28, 137.48, 130.75, 130.48, 125.19, 124.79, 119.76, 119.68, 109.94, 109.85, 109.69, 73.32, 57.89, 56.26, 55.29, 47.93,29.30, 20.73, 19.30, 17.97, 15.80, 15.75.
Figure imgf000426_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.50-8.35 (m, 1H), 8.31 (d,J=5.4Hz, 1H), 7.07 (d, J=3.0Hz, 1H),6.97 (d,J= 5.5 Hz, 1H), 6.87 (d,J=3.0 Hz, 1H), 6.80- 6.60 (m, 4H), 5.91 (dq,J=9.9,6.1 Hz, 1H), 4.93 (d,J= 10.0 Hz, 1H), 4.62 - 4.45 (m, 1H), 3.89 (s, 3H), 3.81 (s,
HRMS-ESI (m/z) 3H), 3.74 (s, 3H), 3.71 (s,
(Thin film)
([M+H]+) 3H), 3.70 (s, 3H), 2.38 (s, 3387, 2940,
3H), 1.23 (d,J=6.1Hz, 1771, 1678, calcd for
511 3H), 0.97 (d,J=7.1Hz,
1499, 1223, C31H37N2O10,
3H).
1046, 808, 597.2443; found,
732 597.2410
13CNMR(101 MHz, CDC13)5172.29, 168.87, 162.24, 159.40, 153.47, 153.45, 151.89, 151.77, 146.63, 141.73, 137.43, 130.69, 116.44, 115.43, 112.14, 112.11, 111.84, 111.55, 109.63, 73.04, 56.33, 56.29, 56.25, 55.68, 55.59, 47.96, 43.90, 29.30, 20.73, 18.91, 18.13.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.43 (d,J=8.0Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.05
(d,J=8.3Hz, 1H), 7.01- 6.94 (m,2H), 6.90 (d,J=2.7 Hz, 1H), 6.82 (d,J=2.7Hz, 1H), 6.63 (ddd,J= 18.7, 8.4, 2.7 Hz, 2H), 5.65 (dq,J = 10.1, 6.1Hz, 1H), 4.59- 4.49 (m, 1H), 4.45 (d,J= 10.0 Hz, 1H), 3.89 (s, 3H),
HRMS-ESI (m/z)
(Thin film) 3.73 (s, 3H), 3.73 (s, 3H),
([M+H]+)
3381,2939, 2.38 (s, 3H), 2.32 (s, 3H),
¾ 1771, 1677, calcd for 2.27 (s, 3H), 1.31 (d,J=6.1
512
1502, 1200, C31H37N2O8, Hz, 3H), 0.97 (d,J=7.1Hz, 1175, 1043, 565.2544; found, 3H).
731 565.2543
13CNMR(101 MHz, CDC13)5172.26, 168.85, 162.28, 159.43, 157.92, 157.89, 146.64, 141.63, 140.31, 139.86, 137.47, 131.43, 131.10, 128.88, 128.61, 114.65, 113.69, 111.27, 111.11, 109.70, 74.59, 56.26, 55.19, 47.90, 47.86, 29.30, 20.73, 19.29, 19.25, 18.90, 17.99.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDCI3) 58.27 (d,J=5.4Hz, 1H), 8.23 (d,J=7.8Hz, 1H), 6.94 (d,J=5.4 Hz, 1H), 6.60 (dddd,J= 13.2, 10.8,3.9,
(Thin film) HRMS-ESI (m/z) 1.8 Hz, 4H), 6.45 (ddt,J= 3381,2940, ([M+H]+) 13.9, 10.5, 2.3 Hz, 2H), 5.76 1740, 1675, -5.63 (m, 3H), 4.57 (p,J= calcd for
513 1592, 1505, 7.3 Hz, 1H), 3.95 (d,J=10.0
C30H33F2N2O9,
1200, 1134, Hz, 1H), 3.90 (s, 3H), 3.77
603.2149; found,
1045, 829, (s, 3H),3.75 (s, 3H),2.06 (s,
603.2137
730 3H), 1.26 (d,J=6.1Hz,
3H), 1.04 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -110.67, -111.20.
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.23 (d,J=7.8Hz, 1H), 6.93 (d,J=5.4Hz, 1H), 6.46 (dd, J=7.4, 2.2 Hz, 4H), 6.28 (dt,J= 16.6, 2.2 Hz, 2H), 5.81- 5.68 (m, 3H), 4.55 (p, J=7.2Hz, 1H), 3.96-3.86
(Thin film) HRMS-ESI (m/z)
(m,4H), 3.76 (s, 6H), 3.74 3382, 2937, ([M+H]+)
(s, 6H), 2.06 (s, 3H), 1.26 (d, 1737, 1675,
calcd for J=6.2Hz, 3H),0.99 (d,J=
514 3» 1593, 1457,
C32H39N2O11, 7.2 Hz, 3H).
1202, 1150,
627.2548; found,
1062, 829,
627.2555 13CNMR(101 MHz, 729
CDC13)5172.37, 170.22, 162.89, 160.96, 160.79, 160.25, 145.70, 143.93, 143.51, 143.26, 142.65, 109.51, 106.49, 106.24, 98.54, 98.43, 89.57, 72.87, 58.24, 56.17, 55.30, 55.28, 48.14, 20.85, 19.25, 17.84. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13)
58.27 (d,J=5.4Hz, 1H), 8.23 (d,J=7.8Hz, 1H), 6.93 (d,J=5.4Hz, 1H), 6.70 (s,
2H),6.65 (dt,J=5.7, 1.9 Hz, 2H), 6.55 (t,J= 1.7 Hz, 1H), 6.50 (t, J= 1.7 Hz, 1H), 5.80- 5.66 (m, 3H), 4.54 (p, J=7.2Hz, 1H), 3.93-3.87 (m,4H), 3.75 (d,J=7.3Hz,
HRMS-ESI (m/z)
(Thin film) 6H), 2.29 (s, 3H), 2.25 (s,
([M+H]+)
3382, 2937, 3H),2.06 (s, 3H), 1.24 (d,J 1738, 1676, calcd for = 6.1 Hz, 3H), 0.95 (d,J=
515 se
1594, 1504, C32H39N2O9, 7.1Hz, 3H).
1293, 1202, 595.2650; found,
1152 595.2647 13CNMR(101 MHz,
CDC13)5172.41, 170.22, 162.88, 160.25, 159.77, 159.65, 145.70, 143.93, 142.79, 142.70, 142.52, 139.73, 139.31, 121.35, 121.30, 112.69, 111.36, 110.92, 109.50, 89.57, 73.19, 57.91, 56.16, 55.15, 55.14, 48.13,29.30,21.67,21.60, 20.85, 19.29, 17.79.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.21 (d,J=7.8Hz, 1H), 7.05 -6.96 (m, 2H), 6.93 (d,J= 5.4 Hz, 1H), 6.81 (td,J= 7.4, 1.6 Hz, 2H), 6.76 (d,J = 1.6 Hz, 1H), 6.72 (d,J= 1.6 Hz, 1H), 5.79 (dq,J= 10.1, 6.2 Hz, 1H), 5.72 (d,J= 1.4 Hz, 2H), 4.55(p,J=7.2Hz, 1H), 3.97 (d,J= 10.2 Hz,
HRMS-ESI (m/z) 1H), 3.90 (s, 3H), 3.80 (s,
(Thin film)
([M+H]+) 3H), 3.79 (s, 3H), 2.14 (s, 3382, 2936,
3H), 2.11 (s, 3H), 2.06 (s, 1737, 1676, calcd for
516 3H), 1.26 (d,J=6.2Hz,
1505, 1202, C32H39N2O9,
3H), 0.94 (d,J=7.2Hz, 1040, 969, 595.2650; found,
3H).
730 595.2639
13CNMR(101 MHz, CDC13)5172.43, 170.21, 162.89, 160.26, 157.85, 157.65, 145.68, 143.94, 142.67, 140.44, 140.28, 130.75, 130.48, 125.19, 124.78, 119.75, 119.67, 109.94, 109.86, 109.52, 89.56, 73.28,57.91,56.17, 55.29, 55.28, 48.16, 20.85, 19.32, 17.82, 15.80, 15.75.
Figure imgf000432_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.25 (dd,J=6.5, 3.4 Hz, 2H), 7.07 (d,J=3.0Hz, 1H), 6.92 (d,J=5.4Hz, 1H), 6.87 (d,J=3.1Hz, 1H), 6.77 (d,J=8.8Hz, 1H), 6.71 (d,J=8.8Hz, 1H), 6.66 (ddd,J= 11.1, 8.9,
3.0 Hz, 2H), 5.92 (dq,J = 9.9, 6.1 Hz, 1H), 5.72 (d,J = 1.7 Hz, 2H), 4.94 (d,J= 10.0 Hz, 1H), 4.56(p,J=7.2Hz,
HRMS-ESI (m/z)
1H), 3.89 (s, 3H), 3.81 (s,
(Thin film) ([M+H]+)
3H), 3.74 (s, 3H), 3.72 (s, 3381,2939,
calcd for 3H), 3.71 (s, 3H), 2.06 (s,
519 1737, 1676,
C32H39N2O11, 3H), 1.25 (d,J=6.3Hz, 1498, 1233,
627.2548; found, 3H), 0.99 (d,J=7.2Hz, 1043, 729
627.2541 3H).
13CNMR(101 MHz, CDC13)5172.39, 170.22, 162.84, 160.23, 153.47, 153.45, 151.89, 151.78, 145.68, 143.88, 142.78, 130.73, 130.69, 116.45, 115.38, 112.14, 112.13, 111.83, 111.55, 109.45, 89.59, 73.02, 56.34, 56.29, 56.15, 55.67, 55.59, 48.17, 43.90, 20.86, 18.91, 17.97.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.26 (d,J=5.4Hz, 1H), 8.23 (d,J=7.8Hz, 1H), 7.05 (d,J=8.5Hz, 1H), 6.98 (d, J=8.4Hz, 1H),6.93 (d,J= 5.4 Hz, 1H), 6.90 (d,J=2.7 Hz, 1H), 6.82 (d,J=2.7Hz, 1H), 6.63 (ddd,J= 18.1, 8.3, 2.7 Hz, 2H), 5.72 (d,J= 1.6 Hz, 2H), 5.66 (dq,J= 10.0, 6.1Hz, 1H), 4.56 (p,J= 7.3
HRMS-ESI (m/z) Hz, 1H), 4.46 (d,J= 10.1
(Thin film)
([M+H]+) Hz, 1H), 3.90 (s, 3H), 3.73 3382, 2937,
(s, 6H), 2.33 (s, 3H), 2.28 (s, 1739, 1677, calcd for
520 3H),2.06 (s, 3H), 1.32 (d,J
1500, 1455, C32H39N2O9,
= 6.1 Hz, 3H), 0.99 (d,J= 1202, 1042, 595.2650; found,
7.2 Hz, 3H).
730 595.2652
13CNMR(101 MHz, CDC13)5172.37, 170.22, 162.89, 160.25, 157.92, 157.89, 145.69, 143.92, 142.66, 140.37, 139.85, 131.44, 131.11, 128.89, 128.62, 114.67, 113.64, 111.28, 111.11, 109.52, 89.57, 74.55,56.17,55.19, 48.13,47.87, 29.30, 20.86, 19.30, 19.26, 18.88, 17.81.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.39(d,J=7.1Hz, 1H),
8.31 (d,J=5.4Hz, 1H), 7.44 (dd,J=8.7, 5.6 Hz, 1H), 7.23 (dd,J=8.7, 5.6 Hz, 1H),7.11 (dd,J=9.6,2.8 Hz, 1H), 7.07 (dd,J=9.7,
2.8 Hz, 1H), 7.00 (d,J=5.5
HRMS-ESI (m/z) Hz, 1H), 6.96- 6.87 (m,
(Thin film)
([M+H]+) 2H), 5.60 (dq,J=8.5,6.2 3380, 2933,
Hz, 1H), 4.69 (d,J=8.8Hz, 1769, 1737, calcd for
521 1H), 4.62 (d,J= 12.4 Hz,
1677, 1496, C31H35F2N2O8,
1H), 4.60-4.53 (m, 1H), 1195, 1174, 602.2389; found,
4.50 (d,J= 12.6 Hz, 1H), 1095 602.2395
4.44 (d,J= 12.5 Hz, 1H), 4.40 (d,J= 12.5 Hz, 1H), 3.90 (s, 3H), 3.43 (s, 3H), 3.38 (s, 3H), 2.39 (s, 3H),
1.28 (d,J=6.2Hz, 3H), 1.04 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.57, -115.90.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.40 (d,J=6.4Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.45 (dd, 7=8.7, 5.6 Hz, 1H), 7.21 (dd,7=8.7, 5.6 Hz, 1H), 7.17-7.05 (m, 2H), 7.00 (d, 7= 5.5 Hz, 1H), 6.97
HRMS-ESI (m/z) -6.82(m, 2H), 5.62 (dq,7 =
(Thin film)
([M+H]+) 8.2, 6.2 Hz, 1H),4.70 (d,7 = 3385, 2976,
8.7 Hz, 1H), 4.67 (d,7= 12.7 1770, 1738, calcd for
522 Hz, 1H), 4.62- 4.50 (m,
1678, 1506, C33H39F2N2O8,
2H), 4.48 (d,7= 12.5 Hz, 1200, 1175, 629.2669; found,
1H), 4.43 (d,7= 12.7 Hz, 1155, 1096 629.2666
1H),3.90 (s, 3H), 3.62- 3.45 (m,4H), 2.39 (s, 3H), 1.30- 1.25 (m, 6H), 1.23 (t, 7= 7.0 Hz, 3H), 1.05 (d,7= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.69, -115.98.
1H NMR (400 MHz, CDC13) 58.41 (d, 7= 6.8 Hz, 1H), 8.30 (d, 7= 5.4 Hz, 1H), 7.36
-7.28(m, 2H), 7.26-7.18
HRMS-ESI (m/z) (m, 2H), 7.18 -7.10 (m, 2H), ([M+H]+) 6.97 (d, 7= 5.5 Hz, 1H), 6.67
-6.46(m,2H), 5.83 (dq,7 =
¾ calcd for
523 9.9, 6.2 Hz, 1H), 4.62 - 4.46
C28H30FN2O7,
(m,2H), 3.87 (s, 3H), 3.82 525.2037; found,
(s, 3H), 2.38 (s, 3H), 1.23 (d, 525.2025
7= 6.2 Hz, 3H),0.91 (d,7= 7.1Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.24.
Figure imgf000437_0001
Figure imgf000438_0001
Figure imgf000439_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.40 (s, IH), 8.30 (d,J= 5.4 Hz, IH), 7.33 (dd,J =
8.7, 5.8 Hz, IH), 7.20 - 7.04
(m,4H), 6.98 (d,J=5.5Hz, IH), 6.84 (td,J= 8.5, 2.9
HRMS-ESI (m/z)
Hz, IH), 6.77 (dd,J=9.6, ([M+H]+)
2.4 Hz, IH), 5.71 (dq,J = calcd for 10.1, 6.1Hz, IH), 4.61-4.45
530
C29H32FN2O6, (m, IH), 4.21 (d,J= 10.1 523.2244; found, Hz, IH), 3.89 (s, 3H),2.38 523.2229 (s, 3H), 2.30 (s, 3H), 2.28 (s,
3H), 1.23 (d,J=6.0Hz, 3H), 0.96 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -117.33.
1H NMR (400 MHz, CDC13) 58.40 (d,J=6.0Hz, IH), 8.30(d,J=5.5Hz, IH), 7.35 - 7.22 (m, 2H), 7.13 (dd,J = 8.3, 6.4 Hz, 1H),6.99 (d,J =
HRMS-ESI (m/z)
5.5 Hz, IH), 6.96 - 6.84 (m, ([M+H]+)
2H), 6.65-6.51 (m, 2H), calcd for 5.79 (dq,J=9.7, 6.2 Hz,
531 ½
C28H29F2N2O7, IH), 4.64 - 4.47 (m, 2H), 543.1943; found, 3.88 (s, 3H), 3.81 (s, 3H), 543.1936 2.38 (s, 3H), 1.23 (d,J=6.1
Hz, 3H), 0.99 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -112.92, -116.48. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.39(d,J=8.2Hz, 1H),
8.31 (d,J=5.4Hz, 1H), 7.29 -7.19(m, 3H),6.99 (d,J=
HRMS-ESI (m/z) 5.5 Hz, 1H), 6.94-6.81 (m, ([M+H]+) 4H), 5.71 (dq,J= 10.1,6.1
Hz, 1H), 4.60 - 4.49 (m, 1H), calcd for
532 4.26 (d,J= 10.0 Hz, 1H),
Figure imgf000441_0001
3.89 (s, 3H), 2.38 (s, 3H), 527.1993; found,
2.35 (s, 3H), 1.25 (d,J=6.2 527.1984
Hz, 3H), 1.02 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.02, -116.38.
1H NMR (400 MHz, CDC13)
58.41 (d,J=5.8Hz, 1H), 8.30(d,J=5.4Hz, 1H), 7.33
-7.18(m, 3H), 7.02-6.89
HRMS-ESI (m/z) (m, 3H), 6.58 (td, J =8.4, 2.5 ([M+H]+) Hz, 1H), 6.52 (dd,J=10.9,
2.6 Hz, 1H), 5.76 (dq,J = calcd for
533 10.0, 6.2 Hz, 1H), 4.60-4.46
C28H29F2N2O7,
(m, 2H), 3.88 (s, 3H), 3.75 543.1943; found,
(s, 3H), 2.38 (s, 3H), 1.21 (d, 543.1928
J=6.2Hz, 3H), 1.01 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.26, -116.11.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.40 (d,J=8.1Hz, 1H),
8.30(d,J=5.4Hz, 1H), 7.33 (dd,J=8.6, 5.7 Hz, 1H), 7.23 -7.13 (m,2H), 7.04-
HRMS-ESI (m/z) 6.92 (m, 3H), 6.86(td,J = ([M+H]+) 8.5, 2.8 Hz, 1H),6.80 (dd,J
= 9.7, 2.8 Hz, 1H), 5.69 (dq, calcd for
534 J= 9.9, 6.2 Hz, 1H), 4.63-
Figure imgf000442_0001
4.45 (m, 1H), 4.24 (d,J=9.8 527.1993; found,
Hz, 1H), 3.89 (s, 3H),2.38 527.1985
(s, 3H), 2.28 (s, 3H), 1.23 (d,
J=6.1Hz, 3H),0.99 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -115.54, -116.80.
1H NMR (400 MHz, CDC13) 58.49- 8.39 (m, 1H), 8.30 (d,J=5.5Hz, 1H), 7.19-
HRMS-ESI (m/z) 7.05 (m,6H), 7.01- 6.92 (m,
(Thin film)
([M+H]+) 3H), 5.78 (dq,J=10.2, 6.1 3385, 2982,
Hz, 1H), 4.59- 4.46 (m,
535 1771, 1737, calcd for
1H), 3.96 (d,J= 10.2 Hz, 1679, 1605, C29H33N206, 505.233;
1H), 3.86 (s, 3H), 2.37 (s, 1508 found, 505.2333
3H), 2.30 (s, 3H), 2.27 (s, 3H), 1.23 (d,J=6.2Hz, 3H), 0.90 (d,J=7.2Hz,
3H).
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.41 (d,J=5.6Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.23 (dd,J=8.5, 6.6 Hz, 1H), 7.16 (dd,J= 8.6, 5.9 Hz, 1H), 6.99 (d,J=5.5Hz, 1H), 6.81 (qd,J=9.1,8.3,
HRMS-ESI (m/z)
2.8Hz,2H), 6.57 (td, J =
(Thin film) ([M+H]+)
8.3, 2.5 Hz, 1H),6.51 (dd,J 3377, 2985,
calcd for = 10.8, 2.5 Hz, 1H), 5.68
536 1771, 1736,
C29H31F2N2O7, (dq,J= 10.0, 6.1Hz, 1H), 1677, 1502,
557.2094; found, 4.74 (d,J= 10.0 Hz, 1H), 1195
557.2082 4.62- 4.49 (m, 1H), 3.90 (s,
3H), 3.76 (s, 3H), 2.42 (s,
3H),2.38(s, 3H), 1.21 (d,J = 5.9 Hz, 3H), 1.04 (d,J= 7.2 Hz, 3H).
19F NMR (376 MHz, CDC13) δ -113.52, -117.02.
1H NMR (400 MHz, CDC13) 58.40 (d,J=6.1Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.31
(dd,J=8.4, 6.7 Hz, 1H),
HRMS-ESI (m/z) 7.23 -7.14 (m, 1H), 6.99 (d,
(Thin film) ([M+H]+) J=5.5Hz, 1H), 6.84-6.68 3376, 2940, (m,2H), 6.58 (td,J= 8.3, 2.5 calcd for
537 1770, 1737, Hz, 1H), 6.52 (dd,J=10.8,
C28H28F3N2O7,
1678, 1601, 2.5 Hz, 1H), 5.86-5.73 (m,
561.1843; found,
1502, 1196 1H), 4.78 (d,J=9.9Hz,
561.1836
1H), 4.65 - 4.43 (m, 1H), 3.90 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 1.24 (d,J=6.1 Hz, 3H), 1.04 (d,J=7.2Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.44- 8.37 (m, 1H), 8.31 (d,J=5.4Hz, 1H), 7.33 (dd, J= 8.5, 5.8 Hz, 1H), 7.04 (dd,J=8.4, 6.8 Hz, 1H), 6.99(d,J=5.5Hz, 1H), 6.88
HRMS-ESI (m/z)
-6.74 (m, 2H), 6.64-6.53
(Thin film) ([M+H]+)
(m, 2H), 5.67 (dq,J=9.8, 3378, 2986,
calcd for 6.1Hz, 1H), 4.74 (d,J=9.8
538 1770, 1736,
C29H31F2N2O7, Hz, 1H), 4.62 - 4.45 (m, 1677, 1501,
557.2094; found, 1H), 3.90 (s, 3H), 3.84 (s, 1196
557.2091 3H), 2.38 (s, 3H), 2.27 (s,
3H), 1.25 (d,J=6.2Hz, 3H), 0.98 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -112.97, -117.43.
1H NMR (400 MHz, CDC13) 58.43 - 8.35 (m, 1H), 8.31 (d,J=5.4Hz, 1H), 7.33 (dd,
HRMS-ESI (m/z) J= 8.6, 5.7 Hz, 1H), 7.19-
(Thin film) ([M+H]+) 7.07 (m, 1H), 7.00 (d,J=5.5 3377, 2983, Hz, 1H), 6.90 - 6.74 (m, calcd for
539 1771, 1738, 4H), 5.68 (dq,J=12.0, 6.1
1677, 1502,
Figure imgf000444_0001
Hz, 1H), 4.62 (d,J=9.9Hz,
545.1894; found,
1201 1H), 4.61-4.49 (m, 1H),
545.1896
3.90 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.27 (d,J=6.1 Hz, 3H), 1.00 (d,J=7.2Hz,
3H). Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (300 MHz, CDC13) 58.43 (d,J=8.0Hz, 1H), 8.31 (d,J=5.4Hz, 1H), 7.37
HRMS-ESI (m/z) -7.21 (m, 5H), 7.24-7.14
(Thin film) ([M+H]+) (m, 1H), 6.98 (d,J=5.5Hz, 3388, 2985, 1H), 6.89-6.84 (m, 1H), calcd for
540 1771, 1737, 6.79- 6.72 (m, 1H), 5.90- 1679, 1572,
Figure imgf000445_0001
5.72 (m, 1H), 4.56 (dq,J =
509.2082; found,
1508, 1452 8.1,7.1Hz, 1H),4.41 (d,J =
509.2078
10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H), 1.24(d,J=6.2Hz, 3H), 1.00 (d,J=7.2Hz, 3H).
1H NMR (400 MHz, CDC13) 58.42 (d,J=8.2Hz, 1H), 8.31 (dd,J=5.5, 1.2 Hz, 1H), 7.29- 7.17 (m, 3H), 7.07-6.89 (m, 3H), 6.87
HRMS-ESI (m/z)
(dd,J=8.0, 1.7 Hz, 1H), ([M+H]+)
(Thin film) 6.80-6.72 (m, 1H), 5.75 3378, 2984, calcd for (dq,J= 9.7, 6.1Hz, 1H),
541 1 1771, 1737, C28H29F2N2O6, 4.62- 4.50 (m, 1H), 4.39 (d,
1679, 1509 527.1988; found, J=9.8Hz, 1H), 3.89 (s, 3H),
527.1975 2.38 (s, 3H), 2.25 (s, 3H),
1.26-1.21 (m, 3H), 1.01 (d, J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) 5-115.67, -118.89.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 8.48 - 8.36 (m, 1H), 8.29 (d,J=5.6Hz, 1H), 7.26- 7.21 (m, 1H), 7.20- 7.16 (m, 2H), 7.07 (d,J=7.9Hz, 2H), 6.96 (d,J=5.5Hz,
HRMS-ESI (m/z)
1H),6.84 (dd,J=8.1, 1.9
(Thin film) ([M+H]+)
Hz, 1H), 6.74 (dd,J=11.3, 3390, 2984,
calcd for 2.2 Hz, 1H), 5.83 -5.73 (m,
542 1772, 1737,
C29H32FN2O6, 1H), 4.63-4.50 (m, 1H), 1678, 1508,
523.2239; found, 4.37 (d,J= 10.1 Hz, 1H), 1452
523.2241 3.86 (s, 3H), 2.37 (s, 3H),
2.27 (s, 3H), 2.22 (s, 3H), 1.24(d,J=6.1Hz, 3H), 1.00 (d,J=7.2Hz, 3H).
19F NMR (376 MHz, CDC13) δ -119.02.
1H NMR (400 MHz, CDC13) 58.42 (d,J=7.9Hz, 1H),
8.31 (d,J=5.4Hz, 1H), 7.24 (dd,J=9.6, 5.7 Hz, 1H),
7.17(t,J=7.9Hz, 1H), 6.99 (d,J=5.5Hz, 1H), 6.88-
HRMS-ESI (m/z)
6.82 (m, 3H), 6.75 (dd,J =
(Thin film) ([M+H]+)
11.3,2.2 Hz, 1H), 5.72 (dq,J 3384, 2983,
calcd for = 9.8, 6.1Hz, 1H),4.63 (d, J
543 1772, 1737,
C29H31F2N2O6, = 10.0 Hz, 1H), 4.62-4.51 1679, 1591,
541.2145; found, (m, 1H), 3.89 (s, 3H), 2.39 1507, 1452
541.2138 (s, 3H), 2.38 (s, 3H), 2.24 (s,
3H), 1.26 (d,J=6.1Hz, 3H), 1.05 (d,J=7.2Hz,
3H).
19F NMR (376 MHz, CDC13) δ -116.51, -118.10. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) δ 8.45 - 8.39 (m, 1H), 8.31 (d,J=5.5Hz, 1H), 7.32-
HRMS-ESI (m/z)
7.20 (m,2H), 6.99 (d,J=5.5
(Thin film) ([M+H]+)
Hz, 1H), 6.88- 6.84 (m, 3381,2984,
calcd for 1H), 6.84-6.73 (m, 3H),
544 1771, 1739,
C28H28F3N2O6; 5.85- 5.74 (m, 1H), 4.70 (d, 1678, 1504,
545.1894; found, J=9.9Hz, 1H), 4.63 -4.52 1453, 1432
545.1885 (m, 1H), 3.89 (s, 3H), 2.38
(s, 3H), 2.25 (s, 3H), 1.27 (d, J=6.1Hz, 3H), 1.04 (d,J= 7.2 Hz, 3H).
1H NMR (500 MHz, CDC13) 58.41 (s, 1H), 8.32 (d,J= 5.5 Hz, 1H), 7.31 -7.27 (m, 2H), 7.22(t,J=7.7Hz, 2H), 7.17(d,J=8.1Hz, 2H), 7.15 -7.10(m, 1H), 7.09 (d,J= 7.9 Hz, 2H), 6.99 (d,J=5.5 Hz, 1H), 5.79 (dq,J= 10.1,
(Thin film)
6.1Hz, 1H), 4.57- 4.47 (m, 3378, 2982,
1H), 4.01 (d,J= 10.1 Hz, 1770, 1734,
ESIMSw/z 491.2 1H), 3.90 (s, 3H), 2.38 (s, 1675, 1508,
([M+H]+) 3H),2.28 (s, 3H), 1.24 (d,J
545 1451, 1309,
= 6.2 Hz, 3H), 0.88 (d,J= 1200, 1174,
7.2 Hz, 3H).
1046, 907,
802, 730,
13CNMR(126 MHz, 699
CDCI3) δ 172.24, 168.91, 162.24, 159.40, 146.64, 141.73, 141.57, 138.27, 137.43, 136.47, 129.44, 128.46, 127.99, 126.56, 109.68, 73.36, 57.53, 56.27, 47.83, 20.97, 20.75, 19.24, 17.92. Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 58.42 (s, 1H), 8.32 (d,J =
5.4 Hz, 1H), 7.29-7.23 (m, 4H), 7.18 (td,J= 6.0, 2.8
Hz, 3H), 7.04 (d,J=7.9Hz, 2H), 6.99 (d,J=5.5Hz, 1H), 5.79 (dq,J=9.8,6.2
(Thin film) Hz, 1H), 4.57- 4.49 (m, 3381,2982, 1H), 4.02 (d,J=9.9Hz, 1770, 1734, 1H), 3.90 (s, 3H), 2.38 (s,
ESIMSw/z 491.2
1675, 1507, 3H),2.25 (s, 3H), 1.23 (d,J
([M+H]+)
546 1435, 1309, = 6.2 Hz, 3H), 0.93 (d,J=
1199, 1174, 7.2 Hz, 3H).
1045, 907,
804, 729, 13CNMR(126 MHz, 699 CDCI3) δ 172.23, 168.92,
162.25, 159.41, 146.64, 141.59, 138.34, 137.44, 136.15, 129.13, 128.72, 128.09, 127.99, 126.77, 109.68, 73.38, 57.41, 56.28, 47.87, 20.94, 20.76, 19.25, 18.00.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 58.41 (s, 1H), 8.32 (d,J= 5.4 Hz, 1H), 7.23 (dd,J = 8.7, 5.3 Hz, 2H), 7.18-7.13 (m,2H), 7.05 (d,J=7.8Hz, 2H), 7.01 - 6.93 (m, 3H), 5.74 (dq,J=9.6, 6.2 Hz, 1H), 4.58-4.50 (m, 1H),
(Thin film) 4.01 (d,J=9.6Hz, 1H), 3.90 3380, 2982, (s, 3H), 2.38 (s, 3H), 2.26 (s, 1770, 1735, 3H), 1.22 (d,J=6.2Hz,
ESIMSw/z 509.1
1676, 1507, 3H), 0.94 (d,J=7.2Hz,
([M+H]+)
547 1451, 1310, 3H).
1200, 1175,
1158, 1047, 13CNMR(126 MHz, 908, 816, CDC13)5172.18, 168.91, 769, 729 162.26, 161.64 (d,J= 245.3
Hz), 159.43, 146.63, 141.54, 138.05, 137.45, 137.32 (d,J= 3.3 Hz), 136.34, 129.56 (d,J= 7.8 Hz), 129.22, 127.94, 115.53
(d,J=21.3Hz), 109.70, 73.21, 56.51, 56.28, 47.85, 20.94, 20.75, 19.15, 17.99.
Figure imgf000450_0001
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (500 MHz, CDC13) 58.39(s, 1H), 8.32 (d,J = 5.5 Hz, 1H), 7.28-7.21 (m, 2H), 7.14(d,J=8.2Hz, 2H), 7.09 (d,J=7.9Hz, 2H), 6.99 (d,J=5.5Hz, 1H), 6.95 - 6.89 (m, 2H), 5.74 (dq,J= 10.0,6.2 Hz, 1H), 4.58-4.50 (m, 1H),
(Thin film)
4.00 (d,J= 10.0 Hz, 1H), 3380, 2983,
3.90 (s, 3H), 2.38 (s, 3H), 1770, 1735,
ESIMSw/z 509.1 2.29 (s, 3H), 1.23 (d,J=6.1 1676, 1507,
([M+H]+) Hz, 3H), 0.97 (d,J=7.1Hz,
549 1451, 1436,
3H).
1310, 1201,
1175, 1046,
13CNMR(126 MHz, 908, 816,
CDC13)5172.18, 168.91, 731
162.27, 161.54 (d,J= 245.1
Hz), 159.44, 146.63, 141.50, 138.06, 137.48 (d, J = 3.6 Hz), 136.65, 129.49 (d,J=8.3Hz), 127.86, 115.24 (d,J=21.3Hz), 109.73, 73.30, 56.66, 56.28, 47.83, 20.98, 20.75, 19.22, 18.02.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.39(d,J=8.1Hz, 1H), 8.32(d,J=5.5Hz, 1H), 7.34 -7.22 (m, 5H), 7.20-7.14 (m, 1H), 6.99 (d,J=5.5Hz, 1H), 6.85 - 6.74 (m, 2H), 5.80 (dtd,J=9.9, 7.3,6.7, 5.4 Hz, lH),4.55(dt,J= 8.1,7.1Hz, 1H),4.41 (d,J = 10.0 Hz, 1H), 3.90 (s, 3H),
(Thin film)
2.38 (s, 3H), 1.27 (d,J=6.1 3380, 2984,
Hz, 3H), 0.92 (d,J=7.2Hz, 1770, 1737, ESIMSw/z 513.2
3H).
1676, 1503, ([M+H]+)
550
1452, 1310,
13CNMR(126 MHz, 1200, 1175,
CDC13)5172.13, 168.91, 1148, 1048,
162.27, 162.03 (dd,J= 907, 731
168.8, 12.1 Hz), 160.96-
159.14 (m), 159.43, 146.64, 141.50, 140.06, 137.46,
129.88 (dd,J=9.6, 5.6 Hz), 128.60, 128.27, 126.99,
124.68- 124.00 (m), 111.60 (dd,J=21.3, 3.6 Hz), 109.72, 104.55- 103.34 (m), 72.51, 56.28, 49.35,
47.80, 20.75, 18.92, 17.92.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.40 (s, 1H), 8.32 (d,J=
5.5 Hz, 1H), 7.25- 7.16 (m, 3H), 7.05 (d,J=7.9Hz, 2H), 6.99 (d,J=5.5Hz, 1H), 6.84-6.73 (m, 2H), 5.77 (dtd,J=9.5, 6.5,5.2 Hz, 1H), 4.59-4.51 (m,
(Thin film) 1H), 4.38(d,J=9.8Hz, 3384, 2983, 1H), 3.90 (s, 3H), 2.38 (s, 1771, 1737, 3H),2.26 (s, 3H), 1.25 (d,J
ESIMS m/z 527.2
1677, 1502, = 6.2 Hz, 3H), 0.96 (d,J=
([M+H]+)
551 1452, 1310, 7.2 Hz, 3H).
i¾
1201, 1175,
1148, 1049, 13CNMR(126 MHz, 966, 908, CDC13)5172.12, 168.92, 732 162.78- 159.09 (m), 146.64,
141.53, 137.46, 136.96, 136.56, 129.88 (d,J= 5.7 Hz), 129.24, 128.16, 124.64 (d,J= 15.0 Hz), 111.52 (d,J = 20.8 Hz), 109.71, 104.49 - 103.84 (m), 72.59, 56.28, 48.90, 47.84, 20.96, 20.75, 18.92, 18.00.
Cmpd. Reg. MP IR NMR
MASS
No. I» (°C) (cm"1) (1H, 13C, 19F)
1H NMR (400 MHz, CDC13) 58.37(d,J=6.0Hz, 1H), 8.32(d,J=5.4Hz, 1H), 7.28 -7.18(m, 3H), 7.00 (d,J= 5.5 Hz, 1H), 6.97- 6.90 (m, 2H), 6.86-6.75 (m, 2H), 5.76 (dtd,J=9.7, 6.5,5.2 Hz, 1H), 4.62 - 4.48 (m,
(Thin film) 1H), 4.39(d,J=9.8Hz, 3384, 2985, 1H), 3.91 (s, 3H), 2.38 (s, 1770, 1737, 3H), 1.26 (d,J=6.1Hz,
ESIMSw/ 531.2
1676, 1503, 3H), 1.00 (d,J=7.2Hz,
([M+H]+)
552 1201, 1175, 3H).
i¾
1160, 1148,
966, 847, 13CNMR(126 MHz, 825, 811, CDCI3) δ 172.05, 168.91, 732 163.09- 159.02 (m), 146.63,
141.42, 137.50, 135.78, 129.82 (d,J=8.2Hz), 124.23 (d,J= 11.3 Hz), 115.42 (d,J=21.3Hz), 111.98- 111.29 (m), 109.77, 104.80- 103.42 (m), 72.42, 56.30, 48.69, 47.81, 20.75, 18.93, 18.00.
Figure imgf000455_0001
*Cmpd. No. - Compound Number Table 3. Biological Testing Rating Scale
Figure imgf000456_0001
Table 4. Biological Activity - PUCCRT and SEPTTR Disease Control in High and Low Volume Applications
Figure imgf000456_0002
HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
110 A D A A C C C C
111 B D B A C C C C
112 D D B B C C C C
113 A B A B C C C C
114 A A A A C C C C
115 B D A A C C C C
116 B D B B C C C C
117 A B A A C C C C
118 A A B A C C C C
119 D D A B C C C C
120 A B A A C C C C
121 A B A A C C C C
122 D D B B C C C C
123 B D B A C C C C
124 A A A A C C C C
125 A A A A C C C C
127 B D B D C C C C
128 B D A B C C C C
129 A B A A C C C C
130 B D A D C C C C
131 A D A A C C C C
132 A B A A C C C C
133 A A A A C C C C
135 B D B D C C C C
136 A B A B C C C C
137 A B A A C C C C
138 C C C C D B A B
139 C C C C A A A A
140 C C C C A B A A
141 C C C C A A A A
142 C C C C A A A A
143 C C C C B D D B
144 C C C C B B B B
145 C C C C A A A A
146 C C C C A A A A
147 C C C C B B B A
148 C C C C A A A A HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
149 C C C C B B A A
150 C C C C A A A A
152 C C C C B B A A
153 C C C C B B A A
155 C C C C A A A A
156 C C C C A A A A
157 C C C C A A A A
158 C C C C A A A A
159 C C C C A A A A
160 C C C C A B A A
161 C C C C D D B A
162 C C C C D D D B
163 C C C C B D B A
164 C C C C D D B D
165 C C C C A B A A
166 C C C C B D B B
167 C C C C A A A A
168 C C C C A B A A
169 C C C C A B A A
170 C C C C B B B B
171 C C C C A A A A
173 C C C C A B A A
174 C C C C A B A A
175 C C C C A A A A
176 C C C C A A A A
178 C C C C B D A A
179 C C C C B D A A
180 C C C C D D B D
181 C C C C D D B B
182 C C C C D B D B
183 C C C C A A A B
184 C C C C A A A A
185 C C C C A B A A
186 C C C C B D A B
187 C C C C A B B B
188 C C C C A B A A
189 C C C C A B A A HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
190 C C C C B D B B
191 C C C C A A A A
192 C C C C A A A A
193 C C C C B D A A
194 C C C C A B A A
195 C C C C A B A B
196 C C C C D D A B
197 C C C C A A A A
198 C C C C A B A A
199 C C C C A A A A
201 C C C C B D A A
202 C C C C D D A A
203 C C C C A B A A
204 C C C C A A A A
206 C C C C A B A A
207 C C C C D D A A
208 C C C C A B A A
209 C C C C A B A A
210 C C C C A B A A
211 C C C C A A A A
212 C C C C A A A A
213 C C C C B B A A
214 C C C C D D D D
215 C C C C A D A A
216 C C C C A B A B
217 C C C C A B A A
218 C C C C A B A A
219 C C C C A D A A
220 C C C C A B A A
221 C C C C B D B A
222 C C C C A D A A
223 C C C C B D B B
224 C C C C B D A A
225 C C C C D D D D
228 C C C C C C C C
229 C C C C D D D B
230 C C C C D D D D
386 B D B D C C C C
387 A B A B C C C C HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
388 B B A A C C C C
389 A D D D C C C C
390 A B A D C C C C
391 A A A A C C C C
392 A B A D C C C C
393 C C C C C C C C
394 B D A B C C C C
395 A A A A C C C C
396 A A A A C C C C
397 A D A A C C C C
398 B B B B C C C C
399 A A A A C C C C
400 A A A A C C C C
401 A B A A C C C C
402 A B A B C C C C
403 A B A A C C C C
404 A A A A C C C C
405 A A A A C C C C
406 A A A A C C C C
407 A A A A C C C C
408 A B A A C C C C
409 A D A A C C C C
410 B D B B C C C C
411 A B A A C C C C
412 C C C C C C C C
413 A B A A C C C C
414 B D A B C C C C
415 A B A A C C C C
416 A D A B C C C C
417 A D B B C C C C
418 A A A A C C C C
419 B D B B C C C C
420 B D B D C C C C
421 D D D D C C C C
422 D D B D C C C C
423 A A A A C C C C
424 A B A A C C C C
425 A A A A C C C C
426 A D A A C C C C HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
427 B D B B C C C C
428 B D B A C C C C
429 B D B B C C C C
430 A B A A C C C C
431 A A A A C C C C
432 B A A A C C C C
433 A A A A C C C C
434 A A A A C C C C
435 A A A A C C C C
436 A A A A C C C C
437 A A A A C C C C
438 A A A A C C C C
439 A A A A C C C C
440 A A A A C C C C
441 A B A A C C C C
442 A A A A C C C C
443 A A A A C C C C
444 A A A A C C C C
445 A B A A C C C C
446 A B A A C C C C
447 A A A A C C C C
448 A A A A C C C C
449 A A A A C C C C
450 A B A A C C C C
451 A A A A C C C C
452 A A A A C C C C
453 A A A A C C C C
454 A A A A C C C C
455 A A A A C C C C
456 A A A A C C C C
457 A A A A C C C C
458 A A A A C C C C
459 A A A A C C C C
460 A A A A C C C C
461 A A A A C C C C
462 C C C C D D D B
463 C C C C D D D B HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
464 C C C C A A A A
465 C C C C B D D D
466 C C C C B D A B
467 C C C C B B A B
468 C C C C A B A A
469 C C C C B D D D
470 C C C C B B B B
471 C C C C A B A A
472 C C C C A A A A
473 C C C C B B A A
474 C C C C B D A A
475 C C C C A A A A
476 C C C C A A A A
477 C C C C B B A A
478 C C C C B D A B
479 C C C C D D A B
480 C C C C D B D D
481 C C C C B B B A
482 C C C C B A B A
483 C C C C B B A B
484 C C C C A B A B
485 C C C C A A A A
486 C C C C A B A A
487 C C C C A A B A
488 C C C C A B A A
489 C C C C A A A A
490 C C C C A B A A
491 C C C C A B A A
492 C C C C B B A A
493 C C C C B B B B
494 C C C C B B B B
495 C C C C B B B D
496 C C C C A B A A
497 C C C C A B A B
498 C C C C A B A A
499 C C C C B D A A
500 C C C C A B A A
501 C C C C B B A B HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SEF TR* PUCCRT* SEF TR*
502 C C C C A B B D
503 C C C C A B A A
504 C C C C A D B B
505 C C C C B D B D
506 C C C C D D D D
507 C C C C D D B D
508 C C C C A A A A
509 C C C C A B B B
510 C C C C A A A A
511 C C C C D B D D
512 C C C C D D D D
513 C C C C B D D D
514 C C C C D D D D
515 C C C C D D D D
516 C C C C A A A A
517 C C C C A B D B
518 C C C C A A A A
519 C C C C B B A B
520 C C C C D D D D
521 C C C C B B A B
522 C C C C B D A B
523 C C C C A A A A
524 C C C C A A A A
525 C C C C A A A A
526 C C C C A B A A
527 C C C C A B A A
528 C C C C A B A A
529 C C C C A B A A
530 C C C C A D A A
531 C C C C A A A A
532 C C C C A A A A
533 C C C C A A A A
534 C C C C A B A A
535 C C C C A A A A
536 C C C C A B A A
537 C C C C A A A A
538 C C C C A B A A
539 C C C C A B A A
540 C C C C A B A A HV activity at 100 ppm LV activity at 121.5 g/H
PUCCRT* SE TR* PUCCRT* SEPr TR*
541 C C C C A B A A
542 C C C C A B A A
543 C C C C A B A A
544 C C C C A A A A
545 C C C C A A A A
546 C C C C A A A A
547 C C C C A A A A
548 C C C C A A A A
549 C C C C A A A A
550 C C C C A A A A
551 C C C C A A A A
552 C C C C A A A A
553 C C C C A A A A
554 C C C C A A A A
Cmpd. No. - Compound Number
PUCCRT - Wheat Brown Rust {Puccinia triticina)
SEPTTR - Wheat Leaf Blotch {Zymoseptoria tritici)
IDP - 1 Day Protectant
3DC - 3 Day Curative
g/H - Grams Per Hectare
ppm - Parts Per Million
Table 5. Biological Activity - Disease Control at 100 ppm
Figure imgf000464_0001
ALTESO* CERCBE* COLLLA* LEPTNO*
Cmpd. No. IDP*
174 B A A A
176 B A A A
199 A A A A
204 A A A A
464 B A A A
468 A A A A
472 B A A A
475 B A A A
524 A A A A
528 B A A A
532 B A A A
Cmpd. No. - Compound Number
ALTESO - Tomato Early Blight {Alternaria solani)
CERCBE - Leaf Spot of Sugar Beets {Cercospora beticola)
COLLLA - Cucumber Anthracnose {Colletotricum lagenarium)
LEPTNO - Wheat Glume Blotch {Leptosphaeria nodorum)
*1DP - 1 Day Protectant
Table 6. Biological Activity - Disease Control at 100 ppm
PYRIOR* RHYNSE* VENTIN*
Cmpd. No. IDP*
92 C A C
139 A A A
140 A C A
141 A A A
142 A A A
145 A A A
146 A A A
148 A A A
150 A A A
167 A A C
171 A A C
174 A A B
176 A A A
199 A A C
204 A A C PYRIOR* RHYNSE* VENTIN*
Cmpd. No. IDP*
468 A A A
472 A A A
475 A A B
524 A A A
528 A A A
532 C A C
Compound Number
PYRIOR -. Rice Blast {Pyricularia oryzae)
RHYNSE - Barley Scald {Rhyncosporium secalis)
VENTIN - Apple Scab {Venturia inaequalis) *1DP - 1 Day Protectant
Table 7. Biological Activity - Disease Control at 25 ppm
Figure imgf000466_0001
PHAKPA*
Cmpd. No. IDP* 3DC*
210 A D
211 A B
212 B D
213 A B
464 A A
468 A B
472 A B
475 A B
493 D D
494 D D
495 B D
496 B D
497 D D
498 A B
499 B B
500 A B
501 B B
502 B D
503 A D
504 B D
505 D D
506 D D
507 D D
508 B D
509 D D
510 B D
511 D D
512 D D
513 D D
514 D D
515 D D
516 B D
517 B D
518 B D
519 D B
520 D D
521 B D
522 B D
523 A B PHAKPA*
Cmpd. No. IDP* 3DC*
524 A B
525 A B
526 A D
527 A B
528 A B
529 A B
530 A B
531 A B
532 A B
533 A B
534 A B
535 B D
536 A B
537 A B
538 B B
539 A B
540 A B
541 A B
542 B D
543 A B
544 A B
545 B D
546 A B
547 A B
548 A D
549 B D
550 A B
551 A B
552 A B
553 B D
554 B D
Cmpd. No. - Compound Number
PHAKPA - Asian Soybean Rust {Phakopsora pachyrhizi) *1DP - 1 Day Protectant
5 3DC - 3 Day Curative

Claims

CLAIMS What is claimed is:
1. A composition for the control of a fungal pathogen including mixtures of at least one of the compounds of Formula 1
Figure imgf000469_0001
wherein:
X is hydrogen or C(0)R5;
Y is hydrogen, C(0)R5, or Q;
Q is
Figure imgf000469_0002
wherein: Z is N or CH:
Ri is hydrogen or alkyl, substituted with 0, 1 or multiple R8;
R2 is methyl;
R3 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple Rs; R4 is chosen from hydrogen, halo, hydroxyl, alkyl or alkoxy;
R5 is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple
R8
R6 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple Rs;
R7 is chosen from hydrogen, -C(0)R9, or -CH2OC(0)R9; R8 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, each optionally substituted withO, 1, or multiple R10;
R9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple
R8;
Rio is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl;
Ru is chosen from hydrogen or alkyl, substituted with 0, 1 or multiple R8;
Ri2 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple Rs; and
a phytologically acceptable carrier material.
2. The composition according to Claim 1, wherein X is hydrogen and Y is Q.
3. The composition according to Claim 2, wherein Z is N.
4. The composition according to Claim 3, wherein 5 is alkoxy.
5. The composition according to Claim 4, wherein R7 is hydrogen.
6. The composition according to Claim 5, wherein Ri and Ru are independently chosen from hydrogen or alkyl, R3 and R12 are independently aryl, each optionally substituted with 0, 1 or multiple Rs, and R4 is H.
The composition according to Claim 4, wherein R7 is chosen from -C(0)Rg, -CH2OC(0)R9.
8. The composition according to Claim 7, wherein R9 is alkyl, optionally substituted with 0, 1 or multiple R8.
The composition according to Claim 8, wherein Ri and Rn are independently chosen from hydrogen or alkyl, R3 and Ri2 are independently aryl, each optionally substituted with 0, 1 or multiple Rs, and R4 is H.
10. The composition according to Claim 9, wherein R9 is chosen from -CH3, - CH2OCH2CH3, -CH2CH2OCH3, -CH(CH3)2, -CH2CH2CH2CH3, -cyclopropyl.
11. The composition according to Claim 1 wherein the fungal pathogen is one of Leaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Puccinia triticina), Stripe Rust (Puccinia striiformis), Scab of Apple (Venturia inaequalis), Blister Smut of Maize (Ustilago maydis), Powdery Mildew of Grapevine (Uncinula necator), Barley scald (Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust of Soybean
(Phakopsora pac yrhizi), Glume Blotch of Wheat (Leptosphaeria nodorum), Powdery Mildew of Wheat (Blumeria graminis f. sp.tritici), Powdery Mildew of Barley (Blumeria graminis f. sp. hordei), Powdery Mildew of Cucurbits (Erysiphe cichoracearum), Anthracnose of Cucurbits (Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola), Early Blight of Tomato (Alternaria solani), and Net Blotch of Barley
(Pyrenophora teres).
12. The composition according to Claim 6 wherein the fungal pathogen is one of Leaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Puccinia triticina), Scab of Apple (Venturia inaequalis), Barley scald (Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust of Soybean (Phakopsora pachyrhizi), Glume Blotch of Wheat
(Leptosphaeria nodorum), Anthracnose of Cucurbits (Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola), and Early Blight of Tomato (Alternaria solani).
13. The composition according to Claim 7 wherein the fungal pathogen is one Leaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Puccinia triticina), Scab of Apple (Venturia inaequalis), Barley scald (Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust of Soybean (Phakopsora pachyrhizi), Glume Blotch of Wheat
(Leptosphaeria nodorum), Anthracnose of Cucurbits (Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola), and Early Blight of Tomato (Alternaria solani)
14. The composition according to Claim 9 wherein the fungal pathogen is one of Leaf Blotch of Wheat (Zymoseptoria tritici), Wheat Brown Rust (Puccinia triticina), Scab of Apple (Venturia inaequalis), Barley scald (Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust of Soybean (Phakopsora pac yrhizi), Glume Blotch of Wheat
(Leptosphaeria nodorum), Anthracnose of Cucurbits (Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola), and Early Blight of Tomato (Alternaria solani).
15. The composition according to Claim 10 wherein the fungal pathogen is one of Leaf Blotch of Wheat Zymoseptoria tritici), Wheat Brown Rust (Puccinia triticina), Scab of Apple {Venturia inaequalis), Barley scald (Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust of Soybean (Phakopsora pachyrhizi), Glume Blotch of Wheat (Leptosphaeria nodorum), Anthracnose of Cucurbits (Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola), and Early Blight of Tomato (Alternaria solani).
16. A method for the control and prevention of fungal attack on a plant, the method including the step of:
applying a fungi ci dally effective amount of at least one of the compositions of Claim 6 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.
17. A method for the control and prevention of fungal attack on a plant, the method including the step of:
applying a fungicidally effective amount of at least one of the compositions of Claim 9 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.
18. A method for the control and prevention of fungal attack on a plant, the method including the step of:
applying a fungicidally effective amount of at least one of the compositions of Claim 10 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.
19. A method for the control and prevention of fungal attack on a plant, the method including the step of:
applying a fungicidally effective amount of at least one of the compositions of Claim 11 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.
20. A method for the control and prevention of fungal attack on a plant, the method including the step of:
applying a fungicidally effective amount of at least one of the compositions of Claim 15 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.
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