AU2018436544B2 - Quaternary triphenylphosphonium salt compound, preparation method therefor, and uses thereof - Google Patents

Quaternary triphenylphosphonium salt compound, preparation method therefor, and uses thereof Download PDF

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AU2018436544B2
AU2018436544B2 AU2018436544A AU2018436544A AU2018436544B2 AU 2018436544 B2 AU2018436544 B2 AU 2018436544B2 AU 2018436544 A AU2018436544 A AU 2018436544A AU 2018436544 A AU2018436544 A AU 2018436544A AU 2018436544 B2 AU2018436544 B2 AU 2018436544B2
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iia
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AU2018436544A1 (en
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Jiaqi Li
Xuelian LIU
Zhaohai Qin
Dachao TANG
Jiayao WANG
Yumei Xiao
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China Agricultural University
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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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
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  • Environmental Sciences (AREA)
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  • Molecular Biology (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Disclosed are a quaternary triphenylphosphonium salt compound, a preparation method therefor, and the uses thereof. The structure of the quaternary compound is as shown in formula I. The preparation method comprises carrying out a nucleophilic reaction of the compound shown of formula VII and triphenylphosphine in an organic solvent with or without a catalyst to obtain the compound as shown in formula I. The compound as shown in formula I can be used for preventing and treating diseases caused by a plurality of germs such as oomycetes, basidiomycetes, ascomycetes and semi-known fungi on a variety of plants. Excellent results have been obtained in powdery mildew, corn rust, watermelon anthracnose and the like, and a good control effect can be ensured at low concentrations.

Description

TRIPHENYLPHOSPHONIUM SALT COMPOUNDS, PREPARATION METHOD AND USE THEREOF
Field of the Invention
The present invention relates to the technical field of pesticides, and in particular to
a class of triphenylphosphonium salt compounds, and preparation methods and use thereof.
Background of the Invention
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common
general knowledge in the field. Quaternary phosphonium salts and derivatives thereof have been developed rapidly
since the synthesis of tetrahydroxymethyl phosphonium salts by Messinger et al. in 1888.
Alkyl quaternary phosphonium salt compounds, which have been produced and used since 1990, are a new generation of efficient and broad-spectrum fungicides. With the
advantages of high efficiency, broad spectrum, strong surface activity, strong slime
stripping and cleaning effects, low foaming, low dose, low toxicity, no environmental pollution, good compatibility, wide use ranges of pH values (pH 2-12), good chemical
stability, etc., this kind of fungicides is the representative of a new generation cationic surfactant fungicides, and widely used in various fields such as medical and health, oil field exploitation, water treatment, food industry, agriculture, and daily life.
At the same time, due to high affinity to mitochondria, the phosphonium salts are
widely used in the field of mitochondrial targeted delivery of drugs. The phosphonium salts have a 1000 times higher targeted aggregation ability in mitochondria than
non-targeted drugs, and help to reduce the amount of drugs used and decrease side
effects. It is an object of the present invention to overcome or ameliorate at least one of the
disadvantages of the prior art, or to provide a useful alternative.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an
inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense
of "including, but not limited to".
Although the invention will be described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.
Summary of the Invention According to a first aspect of the invention there is provided a compound having a general structural formula as shown in formula I: Ph Ph' X Y
Formula I wherein in formula I, X is selected from the group consisting of CH 2, NH, S, and 0; z is an integer in the range of 1 to 2; when z is 1, Y is any one selected from the group consisting of halogen, CH3 SO 3 , CF 3 CO2 , CH 3 CO2 , CF3 SO 3 , PhCO2 , HOC 6H4 CO 2 and formula W; when z is 2, Y is either one selected from the group consisting of (CH 2 CO 2 ) 2 and (CHCO 2 ) 2 ; the halogen is any one selected from the group consisting of chlorine, bromine, and iodine; n is an integer in the range from 0 to 16; and Q is selected from formula Ia or formula lb below; 0 11N'Ar R, SO3 U'-0 Q1 w Ia Ib
wherein in formula W, Ri represents H or C-C12 alkyl; wherein in formula Ia, Ar is any one selected from the group consisting of A-A 4 and A 6-A8 below, and Qi is any one selected from the group consisting of H and B1-Bii; and
(R2 )m (R4)
AI A2= A3= ' A4
(RO (R) 0
- N A6= A7= A8=F3 l /aCN F C 3 C1
la
O O O 0 0 O
B1= B2= B3= / B4= N C 3 0 0
o R 0 C 2H5 0
BB 6= N B7= NF B= N R8 "C 2 H5 HN B0= 0B1o B11 N0 N0
wherein in formula Ib, U is any one selected from the group consisting of 0, NH, S, OC=, SC=, NHC=, and NHC=S, and Q2 is any one selected from the group consisting of CI-C 4;
0 0 C1=1 C2=~ C3 C4=I MCH3 N OCH3 MCH3 N OCH3 OCH3 H 3CO'Z OCH3 H 3CO'Z
wherein, in formulas Ai and A 2 among Ai-A, R 2, R3 , R4 and R 5 are each at least one selected from the group consisting of hydrogen, C-C8 alkyl, C-C8 alkoxy, CI-C8 alkylthio, CI-C8 fluoroalkyl, CI-C8 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, methanesulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; o and q are each integers in the range from 0 to 5; m is an integer in the range from 0 to 4; p is an integer in the range from 0 to 3; and the binding sites of R2, R3 and R 5 are at least one of remaining five binding sites, wherein, when m, o and q > 1, R2 , R3 and R 5 are the same or different; and the binding sites of R4 are at least one of remaining three binding sites, wherein, when p > 1, R4 are the same or different; in formula A2 , N is at any site of sites 3, 4, 5, and 6; wherein in formula Bi among BI-B 1o, R7 is at least one selected from the group consisting of hydrogen, C1 -C5 alkyl, C1 -C5 alkoxy, C1 -C5 fluoroalkyl, C1 -C5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methylsulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; s is an integer in the range from 0 to 5; the binding sites of R7 are at least one of remaining 5 binding sites, wherein R7 are the same or different when s > 1; in formula B6 , R8 and R 9 are each any one
1b selected from the group consisting of hydrogen, C1 -C alkyl, C1 -C alkoxy, C1 -C fluoroalkyl, C 1-C 5 fluoroalkoxy, and halogen; and wherein in formulas C 1 and C 3 among formulas C-C4, Z is N or CH, and M is NH or 0. According to a second aspect of the invention there is provided a preparation method of the compound of formula I described above, comprising the step of: carrying out a nucleophilic reaction between a compound of formula VII and triphenylphosphine, in the presence or absence of a catalyst, to obtain the compound of formula I; n formula VII wherein in formula VII, Y, Q, X, and n are each defined in the same way as in formula I. According to a third aspect of the invention there is provided a compound with a general structural formula as shown in formula VII: n formula VII wherein in formula VII, Y, Q, X, and n are each defined in the same way as in formula I. According to a fourth aspect of the invention there is provided a preparation method of the compound of formula VII according to the third aspect of the invention, comprising the steps of: reacting a compound of formula IV with a compound of formula VI in the presence of a catalyst, or reacting a compound of formula V with the compound of formula VI, in the presence of an acid binding agent, to obtain the compound of formula VII; H Q 2 -Br/SH Y XU'H Q1N'Ar formula IV formula V formula VI wherein in formula IV, Qi and Ar are each defined in the same way as in formula Ia in the first aspect of the invention; in formula V, Q2 is defined in the same way as in formula Ib in the first aspect of the invention; in formula VI, X, Y, and n are each defined in the same way as in formula I, and U is defined in the same way as in formula lb in the first aspect of the invention; when the compound of formula IV reacts with the compound of formula VI, U is OC=O group.
1c
According to a fifth aspect of the invention there is provided a composition,
comprising the compound as shown in formula I according to the first aspect of the invention
and an agriculturally acceptable carrier. According to a sixth aspect of the invention there is provided use of the compound of formula I according to the first aspect of the invention and/or the composition according to the fifth aspect of the invention in the preparation of a plant fungicide and/or soil fungicide. The triphenylphosphonium salt compound provided by the present invention has a general structural formula as shown in formula I: Ph Ph, i Ph- X' Y- n
Formula I
1d wherein in formula I, X is selected from the group consisting of CH2, N, S, and 0; Y is any one selected from the group consisting of halogen (Cl, Br, or I), CH3SO3, CF3CO2, CH3CO2, CF3SO3, PhCO2, HOC6H4CO2, (CH2CO2)2, (CHCO2)2, and formula W; n is an integer in the range from 0 to 16; and Q is selected from the group consisting of formula Ia and formula Ib; O Ar R, SO 3 I QI
W Ia lb
wherein in formula W, Ri represents H or C-C12 alkyl; wherein in formula Ia, Ar is any one selected from the group consisting of Ai-A below, and Qi is any one selected from the group consisting of H and Bi-Bii; R2)m(R4)P
(R3). -- (R5)
N
A5= -(R = A 6 6), A 7= N As= F3C C1
0 0 0 0 00
B, ,=B2 CN /B3= B4=- A N F3 0
o R9 C,H
B5= N N C/ R8 B7= B FN N~ $B BS= 8 N
8 C2H 5HN
B9= B(=NB 11= 0
0 S and wherein in formula Ib, U is any one selected from the group consisting of 0, NH, S, OC=O, SC=, NHC=, and NHC=S, and Q2 is any one selected from the group consisting of C-C 4 ;
0 0 C1= C2= C 3= 0C= 01= MCH3 N OCH 3 MCH 3 N OCH 3 H 3CO'Z OCH H 3CO'Z OCH3
wherein, in formulas Ai, A2, and A5 among Ai-A8, R2, R3, R4, R5, and R6 are each at least one selected from the group consisting of hydrogen, C-C8 alkyl, C-C alkoxy, C-C alkylthio,
Ci-C8 fluoroalkyl, Ci-C8 fluoroalkoxy, halogen, nitro, cyano, phenoxyl, pyridyloxyl, methanesulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; m is an integer in the range from 0 to 4; o, q, and r are each integers in the range from 0 to 5; p is an integer in the range from 0 to 3; and the binding sites of R2, R3, Rs and R6 are at least one of remaining five binding sites, wherein, when m, o, q, and r > 1, R2, R3, Rs, and R6 may be the same or different; and the binding sites of R4 are at least one of remaining three binding sites, wherein, when p > 1, R4 may be the same or different; in formula A2, N may be at any site of sites 3, 4, 5, and 6; wherein in formula Bi among Bi-Bio, R7 is at least one selected from the group consisting of hydrogen, CI-Cs alkyl, C1-Cs alkoxy, C-C fluoroalkyl, C1-C fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methylsulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; s is an integer in the range from 0 to 5; the binding sites of R7 are at least one of remaining 5 binding sites, wherein R7 may be the same or different when s > 1; in formula B6, R8 and R9 are each any one selected from the group consisting of hydrogen, C1-C5 alkyl, C1-Cs alkoxy, C1-C fluoroalkyl, CI-Cs fluoroalkoxy, and halogen; and wherein in formulas Ci and C3 among CI-C4, Z is selected from the group consisting of N and CH, and M is selected from the group consisting of NH and 0. The general structural formula of the phosphonium salt compounds provided by the present invention is shown in formula I. Preferably, in formula I, X is CH2 or 0; Y is any one selected from the group consisting of halogen, AcO(CH3CO2), p-toluenesulfonyl (TsO), PhCO2, and HOC6H4CO2; n is an integer in the range from 4 to 11; and Q is Ia or lb. More preferably, in formula Ia, Ar is Ai, A3, A4, or A6, and Qi is H; and in formula Ib, U is any one selected from the group consisting of 0, OC=0, and SC=0, and Q2 is any one selected from the group consisting of C1-C4. The terms as used in the definitions of the compound of formula I of the present invention represent the following substituents. The term "halogen" refers to fluorine, chlorine, bromine, and iodine. The term "alkyl" represents straight or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and tert-amyl. The aryl and the aryl moiety in the aryloxy include phenyl, pyridyl, furyl, etc. In addition, in the compounds of formula I of the present invention, geometric isomers are formed due to the connection to different substituents by a carbon-carbon double bond or a carbon-nitrogen double bond (different configurations are represented by Z and E, respectively). The compound of formula I of the present invention can be a Z-isomer, an E-isomer, or a mixture at any proportions of the two. The compound of formula I of the present invention can be in particular selected from the compound numbered as follows.
Ph O Ph 0
N'Ar P O NAr y n Iy n 01 Q
Iana Ianb
Number Y Q1 Ar Ia4-ia-1Ia4-ib-1 Br H A1/[(R2)m=H (R3)o=H] Ia4-Iia-2-a4-iib-2 H A1/[(R2)m=H (R3)o=2-Cl] Ia4-Iia-3-a4-iib-3 H A1/[(R2)m=H (R3)o=3-Cl] Ia4-Iia-4-a4-iib-4 H A1/[(R2)m=H (R3)o=4-Cl] Ia4-Iia-5-a4-iib-5 H A1/[(R2)m=H (R3)o=3,4-2Cl] Ia4-Iia-6-a4-iib-6 H A1/[(R2)m=H (R3)o=2-CH3] Ia4-Iia-7-a4-iib-7 H A1/[(R2)m=H (R3)o=3-CH3] Ia4-Iia-8-a4-iib-8 H A1/[(R2)m=H (R3)o=4-CH3] Ia4-iia-9-a4-iib-9 H Ai/[(R2)m=H (R3)o=3,5-2CH3] Ia4-iia-10-a4-iib-10 H Ai/[(R2)m=H (R3)o=4-C(CH3)3] Ia4-iia-lI-4a4-ib-II H Ai/[(R2)m=H (R3)o=4-SCH3] Ia4-iia-12-a4-iib-12 H Ai/[(R2)m=H (R3)o=4-Br] Ia4-iia-13-a4-iib-13 H Ai/[(R2)m=H (R3)o=4-F] Ia4-iia-14~Ia4-iib-14 H Ai/[(R2)m=H (R3)o=3-F] Ia4-iia-15-a4-iib-15 H Ai/[(R2)m=H (R3)o=2,4-2F] Ia4-iia-16-a4-iib-16 H Ai/[(R2)m=H (R3)o=3,4-2F] Ia4-iia-17-a4-iib-17 H Ai/[(R2)m=H (R3)o=3,4,5-3F] Ia4-iia-18-a4-iib-18 H Ai/[(R2)m=H (R3)=4-OCH3] Ia4-iia-19-a4-iib-19 H Ai/[(R2)m=H (R3)=3-OCH3] Ia4-iia-20-a4-iib-20 H Ai/[(R2)m=H (R3)o=4-CF3] Ia4-iia-21-a4-iib-21 H Ai/[(R2)m=H (R3)o=4-CN] Ia4-Iia-22-a4-iib-22 H Ai/[(R2)m=4-F (R3)=H] Ia4-iia-23-a4-iib-23 H Ai/[(R2)m=4-F (R3)=2-Cl] Ia4-iia-24-a4-iib-24 H Ai/[(R2)m=4-F (R3)=3-Cl] Ia4-iia-25-a4-iib-25 H Ai/[(R2)m=4-F (R3)=4-Cl] Ia4-iia-26-a4-iib-26 H Ai/[(R2)m=4-F (R3)=3,4-2Cl] Ia4-1ia-27~Ia4-1ib-27 H Ai/[(R2)m=4-F (R3)=2-CH3] Ia4-iia-28-a4-iib-28 H Ai/[(R2)m=4-F (R3)=3-CH3] Ia4-iia-29-a4-iib-29 H Ai/[(R2)m=4-F (R3)=4-CH3] Ia4-iia-30-a4-iib-30 H Ai/[(R2)m=4-F (R3) 0=3,5-2CH3] Ia4-iia-31-a4-iib-31 H Ai/[(R2)m=4-F(R3)o=4-C(CH3)3]
Ia4-1ia-32-a4-1ib-32 H A1/[(R2)m=4-F (R3)=4-SCH3] Ia4-ia-33-a4-ib-33 H A1/[(R2)m=4-F (R3)o=4-Br] Ia4-ia-34-a4-ib-34 H A1/[(R2)m=4-F (R3)o=4-F] Ia4-ia-35-a4-ib-35 H A1/[(R2)m=4-F (R3)o=3-F] Ia4-ia-36-a4-ib-36 H A1/[(R2)m=4-F (R3)o=2,4-2F] Ia4-ia-37-a4-ib-37 H A1/[(R2)m=4-F (R3)o=3,4-2F] Ia4-ia-38-a4-ib-38 H A1/[(R2)m=4-F(R3)o=3,4,5-3F] Ia4-ia-39-a4-ib-39 H A1/[(R2)m=4-F (R3)o=4-OCH3] Ia4-ia-40-a4-ib-40 H A1/[(R2)m=4-F (R3)o=3-OCH3] Ia4-Iia-41~Ia4-Iib-41 H A1/[(R2)m=4-F (R3)o=4-CF3] Ia4-ia-42-a4-iib-42 H A1/[(R2)m=4-F (R3)o=4-CN] Ia4-lla-43-a4-llb-43 H A2/N=site 3 [(R4)p=H (R5)q=H] Ia4-ila-44~Ia4-ib-44 H A2/[N=site 3 (R4)p=H (R5)q=2-Cl] Ia4-ia-45-a4-iib-45 H A2/[N=site 3 (R4)p=H (R5)q=3-Cl] Ia4-lla-46-a4-llb-46 H A2/[N=site 3 (R4)p=H (R5)q=4-Cl] Ia4-ia-47-a4-iib-47 H A2/[N=site (R4)P=H (R5)q=3,4-2C] Ia4-ia-48-a4-iib-48 H A2/[N=site 3 (R4)p=H (R5)q=2-CH3] Ia4-ia-49-a4-iib-49 H A2/[N=site 3 (R4)p=H (R5)q=3-CH3] Ia4-iia-50-a4-iib-50 H A2/[N=site 3 (R4)p=H (R5)q=4-CH3]
4-lla-51-W-llb-51 H A2/[N=site 3 (R4)p=H (R5)q=3,5-2CH3]
1a4-lla-52-a4-llb-52 H A2/[N=site 3 (R4)p=H (R5)q=4-C(CH3)3] 1a4-lla-53-a4-llb-53 H A2/[N=site 3 (R4)P=H (R5)q=4-SCH3] Ia4-ia-54-a4-iib-54 H A2/[N=site 3 (R4)p=H (R5)q=4-Br] Ia4-lla-55-a4-llb-55 H A2/[N=site 3 (R4)p=H (R5)q=4-F] Ia4-iia-56-a4-iib-56 H A2/[N=site 3 (R4)p=H (R5)q=3-F] Ia4-iia-57-a4-iib-57 H A2/[N=site 3 (R4)p=H (R5)q=2,4-2F]
1a4-lla-58-a4-llb-58 H A2/[N=site 3 (R4)p=H (R5)q=3,4,5-3F]
1a4-lla-59-a4-llb-59 H A2/[N=site 3 (R4)P=H (R5)q=4-OCH3] 1a4-la-60-1a4-1ib-60 H A2/[N=site 3 (R4)P=H(R5)q=3-OCH3] Ia4-ila-61~Ia4-ib-61 H A2/[N=site 3 (R4)p=H (R5)q=4-CF3] Ia4-lla-62-a4-llb-62 H A2/[N=site 3 (R4)p=H (R5)q=4-CN] Ia4-lla-63-a4-llb-63 H A3 Ia4-lia-64-a4-llb-64 H A4 Ia4-ia-65-a4-ib-65 H A5/[(R6)r=H] Ia4-ia-66-a4-ib-66 H A5/[(R6)r=2-CH3] Ia4-ia-67-a4-ib-67 H A5/[(R6)r=3-CH3] Ia4-ia-68-a4-ib-68 H A5/[(R6)r=2-CN] Ia4-ia-69-a4-ib-69 H A5/[(R6)r=2-CF3]
1a4-1la-70-la4-1 ib-70 H A5/[(R6)r=2,6-2CH3] 1a4-1 ia-71I-la4-1 ib-71 H A5/[(R6)=2-C-4-NO2] 1a4-1a-72-la4- ib-72 H A5/[(R6)=2-NO2-4CF3] 1a4-1la-73-la4-1 ib-73 H A5/[(R6)r2,32C1-40H] 1a4-1la-74-la4-1 ib-74 H A5/[(R6)r=2,6-2C1-40CF3] 1a4-11a-75la41 ib75 H A5/[(R6)=3-C-4-CH3] 1a4-1la-76-la4-1 ib-76 H A5/[(R6)=3-OCH(CH3)2] 1a4-1la-77-la4-1 ib-77 H A5/[(R6)=4-CHCH3CH2CH (CH3)2] la4-llia-78-la4-llib-78 H A6 la4-llia-79-la4-llib-79 H A7 la4-llia-80-la4-llib-80 H A8
1a4-1 ia-81K-la4-11ib-81 B i[(R7)=2 A3 -1] 1a4-11ia-82-la4-1 ib-82 B1i[(R7)=2 A4 -1]
Ia4-11ia-83-la4-11ib-83 Bi[(R7)s=2 A5/[(R6)r=H] -1]
1a4-11ia-84-la4-1 ib-84 B1i[(R7)=2 A6 -1]
Ia4-11ia-85-la4-11ib-85 B1i[(R7)=2 A3 -CH3] la4- i a86-l4-1 b-86B1i[(R7)=2 A4 Ia4~1a~6K~a~11~86-CH3]
la4- i a87-l4-1 b-87Bi[(R7)s=2 A5/[(R6)=3-OCH(CH3)2] Ia4~1a~7K~a~11~87-CH3]
1a4-11ia-8 8-la4-1 ib-8 8 B i[(R7)=2 A6 -CH3] la4- i a89-l4-1 b-89B1i[(R7)=2 A3 Ia4~1a~9K~a~11~89-CF3]
la4- i a90-l4-1 b-90B1i[(R7)=2 A4 1a4-la-0-4a-1i-90-CF3]
1a4-1 ia-91IKla41ib-91 Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH3)2] -CF3] la4- i a92-l4-1 b-92B1i[(R7)=2 A6 1a4-la-2-4a-1i-92-CF3]
la4- i a93-l4-1 b-93B1i[(R7)=2 A8 1a4-1a~3K~a~1i-93-CF3]
la4- i a94-l4-1 b-94B1i[(R7)=2 A3 1a4-1a-94a4-1b-94,6-2C1]
la4- i a95-l4-1 b-95B1i[(R7)=2 A4 1a4-1a~5K~a~1i-95,6-2C1]
la4- i a96-l4-1 b-96B1i[(R7)=2 A6 1a4-la-6-4a-1i-96,6-2C1]
1a4-1 ia-97-la4-i ib-97 B i[(R7)=2 A8 ,6-2C1] B1[(R7)s=3 A3 1a4-1 ia-98-la4-1ib-98 A45,6-40 _______________-2-COGH] ___________
B1[(R7)s=3 A4 1a4-1 ia-99-la4-i ib-99 A45,6-40 -2-COGH] Bi[(R7)s=3 A5/[(R6)r=2,3-2C1 la4-llia-1I00-la4-llib- 100 A45,6-40 -2-COGH] Bi[(R7)s=3
-2-COGH] 1a4- i a- I02-la4-i ib- 102 B2 Ai/[(R2)=H (R3).=3,4-2F] Ia4-11a-1O3-la4-11b-1O3 B2 A3 la4-lla-104-la4-llb-104 B2 A4 Ia4-11a-105-la4-11b-105 B2 A6 1a4-ia-i06-la4-iib-106 B3 Ai/[(R2)=H (R3).=H] la4-lla-107-la4-llb-107 B3 A3 Ia4-11a-108-la4-11b-108 B3 A4 1a4-ia-i09-la4-ib-109 B3 A5/[(R6)r=H] la4-lla- 10-la4-llb-1 10 B3 A6 la4-lla-11I14-a4-llb-11I1 B4 A3 la4-lla-1 12-la4-llb-1 12 B4 A4 1a4-ia-i 3-la4-ib1I13 B4 A5/[(R6)r=H] la4-lla-1 14-la4-llb-1 14 B4 A6 1a4-ia-i 5-la4-iib-1 15 B5 Ai/[(R2)=H (R3)=4-C1] la4-lla-1 16-la4-llb-1 16 B5 A3 la4-lla- 17-la4-llb-1 17 B5 A4 1a4-ia-i 8-la4-ib1I18 B5 A5/[(R6)r=H] 1a4-ia-i 9-la4-ib1I19 B5 A5/[(R6)=2-CH2CH3] 1a4-ia-i20-la4-iib-120 B5 A5/[(R6)=2-OCH2CH3] 1a4-iia-121-la4-iib-121 B5 A5/[(R6)r=2-OCH(CH3)2] 1a4-iia-i22-la4-iib-122 B5 A5/[(R6)r=3-CH2CH3] 1a4-iia-i23-la4-iib-123 B5 A5/[(R6)r=3-OCH2CH3] 1a4-iia-i24-la4-iib-124 B5 A5/[(R6)r=3-OCH(CH3)2] Ia4-lia-125-la4-lib-125 B5 A6
la4lia126la4lib126B6/[R8=H; A3 1a4-ia-i6-4~iib126R9=CF3] A4 la4lia127la4lib127B6/[R8=H; 1a4-ia-274aiib127R9=CF3]
Ia4-iia-128-la4-ib-128 B6/[R8=H; A5/[(R6)r=H] ___________________R9=CF3]
Ia4-ia-129-a4-iib-129 B6/[R8=H; A5/[(R6)r=2-CH2CH3] R9=CF3]
Ia4-1ia-130-a4-iib-130 B6/[R8=H; A5/[(R6),=2-OCH2CH3] R9=CF3]
Ia4-ila-131I-a4-lib-131 B6/[R8=H; A5/[(R6),=2-OCH(CH3)2] R9=CF3]
Ia4-ila-132-a4-ilb-132 B6/[R8=H; A5/[(R6)r=3-CH2CH3] R9=CF3]
Ia4-1ia-133-a4-iib-133 B6/[R8=H; A5/[(R6)r=3-OCH2CH3] R9=CF3]
Ia4-ila-134-a4-ilb-134 B6/[R8=H; A5/[(R6)r=3-OCH(CH3)2] R9=CF3] B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH Ia4-ia-135~Ia4-iib-135 R9=CF3] (CH3 ) 2 ]
Ia4-1ia-136-a4-iib-136 B6/[R8=H; A6 R9=CF3]
Ia4-1ia-137-a4-iib-137 B6/[R8=H; A7 R9=CF3] B6/[R8=C1 A3 1a4-1 ia-138-1a4-i ib-138 ; R9=CH3] B6/[R8=C1 A4 1a4-ia-139--1a4-iib-139 ; R9=CH3]
Ia4-ia-140-a4-iib-140 B6/[R8=C1 A5/[(R6)r=H] BRs=CH3]
Ia4-ia-141-a4-1ib-141 B6/[R8=C1 A5/[(R6)r=2-CH2CH3] BRs=CH3]
Ia4-ia-142-a4-iib-142 B6/[R8=C1 A5/[(R6)r=2-OCH2CH3] BRs=CH3]
Ia4-ia-143-a4-iib-143 B6/[R8=C1 A5/[(R6)r=2-OCH(CH3)2] ;R9=CH3]
1a4-ia-i44-la4-iib-144 B6/[R8=C1 A5/[(R6)r=4-CHCH3CH2CH ; R9=CH3] (CH3 ) 2 ]
1a4-ia-i45-la4-iib-145 B6/[R8=C1 ; R9=CH3] A6 1a4-ia-i46-1a4-ib-i46 B6/[R8=C1 ; R9=CH3] A7 1a4-ia-i47-la4-iib-147 B6/[R8=H; A3 R9=CF3] 1a4-ia-i48-1a4-ib-i48 B6/[R8=H; A4 R9=CF3]
Ia4-iia-149-a4-iib-149 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
Ia4-iia-150-a4-iib-150 B6/[R8=H; A5/[(R6)r=2-CH2CH3] 8R=CF3]
Ia4-1ia-151I-a4-1ib-151 B6/[R8=H; A5/[(R6),=2-OCH2CH3] R9=CF3] Ia4-ila-152-a4-ilb-152 B6/[R8=H; A5/[(R6),=2-OCH(CH3)2] R9=CF3] B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH Ia4-ia-153~Ia4-iib-153 R9=CF3] (CH3 ) 2 ]
Ia4-ila-154-a4-ilb-154 B6/[R8=H; A6 R9=CF3] Ia4-ia-15I5-a4-iib-155 B6/[R8=H; A7 R9=CF3] 1a4-llia-1I56-1a4-llib-1 56 B7 A3 Ia4-ila-157-a4-ilb-157 B7 A4 Ia4-1ia-I58-a4-iib-158 B7 A5/[(R6)r=H] Ia4-1ia-I59-a4-iib-159 B7 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-ila-160-a4-ilb-160 B7 A6 Ia4-ila-161I-a4-ilb-161 B7 A7 Ia4-ila-162-a4-ilb-162 B8 A3 Ia4-ila-163-a4-ilb-163 B8 A4 Ia4-1ia-I64-a4-ib-164 B8 A5/[(R6)r=H] Ia4-1ia-I65-a4-iib-165 B8 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-ila-166-a4-ilb-166 B8 A6 Ia4-iia-167-a4-iib-167 B8 A7 Ia4-iia-168-a4-iib-168 B9 A3 Ia4-iia-169-a4-iib-169 B9 A4 Ia4-iia-I70-a4-iib-170 B9 A5/[(R6)r=H] Ia4-iia-171~I-a4-iib-171 B9 A6 Ia4-iia-172-a4-iib-172 B9 A7 Ia4-iia-173-a4-iib-173 Bio A3 Ia4-iia-174-a4-iib-174 Bio A4 Ia4-iia-I75-a4-iib-175 Bio A5/[(R6)r=H] Ia4-iia-I76-a4-iib-176 Bio A5/[(R6)r=3-C1-4 CH3 ] Ia4-iia-177-a4-iib-177 Bio A6 Ia4-iia-178-a4-iib-178 Bio A7 Ia4-iia-179-a4-iib-179 B1 A3 Ia4-iia-180-a4-iib-180 B1 A4 Ia4-iia-181-a4-iib-181 B1 A5/[(R6)r=H] Ia4-iia-182-a4-iib-182 B1 A5/[(R6)r=2,6-2CH3] Ia4-iia-183-a4-iib-183 B1 A6 Ia4-iia-184-a4-iib-184 B1 A7 Ia4-iia-185-a4-iib-185 AcO H Ai/[(R2)m=H (R3)o=H] Ia4-iia-186-a4-iib-186 H Ai/[(R2)m=H (R3)o=2-Cl] Ia4-iia-187-a4-iib-187 H Ai/[(R2)m=H (R3)o=3-Cl] Ia4-iia-188-a4-iib-188 H Ai/[(R2)m=H (R3)o=4-Cl]
Ia4-iia-I89-a4-iib-189 H Ai/[(R2)m=H (R3)o=3,4-2C] Ia4-iia-190-a4-iib-190 H A1/[(R2)m=H (R3)o=2-CH3] Ia4-ia-191-a4-iib-191 H A1/[(R2)m=H (R3)o=3-CH3] Ia4-iia-192-a4-iib-192 H Ai/[(R2)m=H (R3)o=4-CH3] Ia4-iia-193-a4-iib-193 H Ai/[(R2)m=H (R3)o=3,5-2CH3] Ia4-iia-194-a4-iib-194 H Ai/[(R2)m=H (R3)o=4-C(CH3)3] Ia4-iia-195-a4-iib-195 H Ai/[(R2)m=H (R3)o=4-SCH3] Ia4-iia-196-a4-iib-196 H Ai/[(R2)m=H (R3)o=4-Br] Ia4-iia-197-a4-iib-197 H Ai/[(R2)m=H (R3)o=4-F] Ia4-iia-198-a4-iib-198 H Ai/[(R2)m=H (R3)o=3-F] Ia4-iia-199-a4-iib-199 H Ai/[(R2)m=H (R3)o=2,4-2F] Ia4-iia-200-a4-iib-200 H Ai/[(R2)m=H (R3)o=3,4-2F] Ia4-iia-201-a4-iib-201 H Ai/[(R2)m=H (R3)o=3,4,5-3F] Ia4-iia-202-a4-iib-202 H Ai/[(R2)m=H (R3)o=4-OCH3] Ia4-iia-203-a4-iib-203 H Ai/[(R2)m=H (R3)o=3-OCH3] Ia4-iia-204-a4-iib-204 H Ai/[(R2)m=H (R3)o=4-CF3] Ia4-iia-205-a4-iib-205 H Ai/[(R2)m=H (R3)o=4-CN] Ia4-iia-206-a4-iib-206 H Ai/[(R2)m=4-F (R3)=H] Ia4-iia-207-a4-iib-207 H Ai/[(R2)m=4-F (R3)=2-Cl] Ia4-iia-208-a4-iib-208 H Ai/[(R2)m=4-F (R3)=3-Cl] Ia4-iia-209-a4-iib-209 H Ai/[(R2)m=4-F (R3)=4-Cl] Ia4-iia-210-a4-iib-210 H Ai/[(R2)m=4-F (R3)=3,4-2C] Ia4-ia-211-a4-iib-211 H Ai/[(R2)m=4-F (R3)=2-CH3] Ia4-iia-212-a4-iib-212 H Ai/[(R2)m=4-F (R3)=3-CH3] Ia4-iia-213-a4-iib-213 H Ai/[(R2)m=4-F (R3)=4-CH3] Ia4-iia-214-a4-iib-214 H Ai/[(R2)m=4-F (R3)=3,5-2CH3] Ia4-iia-215-a4-iib-215 H Ai/[(R2)m=4-F (R3) 0=4-C(CH3)3] Ia4-iia-216-a4-iib-216 H Ai/[(R2)m=4-F (R3)=4-SCH3] Ia4-1ia-217-a4-iib-217 H Ai/[(R2)m=4-F (R3)o=4-Br] Ia4-iia-218-a4-iib-218 H Ai/[(R2)m=4-F (R3)o=4-F] Ia4-iia-219-a4-iib-219 H Ai/[(R2)m=4-F (R3)o=3-F] Ia4-iia-220-a4-iib-220 H Ai/[(R2)m=4-F (R3)o=2,4-2F] Ia4-iia-221-a4-iib-221 H Ai/[(R2)m=4-F (R3)o=3,4-2F] Ia4-iia-222-a4-iib-222 H Ai/[(R2)m=4-F (R3)o=3,4,5-3F] Ia4-iia-223-a4-iib-223 H Ai/[(R2)m=4-F (R3)o=4-OCH3] Ia4-iia-224-a4-iib-224 H Ai/[(R2)m=4-F (R3)o=3-OCH3] Ia4-iia-225-a4-iib-225 H Ai/[(R2)m=4-F (R3)o=4-CF3] Ia4-iia-226-a4-iib-226 H Ai/[(R2)m=4-F (R3)o=4-CN] Ia4-iia-227-a4-iib-227 H A2/N=site 3 [(R4)p=H (R5)q=H] Ia4-iia-228-a4-iib-228 H A2/[N=site 3 (R4)=H (R5)q=2-Cl] Ia4-iia-229-a4-iib-229 H A2/[N=site 3 (R4)=H (R5)q=3-Cl] Ia4-iia-230-a4-iib-230 H A2/[N=site 3 (R4)=H (R5)q=4-Cl] Ia4ia231la l31 H A2/[N=site 3 (R4)P=H ia-2 Ia4-iiu-2 (R5)q=3,4-2C]
1a4-11a-232-la41ib-232 H A2/[N=Site 3 (li)P=H(R5)q=2CH3] Ia4-11a-233-la4-11b-233 H A2/[N=Site 3 (li)P=H(R5)q=3CH3] 1a4-11a-234-la4ib-234 H A2/[N=Site 3 (li)P=H(R5)q=4CH3]
Ia4-11a-235-la4-11b-235 H A2/[N=Site 3 (R4)P=H (R5)q=3,5-2CH3]
Ia4-11a-236-la4-11b-236 H A2/[N=Site 3 (R4)P=H (R5)q=4C(CH3)3] Ia4-11a-237-la4-11b-237 H A2/[N=Site 3 (R4)P=H (R5)q=4SCH3] 1a4-11a-238-la4-ib-238 H A2/[N=Site 3 (li)P=H(R5)q=4Br] 1a4-1a-239-la4-ib-239 H A2/[N=Site 3 (li)P=H(R5)q=4F] Ia4-11a-24OKla4-11b-24O H A2/[N=Site 3 (li)P=H(R5)q=3F] 1a4-1a-241-la4-iib-241 H A2/[N=Site 3(R)P=H (R5)q=2,4-2F]
la4-lla-242-la4-llb-242 H A2/[N=Site 3 (R4)P=H (R5)q=3,4,5-3F]
1a4-11a-243-la4ib-243 H A2/[N=Site 3 (R4)P=H (R5)q=4OCH3] la4-lla-244-la4-llb-244 H A2/[N=Site 3 (R4)P=H (R5)q=3OCH3] 1a4-11a-245-la4ib-245 H A2/[N=Site 3 (li)P=H(R5)q=4CF3] la4-lla-246-la4-llb-246 H A2/[N=Site 3(R)P=H (R5)q=4CN] la4-lla-247-la4-llb-247 H A3 la4-lla-248-la4-llb-248 H A4 1a4-1a-249-la4-ib-249 H A5/[(R6)r=H] 1a4-la-250-la4-ib-250 H A5/[(R6)=2-CH3] 1a4-ia-251K-la4-ib-251 H A5/[(R6)=3-CH3] 1a4-la-252-la4-ib-252 H A5/[(R6)=2-CN] 1a4-11a-253-la4ib253 H A5/[(R6)=2-CF3] 1a4-la-254-la4-ib-254 H A5/[(R6)r=2,6-2CH3] 1a4-11a-255-la4ib255 H A5/[(R6)=2-C-4-NO2] 1a4-la-256-la4-ib-256 H A5/[(R6)=2-NO2-4CF3] 1a4-la-257-la4-ib-257 H A5/[(R6)r2,32C1-40H] 1a4-ia-258-la4-ib-258 H A5/[(R6)r=2,6-2C1-40CF3] 1a4-la-259-la4-ib-259 H A5/[(R6)=3-C-4-CH3] 1a4-la-260-la4-ib-260 H A5/[(R6)=3-OCH(CH3)2] 1a4-ia-261-la4-1ib-261 H A5/[(R6)=4-CHCH3CH2CH (CH3)2] la4-lla-262-la4-llb-262 H A6 la4-lla-263-la4-llb-263 H A7 la4-lla-264-la4-llb-264 H A8
1a4-11a-265-la4-ib-265 B1i[(R7)=2 A3 -1]
1a4-1la-266-la4-1 ib-266 B1i[(R7)=2 A4
1a4-1a-267-la4-1 ib-267 Bi[(R7)=2 A5/[(R6)r=H] -1]
1a4-11a-268-la4-ib-268 Bi[(R7)=2 A6 -1] la4-ia-29-la-lib269B1[(R7)=2 A3 1a4-la-29-4a-1ib269-CH3] la4-ia-20-la-lib270B1[(R7)=2 A4 1a4-la-20-4a-1ib270-CH3]
la4-la-271la4-lb-271Bi[(R7)s=2 A5/[(R6)r=3OCH(CH3)2] 1a4-la-21-4a-llb271-CH3]
la4-ia-22-la-lib272B1[(R7)=2 A6 1a4-la-22-4a-1ib272-CH3]
1a4-11a-273-la4-11b-273 Bi[(R7)=2 A3 -CF3] la4-ia-24-la-lib274B1[(R7)=2 A4 1a4-la-24-4a-1ib274-CF3]
1a4-11a-275-la4-ib-275 Bi[(R7)=2 A5/[(R6)r=3OCH(CH3)2] -CF3] la4-ia-26-la-lib276B1[(R7)=2 A6 1a4-la-26-4a-1ib276-CF3]
la4-ia-27-la-lib277B1[(R7)=2 A8 1a4-la-274a-1ib277-CF3]
1a4-11a-278-la4-ib-278 Bi[(R7)=2 A3 ,6-2C1] la4-ia-29-la-lib279B1[(R7)=2 A4 1a4-la-29-4a-1ib279,6-2C1]
la4-ia-20-la-lib280B1i[(R7)=2 A6 1a4-la-20-4a-llb280,6-2C1]
la4- i -28I -a4- ib281B1i[(R7)=2 A8 Ia4~1a~21K~a~11b281,6-2C1] B1[(R7)s=3 A3 1a4-1la-282-la4-1 ib-282 A45,6-40 -2-COGH] B1[(R7)s=3 A4 Ia4-11ia-283-la4-11ib-283 A45,6-40 -2-COGH] Bi[(R7)s=3 A5/[(R6)r=2,3-2C1 1a4-1a-284-la4-1 ib-284 A45,6-40 -2-COGH] Bi[(R7)s=3 Ia4-11ia-285-la4-11ib-285 A45,6-40 A6 -2-COGH] 1a4-1a-286-la4-1 ib-286 B2 A1/[(R2)=H (R3)&=3,4-2F] la4-lla-287-la4-llb-287 B2 A3
Ia4-11ia-288-la4-11b-288 B2 A4 la4-llia-289-la4-llib-289 B2 A6 la4-llia-290-la4-llib-290 B3 A1/[(R2)mH(R3),=H] la4-lla-291-la4-llb-291 B3 A3 la4-lla-292-la4-llb-292 B3 A4 1a4-11a-293-la4ib293 B3 A5/[(R6)r=H] la4-lla-294-la4-llb-294 B3 A6 la4-lla-295-la4-llb-295 B4 A3 la4-lla-296-la4-llb-296 B4 A4 1a4-la-297-la4-ib-297 B4 A5/[(R6)r=H] la4-lla-298-la4-llb-298 B4 A6 1a4-la-299-la4-1ib-299 B5 A1/[(R2)mH(R3)=4-C1] la4-lla-300-la4-llb-300 B5 A3 Ia4-11a-3O1-la4-11b-3O1 B5 A4 1a4-11a-3O2-la4ib302 B5 A5/[(R6)r=H] 1a4-11a-3O3-la4ib303 B5 A5/[(R6)=2-CH2CH3] 1a4-la-304-la4-ib-304 B5 A5/[(R6)=2-OCH2CH3] 1a4-11a-3O6-la4-ib-305 B5 A5/[(R6)=2-OCH(CH3)2] 1a4-11a-3O7-la4ib307 B5 A5/[(R6)=3-CH2CH3] 1a4-11a-3O8-la4ib308 B5 A5/[(R6)=3-OCH2CH3] 1a4-11a-3O9-la4ib309 B5 A5/[(R6)=3-OCH(CH3)2] Ia4-11a-3 1OKla4-1b-3 10 B5 A6
1a4-1ia-311KIla4-ib-311 B6/[R8=H; A3 R9=CF3]
1a4-1ia-312-la4-ib-312 B6/[R8=H; A4 R9=CF3]
Ia4-11a-313-la4-11b-313 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
1a4-1ia-314-la4-ib-314 B6/[R8-H; 5[R)=-HC3 R9=CF3] A/(R)CH H]
Ia4-11a-315-la4-11b-315 B6/[R8=H; A5/[(R6)=2-OCH2CH3] R9=CF3]
1a4-ia-316-la4-ib-316 B6/[R8=H; A5/[(R6)=2-OCH(CH3)2] R9=CF3]
1a4-ia-317-la4-ib-317 B6/[R8=H; A5/[(R6)=3-CH2CH3] R9=CF3]
1a4-1ia-318-la4-ib-318 B6/[R8=H; A5/[(R6)=3-OCH2CH3] R9=CF3]
1a4-1ia-319-la4-ib-319 B6/[R8=H; A5/[(R6)=3-OCH(CH3)2] R9=CF3] la4-ia-30-la-lib320B6/[R8=H; A5/[(R6)r=4CHCH3CH2CH 1a41la3204a41ib320R9=CF3] (CH3)2]
Ia4-11a-321-la4-11b-321 B6/[R8=H; A6 __________________ ______R9=CF3] ________________
Ia4-1ia-322-a4-1ib-322 B6/[R8=H; A7 R9=CF3] B6/[R8=C1 A3 1a4-1la-323-1a4-1 ib-323 ; R9=CH3] B6/[R8=C1 A4 1a4-la-324-1a4-ib-324 ; R9=CH3] Ia4-ia-325-a4-ib-325 B6/[R8=C1 A5/[(R6)r=H] BRs=CH3]
Ia4-ia-326-a4-ib-326 B6/[R8=C1 A5/[(R6)r=2-CH2CH3] BRs=CH3]
Ia4-ia-327-a4-ib-327 B6/[R8=C1 A5/[(R6),=2-OCH2CH3] BRs=CH3]
Ia4-ia-328-a4-ib-328 B6/[R8=C1 A5/[(R6),=2-OCH(CH3)2] ;R9=CH3]
1a4-la-329-1a4-ib-329 B6/[R8=C1 A5/[(R6)r=4-CHCH3CH2CH ; R9=CH3] (CH3 ) 2 ]
Ia4-ia-330-a4-ib-330 B6/[R8=C1 A6 BRs=CH3]
Ia4-ia-331-a4-ib-331 B6/[R8=C1 A7 ;R9=CH3]
1a4-la-332-1a4-ib-332 B6/[R8=H; A3 R9=CF3] 1a4-la-333-1a4-ib-333 B6/[R8=H; A4 R9=CF3] Ia4-ia-334-a4-ib-334 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
Ia4-lla-335-a4-llb-335 B6/[R8=H; A5/[(R6)r=2-CH2CH3] R9=CF3]
Ia4-ia-336-a4-ib-336 B6/[R8=H; A5/[(R6),=2-OCH2CH3] R9=CF3]
Ia4-ia-337-a4-ib-337 B6/[R8=H; A5/[(R6),=2-OCH(CH3)2] R9=CF3] B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH Ia4-ia-338~Ia4-1ib-338 R9=CF3] (CH3 ) 2 ]
Ia4-ia-339-a4-ib-339 B6/[R8=H; A6 R9=CF3]
Ia4-ia-340-a4-ib-340 B6/[R8=H; A7 R9=CF3] Ia4-lla-341-a4-llb-341 B7 A3 Ia4-lla-342-a4-llb-342 B7 A4 Ia4-ia-343-a4-ib-343 B7 A5/[(R6)r=H] Ia4-ia-344-a4-ib-344 B7 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-lla-345-a4-llb-345 B7 A6 Ia4-lla-346-a4-llb-346 B7 A7 la4-llia-347-la4-llib-347 B8 A3 Ia4-11ia-348-la4-11b-348 B8 A4 1a4-11ia-349-la4-1 ib-349 B8 A5/[(R6)r=H] 1a4-11ia-35OKla4-1 ib-350 B8 A5/[(R6)r=2,6-2Br-4OCF3] Ia4-11ia-351-la4-11b-351 B8 A6 Ia4-11ia-352-la4-11b-352 B8 A7 Ia4-11ia-353-la4-11ib-353 B9 A3 Ia4-11ia-354-la4-11b-354 B9 A4 1a4-11a-355-la41 ib355 B9 A5/[(R6)r=H] Ia4-11ia-356-la4-11b-356 B9 A6 Ia4-11ia-357-la4-11b-357 B9 A7 Ia4-11ia-358-la4-11b-358 Blo A3 Ia4-11ia-359-la4-11b-359 Blo A4 1a4-11a-36Ola41 ib360 Bio A5/[(R6)r=H] 1a4-1 ia-361-la4-1 ib-361 Bio A5/[(R6)=3-C1-4CH3] la4-lla-362-la4-llb-362 Bio A6 Ia4-11a-363-la4-11b-363 Bio A7 la4-lla-364-la4-llb-364 B11 A3 Ia4-11a-365-la4-11b-365 B11 A4 1a4-1a366-la4ib366 B11 A5/[(R6)r=H] 1a4-la-367-la4-1ib-367 B11 A5/[(R6)r=2,6-2CH3] Ia4-11a-368-la4-11b-368 B11 A6 la4-lla-369-la4-llb-369 Bil A7 1a4-lla-370-la4-llb-370 TsO H A1/[(R2)=H (R3).=H] 1a4-1ia-371-la4-ib-371 H A1/[(R2)=H (R3)=2-C1] 1a4-la-372-la4-ib-372 H A1/[(R2)=H (R3)=3-C1] 1a4-11a-373-la4-ib-373 H A1/[(R2)=H (R3)=4-C1] 1a4-la-374-la4-1ib-374 H A1/[(R2)=H (R3).=3,4-2C1] 1a4-11a-375-la4-ib-375 H A/[(R2)m=H (R3)=2CH3] 1a4-la-376-la4-1ib-376 H A/[(R2)=H (R3)=3-CH3] 1a4-la-377-la4-1ib-377 H A1/[(R2)=H (R3)=4-CH3] 1a4-11a-378-la4-ib-378 H A1/[(R2)=H (R3).=3,5-2CH3] 1a4-la-379-la4-1ib-379 H A1/[(R2)=H (R3)=4-C(CH3)3] 1a4-ia-380-la4-1ib-380 H A1/[(R2)=H (R3)=4-SCH3] 1a4-ia-381-la4-ib-381 H A1/[(R2)=H (R3).=4-Br] 1a4-ia-382-la4-ib382 H A1/[(R2)=H (R3)=4-F] 1a4-ia-383-la4-ib383 H A1/[(R2)=H (R3)=3-F] 1a4-ia-384-la4-ib-384 H A1/[(R2)=H (R3).=2,4-2F] 1a4-ia-385-la4-ib385 H A1/[(R2)=H (R3).=3,4-2F] 1a4-ia-386-la4-ib386 H A1/[(R2)=H (R3).=3,4,5-3F] 1a4-ia-387-la4-1ib-387 H A/[(R2)m=H (R3)=4OCH3] 1a4-1ia-388-la4-ib-388 H A/[(R2)m=H (R3)=3OCH3] 1a4-1ia-389-la4-ib-389 H A1/[(R2)=H (R3)=4-CF3] 1a4-la-390-la4-1ib-390 _____H A1/[(R2)m=H (R3)=4-CN]
Ia4-1ia-391I-a4-1ib-391 H A1/[(R2)m=4-F (R3)o=H] Ia4-ia-392-a4-ib-392 H A1/[(R2)m=4-F (R3)o=2-Cl] Ia4-ia-393-a4-ib-393 H A1/[(R2)m=4-F (R3)o=3-Cl] Ia4-ia-394-a4-ib-394 H A1/[(R2)m=4-F (R3)o=4-Cl] Ia4-ia-395-a4-ib-395 H A1/[(R2)m=4-F (R3)o=3,4-2C] Ia4-ia-396-a4-ib-396 H A1/[(R2)m=4-F (R3)o=2-CH3] Ia4-ia-397-a4-ib-397 H A1/[(R2)m=4-F (R3)o=3-CH3] Ia4-ia-398-a4-ib-398 H A1/[(R2)m=4-F (R3)o=4-CH3] Ia4-ia-399-a4-ib-399 H A1/[(R2)m=4-F (R3)o=3,5-2CH3] Ia4-ia-400-a4-ib-400 H A1/[(R2)m=4-F (R3)o=4-C(CH3)3] Ia4-ia-401-a4-1ib-401 H A1/[(R2)m=4-F (R3)o=4-SCH3] Ia4-ia-402-a4-ib-402 H A1/[(R2)m=4-F (R3)o=4-Br] Ia4-ia-403-a4-ib-403 H A1/[(R2)m=4-F (R3)o=4-F] Ia4-ia-404-a4-iib-404 H A1/[(R2)m=4-F (R3)o=3-F] Ia4-ia-405-a4-ib-405 H A1/[(R2)m=4-F (R3)o=2,4-2F] Ia4-ia-406-a4-ib-406 H A1/[(R2)m=4-F (R3)o=3,4-2F] Ia4-ia-407-a4-ib-407 H A1/[(R2)m=4-F (R3)o=3,4,5-3F] Ia4-ia-408-a4-ib-408 H A1/[(R2)m=4-F (R3)o=4-OCH3] Ia4-ia-409-a4-ib-409 H A1/[(R2)m=4-F (R3)o=3-OCH3] Ia4-ia-410-a4-ib-410 H A1/[(R2)m=4-F (R3)o=4-CF3] Ia4-ia-411-a4-ib-411 H A1/[(R2)m=4-F (R3)o=4-CN] Ia4-iia-412-a4-iib-412 H A2/N=site 3 [(R4)p=H (R5)q=H] Ia4-iia-413-a4-iib-413 H A2/[N=site 3 (R4)p=H (R5)q=2-Cl] Ia4-iia-414-a4-iib-414 H A2/[N=site 3 (R4)p=H (R5)q=3-Cl] Ia4-iia-415-a4-iib-415 H A2/[N=site 3 (R4)p=H (R5)q=4-Cl] 1a4-li16llC416 H A2/[N=site 3 (R4)P=H (R5)q=3,4-2C] Ia4-iia-417-a4-iib-417 H A2/[N=site 3 (R4)p=H (R5)q=2-CH3] Ia4-lla-418-a4-llb-418 H A2/[N=site 3 (R4)p=H (R5)q=3-CH3] Ia4-iia-419-a4-iib-419 H A2/[N=site 3 (R4)p=H (R5)q=4-CH3]
1a4-1a-420--1a4-ib-420 A2/[N=site 3 (R4)P=H (R5)q=3,5-2CH3]
1a4-1a-421-1a4-iib-421 H A2/[N=site 3 (R4)P=H (R5)q=4-C(CH3)3] 1a4-lla-422-a4-llb-422 H A2/[N=site 3 (R4)P=H (R5)q=4-SCH3] Ia4-ia-423-a4-iib-423 H A2/[N=site 3 (R4)p=H (R5)q=4-Br] Ia4-lla-424-a4-llb-424 H A2/[N=site 3 (R4)p=H (R5)q=4-F] Ia4-1ia-425-a4-iib-425 H A2/[N=site 3 (R4)P=H (R5)q=3-F] Ia4-1ia-426-a4-iib-426 H A2/[N=site 3 (R4)P=H (R5)q=2,4-2F]
1a4-1a-427--a4-ib-427 H A2/[N=site 3 (R4)P=H (R5)q=3,4,5-3F]
1a4-1a-428--a4-iib-428 H A2/[N=site 3 (R4)P=H Ia4-iia-428~Ia4-iib-42 __(R5)q=4-OCH3]
1a4-1a-429--a4-ib-429 H A2/[N=site 3 (R4)P=H (R5)q=3-OCH3] Ia4-1ia-430-a4-iib-430 H A2/[N=site 3 (R4)p=H (R5)q=4-CF3] Ia4-ia-431-a4-iib-431 H A2/[N=site 3 (R4)p=H (R5)q=4-CN] Ia4-lla-432-a4-llb-432 H A3 Ia4-lla-433-a4-llb-433 H A4 Ia4-ia-434-a4-ib-434 H A5/[(R6)r=H] Ia4-ia-435-a4-ib-435 H A5/[(R6)r=2-CH3] Ia4-ia-436-a4-ib-436 H A5/[(R6)r=3-CH3] Ia4-ia-437-a4-ib-437 H A5/[(R6)r=2-CN] Ia4-ia-438-a4-lb-438 H A5/[(R6)r=2-CF3] Ia4-ia-439-a4-ib-439 H A5/[(R6)r=2,6-2CH3] Ia4-ia-440-a4-iib-440 H A5/[(R6)r=2-Cl-4-NO2] Ia4-ia-441-a4-llb-441 H A5/[(R6)r=2-NO2-4-CF3] Ia4-ia-442-a4-iib-442 H A5/[(R6)r=2,3-2C-4-OH] Ia4-ia-443-a4-ib-443 H A5/[(R6)r=2,6-2Cl-4-OCF3] Ia4-ia-444-a4-iib-444 H A5/[(R6)r=3-Cl-4-CH3] Ia4-ia-445-a4-ib-445 H A5/[(R6)r=3-OCH(CH3)2] 1a4-1a-446--a4-ib-446 H A5/[(R6)r=4-CHCH3CH2CH (CH3) 2] Ia4-lla-447-a4-llb-447 H A6 Ia4-lla-448-a4-llb-448 H A7 Ia4-lla-449-a4-llb-449 H A8
Ia4-ia-450-a4-ib-450 B1[(R7),=2 A3 -I] Ia4-1ia-451I-a4-1ib-451 Bi[(R7),=2 A4 -I] 1a4-1la-452-1a4-1 ib-452 Bi[(R7)s=2 A5/[(R6)r=H] -I] Ia4-1ia-453-Ia4-1ib-453 B1[(R7),=2 A6 -I] Bi[(R7)s=2 A3 1a4-1la-454-1a4-1 ib-454 -CH 3] Bi[(R7)s=2 A4 1a4-1la-45 5-a4-1 ib-455 -CH 3]
1a4-1la-45 6-a4-1 ib-456 Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH3)2] -CH 3] Bi[(R7)s=2 A6 1a4-1la-45 7-a4-1 ib-457 -CH3] Bi[(R7)s=2 A3 Ia4-1la-458~I1a4-llb-458 -CF3] Bi[(R7)s=2 A4 Ia4-1la-459~I1a4-ib-459 -CF3] Ia4-1ia-460-a4-ilb-460 Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH3)2]
-CF3] Bi[(R7)s=2 A6 1a4-1 ia-461-a4-1 ib-461 -CF3] Bi[(R7)s=2 A8 Ia4-1la-462~I1a4-ib-462 -CF3] Bi[(R7)s=2 A3 Ia4-1la-463~I1a4-ib-463 ,6-2C1] Bi[(R7)s=2 A4 1a4-la-464--1a4-llb-464 ,6-2C1] Bi[(R7)s=2 A6 Ia4-1la-465~I1a4-ib-465 ,6-2C1] Bi[(R7)s=2 A8 Ia4-1la-466~I1a4-ib-466 ,6-2C1] Bi[(R7)s=3 A3 Ia4-1ia-467-a4-ilb-467 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 A4 Ia4-1ia-468-a4-1ib-468 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 A5/[(R6)r=2,3-2C Ia4-1ia-469-a4-ilb-469 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 Ia4-1ia-470-a4-1ib-470 ,4,5,6-4C1 A6 -2-COOH] Ia4-1ia-471I-a4-1ib-471 B2 A1/[(R2)m=H (R3)o=3,4-2F] Ia4-lia-472-a4-llb-472 B2 A3 Ia4-lla-473-a4-llb-473 B2 A4 Ia4-lia-474-a4-llb-474 B2 A6 Ia4-ia-475-a4-ib-475 B3 A1/[(R2)m=H (R3)o=H] Ia4-lla-476-a4-llb-476 B3 A3 Ia4-lia-477-a4-llb-477 B3 A4 Ia4-ia-478-a4-ib-478 B3 A5/[(R)r=H] Ia4-lla-479-a4-llb-479 B3 A6 Ia4-lla-480-a4-llb-480 B4 A3 Ia4-lla-481-a4-llb-481 B4 A4 Ia4-ia-482-a4-ib-482 B4 A5/[(R)r=H] Ia4-lla-483-a4-llb-483 B4 A6 Ia4-ia-484-a4-ib-484 B5 A1/[(R2)m=H (R3)o=4-Cl] Ia4-lla-485-a4-llb-485 B5 A3 Ia4-lla-486-a4-llb-486 B5 A4 Ia4-ia-487-a4-ib-487 B5 A5/[(R)r=H] Ia4-ia-488-a4-ib-488 B5 A5/[(R6)r=2-CH2CH3]
Ia4-1ia-489-a4-ib-489 B5 A5/[(R6)r=2-OCH2CH3] Ia4-1ia-490~Ia4-1ib-490 B5 A5/[(R6)r=2-OCH(CH3)2] Ia4-1ia-491Ila4-1ib-491 B5 A5/[(R6)r=3-CH2CH3] Ia4-1ia-492-a4-ib-492 B5 A5/[(R6)r=3-OCH2CH3] Ia4-1ia-493~la4-ib-493 B5 A5/[(R6)r=3-OCH(CH3)2] Ia4-ia-494-a4-ilb-494 B5 A6 B6/[R8=H; A3 1a4-1ia-495-la4-1 ib-495 R9=CF3] B6/[R8=H; A4 1a4-1a-496-a4-1 ib-496 R9=CF3] Ia4-1ia-497~Ia4-1ib-497 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
Ia4-1ia-498-a4-1ib-498 B6/[R8=H; A5/[(R6)r=2-CH2CH3] R9=CF3]
Ia4-1ia-499~Ia4-1ib-499 B6/[R8=H; A5/[(R6)r=2-OCH2CH3] R9=CF3]
Ia4-1ia-500-a4-1ib-500 B6/[R8=H; A5/[(R6)r=2-OCH(CH3)2] R9=CF3]
Ia4-1ia-501~Ia4-1ib-501 B6/[R8=H; A5/[(R6)r=3-CH2CH3] R9=CF3]
Ia4-1ia-502~la4-ib-502 B6/[R8=H; A5/[(R6)r=3-OCH2CH3] R9=CF3]
Ia4-1ia-503~la4-ib-503 B6/[R8=H; A5/[(R6)r=3-OCH(CH3)2] R9=CF3] B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH Ia4-1la-504~Ia4-1ib-504 R9=CF3] (CH3)2]
Ia4-1ia-505~la4-ib-505 B6/[R8=H; A6 R9=CF3]
Ia4-1ia-506~Ia4-1ib-506 B6/[R8=H; A7 R9=CF3] B6/[R8=C1 A3 1a4-1ia-507-la4-1 ib-507 ; R9=CH3] B6/[R8=C1 A4 1a4-11a-5O8-la4-ib-508 ; R9=CH3]
Ia4-iia-509~Ia4-iib-509 B6/[R8=C A5/[(R6)r=H] BRs=CH3]
Ia4-ia-510~la4-iib-510 B6/[R8=C A5/[(R6)r=2-CH2CH3] BRs=CH3]
Ia4-ia-511~la4-iib-511 B6/[R8=C A5/[(R6)r=2-OCH2CH3] BRs=CH3]
Ia4-ia-512~la4-iib-512 B6/[R8=C A5/[(R6)r=2-OCH(CH3)2] ;R9=CH3]
1a4-1ia-513-la4-ib-513 B6/[R8=C1 A5/[(R6)r=4-CHCH3CH2CH Ia4-_a-13~a4-_b-13_ R9=CH3] (CH3)2]
Ia4-ia-514-a4-iib-514 B6/[R8=C1 A6 BRs=CH3]
Ia4-lia-515I-a4-iib-515 B6/[R8=C A7 ;R9=CH3] A B6/[R8=H; A3 1a4-ia-Si6-la4-iib-S16 R9=CF3] 1a4-ia-Si7-la4-iib-S17 B6/[R8=H; A4 R9=CF3] Ia4-ia-518-a4-iib-518 B6/[R8=H; A5/[(R6)r=H] R9=CF3] Ia4-iia-519-a4-iib-519 B6/[R8=H; A5/[(R6)r=2-CH2CH3] R9=CF3] Ia4-iia-520-a4-iib-520 B6/[R8=H; A5/[(R6),=2-OCH2CH3] R9=CF3] Ia4-iia-521-a4-iib-521 B6/[R8=H; A5/[(R6),=2-OCH(CH3)2] R9=CF3] 1a4-lia-S22-a4-iib-S22 B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH R9=CF3] (CH3 ) 2 ]
Ia4-iia-523-a4-iib-523 B6/[R8=H; A6 R9=CF3]
Ia4-iia-524-a4-iib-524 B6/[R8=H; A7 R9=CF3] Ia4-iia-525-a4-iib-525 B7 A3 Ia4-iia-526-a4-iib-526 B7 A4 Ia4-iia-527-a4-ib-527 B7 A5/[(R6)r=H] Ia4-iia-528-a4-ib-528 B7 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-iia-529-a4-iib-529 B7 A6 Ia4-iia-530-a4-iib-530 B7 A7 Ia4-iia-531-a4-iib-531 B8 A3 Ia4-iia-532-a4-iib-532 B8 A4 Ia4-iia-533-a4-ib-533 B8 A5/[(R6)r=H] Ia4-iia-534-a4-iib-534 B8 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-iia-535-a4-iib-535 B8 A6 Ia4-iia-536-a4-iib-536 B8 A7 Ia4-iia-537-a4-iib-537 B9 A3 Ia4-iia-538-a4-iib-538 B9 A4 Ia4-iia-539-a4-ib-539 B9 A5/[(R6)r=H] Ia4-iia-540-a4-iib-540 B9 A6 Ia4-iia-541-a4-iib-541 B9 A7 Ia4-iia-542-a4-iib-542 Bio A3 Ia4-iia-543-a4-iib-543 Bio A4 Ia4-iia-544-a4-ib-544 Bio A5/[(R6)r=H] Ia4-iia-545-a4-ib-545 Bio A5/[(R6)r=3-C1-4 CH3 ] Ia4-iia-546-a4-iib-546 Bio A6 la4-llia-547-la4-llib-547 Blo A7 Ia4-11ia-548-la4-11b-548 B11 A3 la4-llia-549-la4-llib-549 B11 A4 1a4-1ia-55OKla41 ib550 B11 A5/[(R6)r=H] 1a4-1 ia-551K-la4-ib-551 B11 A5/[(R6)r=2,6-2CH3] Ia4-11ia-552-la4-11b-552 B11 A6 Ia4-11ia-553-la4-11ib-553 B11 A7 1a4-1a-554-la4-1 ib-554 PhCO2 H A1/[(R2)=H (R3).=H] 1a4-11a-555-la4-ib-555 H A1/[(R2)=H (R3)=2-C1] 1a4-11a-556-la4-ib-556 H A1/[(R2)=H (R3)=3-C1] 1a4-11a-557-la4-ib-557 H A1/[(R2)=H (R3)=4-C1] 1a4-1ia-558-la4-ib-558 H A1/[(R2)=H (R3).=3,4-2C1] 1a4-11a-559-la4-ib-559 H A/[(R2)m=H (R3)=2CH3] 1a4-la-560-la4-1ib-560 H A/[(R2)=H (R3)=3-CH3] 1a4-1ia-561-la4-ib-561 H A1/[(R2)=H (R3)=4-CH3] 1a4-la-562-la4-ib-562 H A1/[(R2)=H (R3).=3,5-2CH3] 1a4-11a-563-la4-ib-563 H A1/[(R2)=H (R3)=4-C(CH3)3] 1a4-la-564-la4-1ib-564 H A/[(R2)m=H (R3)=4SCH3] 1a4-11a-565-la4ib565 H A1/[(R2)=H (R3).=4-Br] 1a4-la-566-la4-ib-566 H A1/[(R2)=H (R3)=4-F] 1a4-la-567-la4-ib-567 H A1/[(R2)=H (R3)=3-F] 1a4-la-568-la4-ib-568 H A1/[(R2)=H (R3).=2,4-2F] 1a4-la-569-la4-ib-569 H A1/[(R2)=H (R3).=3,4-2F] 1a4-11a-57OKla4ib570 H A1/[(R2)=H (R3).=3,4,5-3F] 1a4-ia-571-la4-1ib-571 H A1/[(R2)=H (R3).=40CH3] 1a4-la-572-la4-1ib-572 H A/[(R2)m=H (R3)=3OCH3] 1a4-11a-573-la4-ib-573 H A1/[(R2)=H (R3)=4-CF3] 1a4-la-574-la4-1ib-574 H A1/[(R2)=H (R3)=4-CN] 1a4-11a-575-la4ib575 H A1/[(R2)m=4-F(R3).=H] 1a4-la-576-la4-1ib-576 H A/[(R2)m=4F(R3)=2-C1] 1a4-la-577-la4-1ib-577 H A/[(R2)m=4F(R3)=3-C1] 1a4-11a-578-la4-ib-578 H A/[(R2)m=4F(R3)=4-C1] 1a4-la-579-la4-1ib-579 H A1/[(R2)m=4-F(R3)=3,4-2C] 1a4-1ia-58OKla4-ib-580 H A/[(R2)m=4F(R3)=2-CH3] 1a4-1ia-581-la4-ib-581 H A/[(R2)m=4F(R3)=3-CH3] 1a4-1ia-582-la4-ib-582 H A/[(R2)m=4F(R3)=4-CH3] 1a4-1ia-583-la4-ib-583 H A1/[(R2)m=4-F(R3)=3,5-2CH3] 1a4-1ia-584-la4-ib-584 H A1/[(R2)m=4-F(R3)=4-C(CH3)3] 1a4-1ia-585-la4-ib-585 H A/[(R2)m=4F(R3)=4-SCH3] 1a4-ia-S86-la4ib586 H Ai/[(R2)m=4-F(R3),=4-Br] 1a4-lia-S87-la4-ib587 H Al/[(R2)m=4F(R3)=4-F] 1a4-lia-S88-la4-ib-588 H Ai/[(R2)m=4F(R3)=3-F] 1a4-lia-S89-la4-ib-589 H Ai/[(R2)m=4-F(R3)=2,4-2f] 1a4-ia-590-la4-ib-590 _____H Ai/[(R2)=4-F (R3)=3,4-2F]
1a4-1 ia-591-la4-1 ib-591 H A/[(R2)m4F(R3),=3,4,5-3F] 1a4-la-592-la4-1ib-592 H A/[(R2)m4F(R3)=4-OCH3] 1a4-11a-593-la4-ib-593 H A/[(R2)m4F(R3)=3-OCH3] 1a4-la-594-la4-1ib-594 H A/[(R2)m4F(R3)=4-CF3] 1a4-la-595-la4-1ib-595 H A/[(R2)m4F(R3)=4-CN] Ia4-11a-596-la4-11b-596 H A2/N=site 3[(R4)pH(R5)q=H] 1a4-lia-597-la4-ib-597 H A2/[N=Site 3 (li)P=H(R5)q=2C] Ia4-11a-598-la4-11b-598 H A2/[N=Site 3 (li)P=H(R5)q=3-C] 1a4-lia-599-la4-iib-599 H A2/[N=Site 3 (li)P=H(R5)q4-C] la4-lla-600-la4-llb-600 H A2/[N=Site 3 (R4)P=H (R5)q=3,4-2C1] Ia4-11a-6O1-la4-11b-6O1 H A2/[N=Site 3 (li)P=H(R5)q=2CH3] 1a4-1a-602-la4-iib-602 H A2/[N=Site 3(R)P=H (R5)q=3-CH3] Ia4-11a-6O3-la4-11b-6O3 H A2/[N=Site 3 (li)P=H(R5)q=4CH3] 1a4-1a-604-la4-iib-604 H A2/[N=Site 3 (R4)P=H (R5)q=3,5-2CH3]
Ia4-11a-6O5-la4-11b-6O5 H A2/[N=Site 3 (R4)P=H (R5)q=4C(CH3)3] la4-lla-606-la4-llb-606 H A2/[N=Site 3 (R4)P=H (R5)q=4SCH3] 1a4-1a-607-la4-iib-607 H A2/[N=Site 3(R)P=H (R5)q4Br] Ia4-11a-6O8-la4-11b-6O8 H A2/[N=Site 3 (li)P=H(R5)q=4F] Ia4-11a-6O9-la4-11b-6O9 H A2/[N=Site 3 (li)P=H(R5)q=3F] 1a4-lia-61O-la4-iib-610 H A2/[N=Site 3(R)P=H (R5)q=2,4-2F]
Ia4-11a-611-la4-11b-611 H A2/[N=Site 3 (R4)P=H (R5)q=3,4,5-3F]
1a4-1ia-612-la4-ib-612 H A2/[N=Site 3 (R4)P=H (R5)q=4OCH3] Ia4-11a-613-la4-11b-613 H A2/[N=Site 3 (R4)P=H (R5)q=3OCH3] Ia4-11a-614-la4-11b-614 H A2/[N=Site 3(R4)P=(R5)q=4CF3] 1a4-lia-615-la4-iib-615 H A2/[N=Site 3 (li)P=H(R5)q=4CN] la4-lla-616-la4-llb-616 H A3 la4-lla-617-la4-llb-617 H A4 1a4-1ia-618-la4-ib-618 H A5/[(R6)r=H] 1a4-ia-619-la4-ib-619 H A5/[(R6)=2-CH3] 1a4-la-620-la4-ib-620 H A5/[(R6)=3-CH3] 1a4-la-621-la4-llb-621 H A5/[(R6)=2-CN] 1a4-1a-622-la4-ib-622 H A5/[(R6)=2-CF3] 1a4-la-623-la4-ib-623 H A5/[(R6)r=2,6-2CH3] 1a4-1a-624-la4-ib-624 H A5/[(R6)=2-C-4-NO2] 1a4-la-625-la4-ib-625 H A5/[(R6)=2-NO2-4CF3] 1a4-la-626-la4-ib-626 H A5/[(R6)r2,32C1-40H] 1a4-la-627-la4-ib-627 H A5/[(R6)r=2,6-2C1-40CF3]
1a4-1a-628-la4-1 ib-628 H A5/[(R6)=3-C-4-CH3] 1a4-1a-629-la4-1 ib-629 H A5/[(R6)=3-OCH(CH3)2] 1a4-1la-630-la4-1 ib-630 H A5/[(R6)=4-CHCH3CH2CH (CH3)2] Ia4-11ia-631Ia4-11b-631 H A6 la4-llia-632-la4-llib-632 H A7 Ia4-11ia-633-la4-11ib-633 H A8 1a4-11ia-634-la4-1 ib-634 B1[(R7)s=2 A3
1a4-11ia-635-la4-1 ib-635 B1[(R7)s=2 A4
1a4-11a-636-la4-1 ib-636 Bi[(R7)s=2 A5/[(R6)r=H]
1a4-11ia-637-la4-1 ib-637 B1[(R7)s=2 A6
la4- ia638la4- ib638B1[(R7)s=2 A3
1a4-11a-639-la4-1 ib-639 Bi[(R7)s=2 A4 -CH3] la4- ia640-a4- ib-40 i[(R7)s=2 A5/[(R6)=3-OCH(CH3)2] 1a4-la-604a-1ib640-CH3]
la4- ia64 Ila41 ib641B1[(R7)s=2 A6 1a4-la-614a-llb641-CH3]
la4- ia642la4- ib642B1[(R7)s=2 A3 1a4-la-62-4a-1ib642-CF3]
la4- ia643la4- ib643B1[(R7)s=2 A4 1a4-la-63-4a-1ib643-CF3]
1a4-1a-644-la4-i ib-644 Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH3)2] -CF3] la4- ia645la4- ib645B1[(R7)s=2 A6 1a4-la-65-4a-1ib645-CF3]
la4- ia646la4- ib646B1[(R7)s=2 A8 1a4-la-664a-1ib646-CF3]
la4- ia647la4- ib647B1[(R7)s=2 A3 1a4-la-67-4a-1ib647,6-2C1]
la4- ia648la4- ib648B1[(R7)s=2 A4 1a4-la-684a-1ib648,6-2C1]
la4- ia649la4- ib649B1[(R7)s=2 A6 1a4-la-694a-1ib649,6-2C1]
la4- ia650la4- ib650B1[(R7)s=2 A8 1a4-la-604a-1ib650,6-2C1] B1[(R7)s=3 A3
_____ _____ ____-2-COGH]
B1[(R7)s=3 A4 1a4-1la-652-la4-1 ib-652 A45,6-40 -2-COGH] B i[(R7),=3 A5/[(R6)r=2,3-2C1 Ia4-11ia-65 3-la4-11ib65 3 A45,6-40 -2-COGH] B1i[(R7)=3 A6 1a4-1ia-654-la4-1 ib-654 A45,6-40 -2-COGH] 1a4-11a-65 5-la41ib655 B2 A1/[(R2)=H (R3).=3,4-2F] la4-lla-656-la4-llb-656 B2 A3 la4-lla-657-la4-llb-657 B2 A4 Ia4-11a-658-la4-11b-658 B2 A6 1a4-la-659-la4-ib-659 B3 A1/[(R2)mH(R3)o=H] la4-lla-660-la4-llb-660 B3 A3 la4-lla-661-la4-llb-661 B3 A4 1a4-1a-662-la4-ib-662 B3 A5/[(R6)r=H] la4-lla-663-la4-llb-663 B3 A6 la4-lla-664-la4-llb-664 B4 A3 la4-lla-665-la4-llb-665 B4 A4 1a4-la-666-la4-lib-666 B4 A5/[(R6)r=H] la4-lla-667-la4-llb-667 B4 A6 1a4-la-668-la4-lib-668 B5 A1/[(R2)mH(R3)=4-C1] la4-lla-669-la4-llb-669 B5 A3 la4-lla-670-la4-llb-670 B5 A4 1a4-la-671-la4-lib-671 B5 A5/[(R6)r=H] 1a4-la-672-la4-lib-672 B5 A5/[(R6)=2-CH2CH3] 1a4-la-673-la4-1ib-673 B5 A5/[(R6)=2-OCH2CH3] 1a4-la-674-la4-1ib-674 B5 A5/[(R6)=2-OCH(CH3)2] 1a4-11a-675-la4ib675 B5 A5/[(R6)=3-CH2CH3] 1a4-la-676-la4-lib-676 B5 A5/[(R6)=3-OCH2CH3] 1a4-la-677-la4-1ib-677 B5 A5/[(R6)=3-OCH(CH3)2] la4-lla-678-la4-llb-678 B5 A6
1a4-la-679-la4-lib-679 B6/[R8=H; A3 R9=CF3]
1a4-la-680-la4-1ib-680 B6/[R8=H; A4 R9=CF3]
Ia4-11a-681-la4-11b-681 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
1a4-la-682-la4-1ib-682 B6/[R8=H; A5/[(R6)=2-CH2CH3] R9=CF3] Ia4-11a-683-la4-11b-683 B6/[R8=H; A5/[(R6)=2-OCH2CH3] R9=CF3] 1a4-la-684-la4-1ib-684 B6/[R8=H; A5/[(R6)=2-OCH(CH3)2]
R9=CF3] Ia4-11a-685-la4-11b-685 B6/[R8=H; A5/[(R6)r=3-CH2CH3] R9=CF3] 1a4-11a-686-la4-ib-686 B6/[R8=H; A5/[(R6)r=3-OCH2CH3] R9=CF3] 1a4-11a-687-la4-ib-687 B6/[R8=H; A5/[(R6)r=3-OCH(CH3)2] R9=CF3] B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH Ia4-11a-688~Ia4-iib-688 R9=CF3] (CH3)2] B6/[R8=H; A6 1a4-la-689-la4-1ib-689 R9=CF3] B6/[R8=H; A7 1a4-la-690-la4-1ib-690 R9=CF3] B6/[R8=C1 A3 1a4-la-691-la4-llb-691 ; R9=CH3] B6/[R8=C1 A4 1a4-la-692-la4-1ib-692 ; R9=CH3] 1a4-11a-693-la4-ib-693 B6/[R8=C1 A5/[(R6)r=H] ; R9=CH3] 1a4-1a-694-la4-iib-694 B6/[R8=C1 A5/[(R6)r=2-CH2CH3] ; R9=CH3] 1a4-la-695-la4-1ib-695 B6/[R8=C1 A5/[(R6)r=2-OCH2CH3] ; R9=CH3]
1a4-la-696-la4-1ib-696 B6/[R8=C1 A5/[(R6)r=2-OCH(CH3)2] ; R9=CH3]
1a4-la-697-la4-1ib-697 B6/[R8=C1 A5/[(R6)r=4-CHCH3CH2CH ; R9=CH3] (CH3)2] B6/[R8=C1 A6 1a4-la-698-la4-1ib-698 ; R9=CH3] B6/[R8=C1 A7 1a4-la-699-la4-1ib-699 ; R9=CH3]
1a4-la-700-la4-1ib-700 B6/[R8=H; A3 R9=CF3]
1a4-la-701-la4-llb-701 B6/[R8=H; A4 R9=CF3]
1a4-la-702-la4-1ib-702 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
1a4-la-703-la4-1ib-703 B6/[R8=H; A5/[(R6)r=2-CH2CH3] R9=CF3] 1a4-la-704-la4-1ib-704 B6/[R8=H; A5/[(R6)r=2-OCH2CH3] R9=CF3]
1a4-la-705-la4-1ib-705 B6/[R8=H; A5/[(R6)r=2-OCH(CH3)2] R9=CF3] Ia4-1ia-706-a4-ib-706 B6/[R8=H; A5/[(R6)r=4-CHCH3CH2CH
R9=CF3] (CH3 ) 2 ] B6/[R8=H; A6 1a4-1la-707-1a4-1 ib-707 R9=CF3] 1a4-1la-708-1a4-1 ib-708 B6/[R8=H; A7 R9=CF3] Ia4-ila-709-a4-ilb-709 B7 A3 Ia4-ila-710~I-a4-ilb-710 B7 A4 Ia4-1ia-711I-a4-1ib-711 B7 A5/[(R6)r=H] Ia4-1ia-712-a4-1ib-712 B7 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-ila-713-a4-ilb-713 B7 A6 Ia4-ila-714-a4-ilb-714 B7 A7 Ia4-ila-715-a4-ilb-715 B8 A3 Ia4-ila-716-a4-ilb-716 B8 A4 Ia4-1ia-717-a4-1ib-717 B8 A5/[(R6)r=H] Ia4-1ia-718-a4-1ib-718 B8 A5/[(R6)r=2,6-2Br-4-OCF3] Ia4-ila-719-a4-ilb-719 B8 A6 Ia4-ila-720-a4-ilb-720 B8 A7 Ia4-ila-721I-a4-ilb-721 B9 A3 Ia4-ila-722-a4-ilb-722 B9 A4 Ia4-1ia-723-a4-1ib-723 B9 A5/[(R6)r=H] Ia4-ila-724-a4-ilb-724 B9 A6 Ia4-ila-725-a4-ilb-725 B9 A7 Ia4-ila-726-a4-ilb-726 Bio A3 Ia4-ila-727-a4-ilb-727 Bio A4 Ia4-1ia-728-a4-1ib-728 Bio A5/[(R6)r=H] Ia4-1ia-729-a4-1ib-729 Bio A5/[(R6)r=3-C1-4 CH3 ] Ia4-lla-730-a4-llb-730 Bio A6 Ia4-lla-731-a4-lib-731 Bio A7 Ia4-lla-732-a4-llb-732 B1 A3 Ia4-lla-733-a4-llb-733 B1 A4 Ia4-ia-734-a4-ib-734 B1 A5/[(R6)r=H] Ia4-ia-735-a4-ib-735 B1 A5/[(R6)r=2,6-2CH3] Ia4-lla-736-a4-llb-736 B1 A6 Ia4-lla-737-a4-llb-737 B1 A7 Ia4-ia-738-a4-ib-738 HOC6H H A1/[(R2)m=H(R3)o=H] Ia4-lla-739-a4-llb-739 4C02 H A1/[(R2)m=H (R3)o=2-Cl] Ia4-ia-740-a4-ib-740 H A1/[(R2)m=H (R3)o=3-Cl] Ia4-ia-741-a4-1ib-741 H A1/[(R2)m=H (R3)o=4-Cl] Ia4-ia-742-a4-ib-742 H A1/[(R2)m=H (R3)o=3,4-2C] Ia4-ia-743-a4-ib-743 H A1/[(R2)m=H (R3)o=2-CH3] Ia4-ia-744-a4-ib-744 H A1/[(R2)m=H (R3)o=3-CH3] Ia4-ia-745-a4-ib-745 H A1/[(R2)m=H (R3)o=4-CH3] Ia4-ia-746-a4-ib-746 H A1/[(R2)m=H (R3)o=3,5-2CH3] Ia4-ia-747-a4-ib-747 H A1/[(R2)m=H (R3)o=4-X(CH3)3]
1a4-1la-748-la4-1 ib-748 H A/[(R2)m=H (R3)=4SCH3] 1a4-la-749-la4-ib-749 H A1/[(R2)=H (R3).=4-Br] 1a4-la-750-la4-ib-750 H A1/[(R2)=H (R3)=4-F] 1a4-ia-751K-la4-ib-751 H A1/[(R2)=H (R3)=3-F] 1a4-la-752-la4-ib-752 H A1/[(R2)=H (R3).=2,4-2F] 1a4-11a-753-la4ib753 H A1/[(R2)=H (R3).=3,4-2F] 1a4-11a-754-la4ib754 H A1/[(R2)=H (R3).=3,4,5-3F] 1a4-la-755-la4-1ib-755 H A/[(R2)m=H (R3)=4OCH3] 1a4-la-756-la4-1ib-756 H A/[(R2)m=H (R3)=3OCH3] 1a4-la-757-la4-1ib-757 H A1/[(R2)=H (R3)=4-CF3] 1a4-ia-758-la4-1ib-758 H A1/[(R2)=H (R3)=4-CN] 1a4-la-759-la4-ib-759 H A1/[(R2)m=4-F(R3).=H] 1a4-la-760-la4-1ib-760 H A/[(R2)m=4F(R3)=2-C1] 1a4-ia-761-la4-1ib-761 H A/[(R2)m=4F(R3)=3-C1] 1a4-la-762-la4-1ib-762 H A/[(R2)m=4F(R3)=4-C1] 1a4-la-763-la4-1ib-763 H A1/[(R2)m=4-F(R3)=3,4-2C] 1a4-la-764-la4-1ib-764 H A/[(R2)m=4F(R3)=2-CH3] 1a4-la-765-la4-1ib-765 H A/[(R2)m=4F(R3)=3-CH3] 1a4-la-766-la4-1ib-766 H A/[(R2)m=4F(R3)=4-CH3] 1a4-la-767-la4-1ib-767 H A1/[(R2)m=4-F(R3)=3,5-2CH3] 1a4-la-768-la4-1ib-768 H A1/[(R2)m=4-F(R3)=4-C(CH3)3] 1a4-la-769-la4-1ib-769 H Ai/[(R2)=4F(R3)=4-SCH3] 1a4-la-770-la4-ib-770 H A1/[(R2)m=4-F(R3),=4-Br] 1a4-ia-771-la4-ib-771 H A/[(R2)m=4F(R3)=4-F] 1a4-1a-772-la4-ib-772 H A1/[(R2)m=4-F(R3).=3-F] 1a4-la-773-la4-ib-773 H A/[(R2)m=4F(R3)=2,4-2f] 1a4-la-774-la4-ib-774 H A/[(R2)m=4F(R3).=3,4-2F] 1a4-11a-775-la4ib775 H A/[(R2)m=4F(R3).=3,4,5-3F] 1a4-la-776-la4-1ib-776 H A/[(R2)m=4F(R3)=4-OCH3] 1a4-la-777-la4-1ib-777 H A/[(R2)m=4F(R3)=3-OCH3] 1a4-la-778-la4-1ib-778 H A/[(R2)m=4F(R3)=4-CF3] la4-lla-779-la4-llb-779 H A/[(R2)m=4FR3)=4-CN] Ia4-11a-78OKla4-11b-78O H A2/N=site 3[(R4)pH(R5)q=H] Ia4-11a-781-la4-11b-781 H A2/[N=Site 3 (li)P=H(R5)q=2C] 1a4-11a-782-la4ib-782 H A2/[N=Site 3 (li)P=H(R5)q=3C] Ia4-11a-783-la4-11b-783 H A2/[N=Site 3 (li)P=H(R5)q4-C] Ia4-11a-784-la4-11b-784 H A2/[N=Site 3 (R4)P=H (R5)q=3,4-2C1] Ia4-11a-785-la4-11b-785 H A2/[N=Site 3(R4)P=H(R5)q=2CH3] Ia4-11a-786-la4-11b-786 H A2/[N=Site 3(R4)P=H(R5)q=3CH3] Ia4-11a-787-la4-11b-787 H A2/[N=Site 3(R4)P=H(R5)q=4CH3] Ia4-11a-788-la4-11b-788 H A2/[N=Site 3 (R4)P=H (R5)q=3,5-2CH3] Ia4-11a-789-la4-11b-789 _____H A2/[N=Site 3 (R4)P=H
(R5)q=4-C(CH3)3]
1a4-lla-790-1a4-llb-790 H A2/[N=site 3 (R4)P=H (R5)q=4-SCH3] Ia4-ila-791I-a4-ilb-791 H A2/[N=site 3 (R4)p=H (R5)q=4-Br] Ia4-ia-792-a4-iib-792 H A2/[N=site 3 (R4)p=H (R5)q=4-F] Ia4-lla-793-a4-llb-793 H A2/[N=site 3 (R4)p=H (R5)q=3-F] Ia4-ia-794-a4-iib-794 H A2/[N=site 3 (R4)p=H (R5)q=2,4-2F]
1a4-lla-795-a4-llb-795 H A2/[N=site 3 (R4)P=H (R5)q=3,4,5-3F]
1a4-lla-796-a4-llb-796 H A2/[N=site 3 (R4)P=H (R5)q=4-OCH3] 1a4-lla-797-a4-llb-797 H A2/[N=site 3 (R4)P=H (R5)q=3-OCH3] Ia4-lla-798-a4-llb-798 H A2/[N=site 3 (R4)p=H (R5)q=4-CF3] Ia4-ia-799-a4-iib-799 H A2/[N=site 3 (R4)p=H (R5)q=4-CN] Ia4-lla-800-a4-llb-800 H A3 Ia4-lla-801-a4-lib-801 H A4 Ia4-ia-802-a4-ib-802 H A5/[(R6)r=H] Ia4-ia-803-a4-ib-803 H A5/[(R6)r=2-CH3] Ia4-ia-804-a4-ib-804 H A5/[(R6)r=3-CH3] Ia4-ia-805-a4-ib-805 H A5/[(R6)r=2-CN] Ia4-ia-806-a4-ib-806 H A5/[(R6)r=2-CF3] Ia4-ia-807-a4-ib-807 H A5/[(R6)r=2,6-2CH3] Ia4-ia-808-a4-ib-808 H A5/[(R6)r=2-Cl-4-NO2] Ia4-ia-809-a4-ib-809 H A5/[(R6)r=2-NO2-4-CF3] Ia4-ia-810-a4-ib-810 H A/[(R6)r=2,3-2Cl-4-OH] Ia4-ia-811I-a4-ib-811 H A5/[(R6)r=2,6-2Cl-4-OCF3] Ia4-ia-812-a4-ib-812 H A5/[(R6)r=3-Cl-4-CH3] Ia4-ia-813-a4-ib-813 H A5/[(R6)r=3-OCH(CH3)2] H A5/[(R6)r=4-CHCH3CH2CH Ia4-ia-814~Ia4-1ib-814 (CH3) 2] Ia4-lla-815-a4-llb-815 H A6 Ia4-lla-816-a4-llb-816 H A7 Ia4-lla-817-a4-llb-817 H A8
Ia4-lla-818-a4-llb-818 B1[(R7),=2 A3 -I]
Ia4-1ia-819-a4-ilb-819 Bi[(R7),=2 A4 -I] 1a4-1la-820-1a4-1 ib-820 Bi[(R7)s=2 A5/[(R6)r=H] -I] Ia4-iia-821I-a4-ilb-821 B1[(R7),=2 A6 -I] Bi[(R7)s=2 A3 1a4-1la-822-1a4-1 ib-822 Ia4-iia-822~Ia4-iib-822 -CH3]
Bi[(R7)s=2 A4 1a4-1la-823-1a4-1 ib-823 -CH 3]
1a4-la-824-1a4-ib-824 Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH3)2] -CH 3] Bi[(R7)s=2 A6 1a4-la-825-1a4-1ib-825 -CH 3] Bi[(R7)s=2 A3 Ia4-1la-826~I1a4-ib-826 -CF3] Bi[(R7)s=2 A4 Ia4-1la-827~I1a4-ib-827 -CF3] Bi[(R7)s=2 A5/[(R6)r=3-OCH(CH 3) 2] Ia4-1la-828~I1a4-ib-828 -CF3] Bi[(R7)s=2 A6 1a4-la-829--1a4-llb-829 -CF3] Bi[(R7)s=2 A8 Ia4-lla-830~-1a4-llb-830 -CF3] Bi[(R7)s=2 A3 1a4-ia-831-la4-llb-831 ,6-2C1] Bi[(R7)s=2 A4 Ia4-lla-832~-1a4-llb-832 ,6-2C1] Bi[(R7)s=2 A6 1a4-lla-833-1a4-llb-833 ,6-2C1] Bi[(R7)s=2 A8 Ia4-lla-834~-1a4-llb-834 ,6-2C1] Bi[(R7)s=3 A3 Ia4-iia-835-Ia4-ilb-835 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 A4 Ia4-iia-836-Ia4-ilb-836 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 A5/[(R6)r=2,3-2C Ia4-iia-837-Ia4-ilb-837 ,4,5,6-4C1 -2-COOH] Bi[(R7)s=3 A6 Ia4-iia-838-Ia4-ilb-838 ,4,5,6-4C1 -2-COOH] Ia4-1ia-839-Ia4-ib-839 B2 A1/[(R2)m=H (R3)o=3,4-2F] Ia4-lla-840-a4-llb-840 B2 A3 Ia4-lla-841-a4-llb-841 B2 A4 Ia4-lla-842-a4-llb-842 B2 A6 Ia4-lla-843-a4-ib-843 B3 A1/[(R2)m=H (R3)o=H] Ia4-lla-844-a4-llb-844 B3 A3 Ia4-lla-845-a4-llb-845 B3 A4 Ia4-lla-846-a4-ib-846 B3 A5/[(R)r=H] la4-llia-847-la4-llib-847 B3 A6 Ia4-11ia-848-la4-11b-848 B4 A3 la4-llia-849-la4-llib-849 B4 A4 1a4-1ia-85OKla41 ib850 B4 A5/[(R6)r=H] Ia4-11ia-851-la4-11b-851 B4 A6 1a4-11ia-852-la4-1 ib-852 B5 A1/[(R2)=H (R3)=4-C1] Ia4-11a-853-la4-11b-853 B5 A3 Ia4-11a-854-la4-11b-854 B5 A4 1a4-11a-855-la4ib855 B5 A5/[(R6)r=H] 1a4-11a-856-la4ib856 B5 A5/[(R6)=2-CH2CH3] 1a4-11a-857-la4ib857 B5 A5/[(R6)=2-OCH2CH3] 1a4-1ia-858-la4-ib-858 B5 A5/[(R6)=2-OCH(CH3)2] 1a4-11a-859-la4ib859 B5 A5/[(R6)=3-CH2CH3] 1a4-la-860-la4-ib-860 B5 A5/[(R6)=3-OCH2CH3] 1a4-ia-861-la4-ib-861 B5 A5/[(R6)=3-OCH(CH3)2] la4-lla-862-la4-llb-862 B5 A6
1a4-11a-863-la4-ib-863 B6/[R8=H; A3 R9=CF3]
1a4-la-864-la4-1ib-864 B6/[R8=H; A4 R9=CF3]
1a4-11a-865-la4-ib-865 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
1a4-la-866-la4-1ib-866 B6/[R8=H; A5/[(R6)=2-CH2CH3] R9=CF3]
1a4-la-867-la4-1ib-867 B6/[R8=H; A5/[(R6)=2-OCH2CH3] R9=CF3]
Ia4-11a-868-la4-11b-868 B6/[R8=H; A5/[(R6)=2-OCH(CH3)2] R9=CF3]
1a4-11a-869-la4-ib-869 B6/[R8=H; A5/[(R6)=3-CH2CH3] R9=CF3]
1a4-11a-87OKla4-ib-870 B6/[R8=H; A5/[(R6)=3-OCH2CH3] R9=CF3]
1a4-1ia-871-la4-ib-871 B6/[R8=H; A5/[(R6)=3-OCH(CH3)2] R9=CF3] la4-ia-82-la-lib872B6/[R8=H; A5/[(R6)=4-CHCH3CH2CH 1a41la8724a41ib872R9=CF3] (CH3)2]
1a4-11a-873-la4-ib-873 B6/[R8=H; A6 R9=CF3]
1a4-la-874-la4-1ib-874 B6/[R8=H; A7 R9=CF3]
1a4-11a-875-la4-ib-875 B6/[R8=C1 A3 ;R9=CH3]
1a4-la-876-la4-1ib-876 B6/[R8=C1 A4 ________________R9=CH3]
1a4-11ia-877-la4-1 ib-877 B6/[R8=C1 A5/[(R6)r=H] ;R9=CH3] 1a4-11a-878-la4-ib-878 B6/[R8=C1 A5/[(R6)=2-CH2CH3] ;R9=CH3]
1a4-la-879-la4-1ib-879 B6/[R8=C1 A5/[(R6)=2-OCH2CH3] ;R9=CH3]
1a4-11a-88OKla4-ib-880 B6/[R8=C1 A5/[(R6)=2-OCH(CH3)2] ;R9=CH3]
1a4-1ia-881-la4-ib-881 B6/[R8=C1 A5/[(R6)=4-CHCH3CH2CH ;R9=CH3] (CH3)2]
1a4-11a-882-la4-ib-882 B6/[R8=C1 A6 ;R9=CH3]
Ia4-11a-883-la4-11b-883 B6/[R8=C1 A7 ;R9=CH3]
1a4-11a-884-la4-ib-884 B6/[R8=H; A3 R9=CF3]
Ia4-11a-885-la4-11b-885 B6/[R8=H; A4 R9=CF3]
Ia4-11a-886-la4-11b-886 B6/[R8=H; A5/[(R6)r=H] R9=CF3]
Ia4-11a-887-la4-11b-887 B6/[R8=H; A5/[(R6)=2-CH2CH3] R9=CF3]
1a4-11a-888-la4-ib-888 B6/[R8=H; A5/[(R6)=2-OCH2CH3] R9=CF3]
Ia4-11a-889-la4-11b-889 B6/[R8=H; A5/[(R6)=2-OCH(CH3)2] R9=CF3] la4-ia-80-la-lib890B6/[R8=H; A5/[(R6)=4-CHCH3CH2CH 1a41la890a4-ib-90R9=CF3] (CH3)2]
Ia4-11a-891-la4-11b-891 B6/[R8=H; A6 R9=CF3] 1a4-la-892-la4-1ib-892 B6/[R8=H; A7 R9=CF3] Ia4-11a-893-la4-11b-893 B7 A3 la4-lla-894-la4-llb-894 B7 A4 1a4-11a-895-la4ib895 B7 A5/[(R6)r=H] 1a4-la-896-la4-1ib-86 B7 A5/[(R6)r=2,6-2Br-4OCF3] la4-lla-897-la4-llb-897 B7 A6 Ia4-11a-898-la4-11b-898 B7 A7 la4-lla-899-la4-llb-899 B8 A3 la4-lla-900-la4-llb-900 B8 A4 1a4-la-901-la4-llb-901 B8 A5/[(R6)r=H] 1a4-la-902-la4-1ib-902 B8 A5/[(R6)r=2,6-2Br-4OCF3] la4-lla-903-la4-llb-903 B8 A6
la4-lla-904-la4-llb-904 B8 A7 la4-llia-905-la4-llib-905 B9 A3 la4-llia-906-la4-llib-906 B9 A4 1a4-1a-907-la4-1 ib-907 B9 A5/[(R6)r=H] la4-llia-908-la4-llib-908 B9 A6 la4-llia-909-la4-llib-909 B9 A7 la4-llia-91I0-la4-llib-9 10 Bio A3 la4-llia-9114-a4-llb-911 Bio A4 1a4-1 ia-912-la4-1 ib-912 Bio A5/[(R6)r=H] 1a4-1 ia-913-la4-1 ib913 Bio A5/[(R6)=3-Cl-4CH3] Wa-lla-9144a4-llb-914 Bio A6
Ia1a915-I1b-915 Bio A7
Wa-lla-916-Wa-llb-916 B11 A3 Wa-lla-917-Wa-llb-917 B11 A4 1a-ia-918-Wa4Iib918 B11 A5/[(R6)r=H] 1a-ia-919-Wa-ib-919 B11 A5/[(R6)r=2,6-2CH3] 1 T6 1a-lla-9204a4-llb-920
[1a-1la-921-Wa-llb-921 tn A7
The compound of formula Iof the present invention can be inparticular selected from
the compounds numbered as follows. Ph Ph 0 Ph, 0 Ph, 1 Ph, I Ph I WQ, Ph< Ph" S r n r n.y n Ibna Jbnb lbnc
Clb= Cjc= Cjd= & 0 C 2= Ik OCk NHCH, OCH, NHCH, OCH, NI CH HC0- N HC0-N HC0'C HC0'C OCH,
C 3a 3C 3b IC3CC HH ~= 0OHC4
ONHCH ( IA AH3H& 3 N CH NN CH CH N 0C 3 H3 C0 H3 C0 H 3 C0 H3 C0' 0CH3
Number Y Q2
lb4- ia-1I4-b4-1 IC-1I Br C1. Nb-Iia-2-Nb4Iic-2 CIb
Nb-Iia-3-Nb4Iic-3 Cic
Nb-Iia-4-Nb4Iic-4 CId
TN-ila-5--4-ic-5 C2
TN-ia-64b4-1ic-6 C3.
TNt-ia-7--4-ic-7 COb
TN-Iia-8--4-ic-8 C3c
TN-Iia-9--l4IiC-9 C3d
1b-Iia-1O--l I4-ic10 C4
1b-Iia-11--lC-I Ic1 AcO Cia 1b-Iia-12--4Iic-12 Cib
1b-Iia-13--4Iic-13 Cic
1b-Iia-14--4Iic-14 Cid
1b-Iia-15--4Iic-15 C2
1b-Iia-16--4Iic-16 C3.
1b-Iia-17--4Iic-17 COb
1b-Iia-18--4Iic-18 C3c
1b-Iia-19--b4I C-1 9 C3d
TN-Iia-20---Iic-20 C4
1b-Iia-21--4Iic-21 TsO Cia
TN-Iia-22--bIic-22 Cib
TN-Iia-234b4-iic-23 Cic
N-Iia-24--bIic-24 Cid
N-Iia-25---Iic-25 C2
N-Iia-26--bIic-26 C3.
N-Iia-27--bIic-27 COb
N-Iia-28---Iic-28 C3c
N-Iia-29--bIic-29 C3d
TN-iia-30--bIic-30 C4
1b-Iia-31--4Iic-31 PhCO2 Cl.
TN-iia-32--bIic-32 Cib
TN-iia-33---iic-33 Cic
IN-iia-34~b4-Iic-34 Cid
IN-iia-35~b4-Iic-35 C2
IN-iia-36~Ib4-Iic-36 C3a
IN-iia-37~Ib4-Iic-37 C3b IN-iia-38~b4-Iic-38 C3c
TNI-iia-39~Ib4-Iic-39 C3d
TNI-iia-40~Ib4-Iic-40 C4
TNI-iia-41~Ib4-Iic-41 HOC6H4CO2 Cia
TNI-iia-42~Ib4-Iic-42 Cib
TNI-iia-43~Ib4-Iic-43 Cic
TNI-iia-44~Ib4-Iic-44 Cid
TNI-iia-45~b4-Iic-45 C2
TNI-iia-46~Ib4-Iic-46 C3a
TNI-iia-47-b4-iic-47 C3b IN-iia-48~b4-Iic-48 C3c
IN-iia-49-b4-iic-49 C3d
IN-iia-50-b4-iic-50 C4
Another objective of the present invention is to provide a preparation method of the above phosphonium salt compounds (the compound as shown in formula I). The preparation method of the phosphonium salt compounds (the compound as shown in formula I) provided by the present invention includes the step of carrying out a nucleophilic reaction between a compound shown in formula VII and triphenylphosphine, in an organic solvent in the presence or absence of a catalyst, to obtain the compound as shown in formula I.
n formula VII
In formula VII, the definitions of Y, Q, X, and n are the same as those in formula I. In the above preparation method, the catalyst is sodium iodide or potassium iodide. The molar ratio of the catalyst to the compound as shown in formula VII may be (0.01-0.1): 1. The reaction temperature of the nucleophilic reaction may be in the range from 25 to 180 °C, preferably in the range from 80 to 115 °C, and in particular may be 82 °C. The reaction time is in the range from 4 to 24 h, and in particular may be in the range from 8 to 12 h. The molar ratio of the compound as shown in formula VII to triphenylphosphine may be 1: (1-2), and in particular may be 1: (1-1.3). The organic solvent may be at least one selected from the group consisting of acetonitrile, glycol dimethyl ether, benzene, toluene, and 1,2-dichloroethane. The nucleophilic reaction can be carried out in the following steps: performing vacuumization and nitrogen filling of the bottle containing catalyst, triphenylphosphine and the compound as shown in formula VII, and magneton; adding the organic solvent under the protection of nitrogen, followed by stirring at room temperature for 5-10 min, and then reacting at temperatures in the range from 80 to 115 °C for 8-12 h to obtain the compound as shown in formula I. In the above preparation method, the compound as shown in formula VII is prepared as follows: reacting a compound shown in formula IV (or a compound shown in formula V) with a compound shown in formula VI in an organic solvent in the presence of a catalyst (or an acid binding agent) to obtain the compound as shown in formula VII.
H Q NAr Q 2-Br/SH n
formula IV formula V formula VI In formula IV, the definitions of Qi and Ar are the same as those in formula Ia; in formula V, the definition of Q2 is the same as that in formula Ib; in formula VI, the definitions of X, Y, and n are the same as those in formula I; and the definition of U is the same as that in formula lb. When formula IV reacts with formula VI, U is OC=O group. In the above preparation method, the acid binding agent may be selected from the group consisting of pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, NMM (N-methylmorpholine), and NaH; and the catalyst may be selected from the group consisting of EDCI/HOBT, CDI, DMAP/DCC, HATU/DIPEA, DIC, etc.
The molar ratio of the acid binding agent to the compound as shown in formula IV may be (2-5): 1, and particularly can be (2-3): 1. The molar ratio of the catalyst to the compound as shown in formula IV may be (1-2.5): 1, and particularly can be (1.2-2): 1. The molar ratio of the compound as shown in IV to the compound as shown in formula VI may be 1: (1-2), and particularly can be 1:1.05. The molar ratio of the acid binding agent to the compound as shown in formula V may be (2-5): 1, and particularly can be (2-3): 1. The molar ratio of the catalyst to the compound as shown in formula V may be (1-2.5): 1, and particularly can be (1.2-2): 1. The molar ratio of the compound as shown in V to the compound as shown in formula VI may be 1: (1-2), and particularly can be 1:1.05. The reaction temperature may be in the range from -20 to 35 °C, and the reaction time may be in the range from 1 to 6 h. The organic solvent may be selected from the group consisting of dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide (DMF), 1,4-dioxane, and toluene. The reaction may be carried out according to the following steps (taking the reaction between the compound as shown in formula IV and the compound as shown in formula VI as an example): performing vacuumization and nitrogen filling of the bottle containing the compound as shown in formula IV, catalyst DMAP/DCC, and magneton; adding the organic solvent under the protection of nitrogen; reducing the temperature to -10 °C in an ice salt bath, followed by stirring for 5-10 min; then diluting the compound of formula V into the solvent, which is dropwise added into the reaction bottle slowly, followed by reactions for 0.5-4 h, to obtain the compound as shown in formula VII.
Ar-NH 2 Q1 -C1 formula II formula III
In the above preparation method, the compound as shown in formula IV may be prepared as follows: reacting the compound as shown in formula II and the acid binding agent with the compound as shown in formula III in an organic solvent to obtain the compound as shown in formula IV. In formula II, Ar is defined as in formula I; in formula III, Ri is defined as in formula I. In the above preparation method, the acid binding agent may be selected from the group consisting of pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, and NaH.
The molar ratio of the catalyst to the compound as shown in formula II may be (2-5): 1, and particularly can be (2-3): 1. The molar ratio of the compound as shown in II to the compound as shown in formula III may be 1: (1-1.2), and particularly can be 1:1.05. The reaction temperature may be in the range from -20 to 35 °C, and the reaction time may be in the range from 1 to 6 h. The organic solvent may be selected from the group consisting of dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide (DMF), 1,4-dioxane, and toluene. The reaction can be particularly carried out in the following steps: performing vacuumization and nitrogen filling of the bottle containingthe acid binding agent and the compound as shown in formula II, and magneton; adding an organic solvent under the protection of nitrogen; reducing the temperature to -10 °C under an ice salt bath, followed by stirring for 5-10 min; then diluting the compound of formula III into the solvent, which is then dropwise added into the reaction bottle slowly, followed by reaction for 0.5-4 h, to obtain the compound as shown in formula IV. The compounds of formula II, formula III, formula V, and formula VI in the present invention can be purchased commercially or obtained through one-step reactions from raw materials. For example, the compound of formula II can be in particular 2-aminobiphenyl comprising various substituents, arylpyridylamines comprising various substituents, anilines comprising various substituents, benzylamines comprising various substituents, and various heterocyclic amines comprising various substituents. the compound as shown in formula III can be obtained through one-step reactions of various substituted benzoic acids, phenylacetic acids, heterocyclic acids, and the like. The present invention further seeks protection of a fungicide composition and a preparation method thereof. The composition comprises the phosphonium salt compound (the compound as shown in formula I) and an agriculturally acceptable carrier, wherein the phosphonium salt compound (active ingredient) in the single agent has a mass percentage content of 0.1-99%, which can be specifically 30-60%. The phosphonium salt compound can be either a single compound of the present invention or a mixture of several compounds of the present invention. The preparation method of the fungicide composition provided by the present invention comprises the following steps: mixing the phosphonium salt compound (the compound as shown in formula I) and an agriculturally acceptable carrier uniformly to obtain the fungicide composition.
The agriculturally acceptable carrier has the following characteristics: 1) after being formulated with an active ingredient, it can be readily administered to a site to be treated such as a plant, a seed or soil; 2) it is convenient for storage, transportation, or operation; and 3) it can be a solid or liquid, including a substance which is usually a gas but has been compressed into a liquid. In a word, all the carriers commonly used in the preparation of agricultural fungicides can be used in the present invention. The agriculturally acceptable carrier can be in particular selected from a solid carrier and/or a liquid carrier. The solid carrier may be at least one selected from the group consisting of a natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum silicate oxide, a natural or synthetic resin, polychlorophenol, starch, bentonite, and wax, wherein the natural or synthetic silicate particularly can be at least one selected from the group consisting of magnesia, talc, aluminum silicate, diatomite, mica, montmorillonite, and calcium silicate; the natural or synthetic resin can be at least one selected from the group consisting of benzofuran resin, a styrene polymer (with a molecular weight in the range from 50,000-200,000), and a styrene copolymer (such as a styrene-butadiene copolymer); and the wax can be selected from the group consisting of beeswax and/or paraffin. The liquid carrier may be at least one selected from the group consisting of water, CI-C4 alcohols, C3-C8 ketones, aromatic hydrocarbons, petroleum fractions, and C-C12 chloroalkanes, wherein the alcohol can in particular be ethanol and/or glycol; the ketone can in particular be at least one selected from the group consisting of acetophenone, acetone, methyl ethyl ketone, and cyclohexanone; the aromatic hydrocarbon can in particular be at least one selected from the group consisting of benzene, toluene, and xylene; the petroleum fraction can in particular be kerosene and/or mineral oil; and the chloroalkane can in particular be at least one selected from the group consisting of carbon tetrachloride, dichloromethane, and trichloroethane. The general fungicide composition is usually processed into the form of a concentrate for transport, and diluted by the user prior to administration. In order to facilitate dilution, the fungicide composition provided by the present invention can also comprise a surfactant. The added amount of the surfactant may be an acceptable amount in agricultural fungicides. The surfactant can be at least one selected from the group consisting of an emulsifier, a dispersant, a wetting agent, and a penetrant.
The emulsifier can be at least one selected from the group consisting of agricultural pesticide emulsifier #500 (calcium alkylbenzenesulfonate), agricultural pesticide emulsifier #600 phosphate (phenylphenol polyoxyethylene ether), agricultural pesticide emulsifier #700 (alkylphenol formaldehyde polyoxyethylene ether), agricultural pesticide emulsifier #1600 (phenylethyl phenol polyoxyethylene polypropylene ether), polyoxyalkenylenealkylaryl ethers, and ethylene oxide-propylene oxide block copolymers. The dispersant can be at least one selected from the group consisting of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, an alkylbenzene sulfonate calcium salt, a benzenesulfonate formaldehyde condensate sodium salt, sodium lauryl sulfate, sodium castor oil sulfate, sodium alkylaryl sulfonate, alkylphenol polyoxyethyleneether, polyoxyethylene fatty acid, and ester polyoxyethylene ether. The wetting agent can in particular be at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzenesulfonate, nekal BX, saponin powder, silkworm sand, and sapindus powder. The penetrant can in particular be at least one selected from the group consisting of siloxane polyoxyethylene ether, sulfonic alkylaryl ester, alcohol ether succinate, and phenol ether succinate. Of course, in the fungicide composition of the present invention, other auxiliary agents can be added appropriately. The added amount of the other auxiliary agents can be an acceptable amount in agricultural fungicides. The other auxiliaries can be at least one selected from the group consisting of a disintegrating agent, a defoamer, an antifreeze, and a thickener. The disintegrating agent is at least one selected from the group consisting of bentonite, urea, ammonium sulfate, aluminum chloride, and glucose. The defoamer is at least one selected from the group consisting of silicone oil, a silicone compound, a C1O-C20 saturated fatty acid compound, and a C-Cio fatty alcohol compound. The antifreeze is at least one selected from the group consisting of glycol, propylene glycol, glycerol, and polyethylene glycol. The thickener is at least one selected from the group consisting of xanthan gum, polyvinyl alcohol, and polyethylene glycol. The fungicide composition prepared by the present invention can be added with corresponding components according to a method known to a person skilled in the art, thus to prepare various formulations such as a wettable powder, a powder, a granule, a concentrated emulsion, emulsifiable oil, a suspending agent, aerosol, or aerosol. At the same time, based on different crops and diseases, effective amounts of the fungicide composition of the present invention can be administered by foliar spray, seed treatment, or soil treatment. The present invention further seeks protection of a composition comprising at least two active components. The active components of the composition comprise the phosphonium salt compound (the compound as shown in formula I) and at least another active compound. Said another active compound can be at least one selected from the group consisting of known fungicides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safety agents, and chemical pheromones, further preferably fungicides and insecticides. The composition is a fungicidal composition, which refers to a composition prepared by the compound as shown in formula I and one or several other fungicides, and a formulation thereof, for expanding the prevention and cure scope of the product. Said other fungicides include: 2-(thiocyanatomethylthio)-benzothibzole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, diphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, bordeaux mixture, boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, cycloimide, carvone, chloroneb, chlorothalonil, chlozolinate, coniothyrium minitans, copper hydroxide, copper isooctanate, copper oxychloride, cupric sulfate, cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diethyl metformin, dichlofluanid, dichlorophen, diclocymet, diclomezin, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianone, dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, chloroquine, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidine, fenpropimorph, fenpyrazamine, triphenyltin, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-alumin, furathiocarb, furalaxyl, furametpyr, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iminoctadine acetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, metalaxyl, metalaxyl-M, mepanioyrim, meproil, metham-sodium, metconazole, methasulfocarb, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, fenfuram, oleic acid, orysastrobin, oxadixyl, oxine-copper, oxpoconazole-fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenol laurate, penthiopyrad, phthalide, picoxystrobin, polyoxins, polyoxorim, thiabendazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyraclostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyrimorph, pyriofenone, chloroqualone, quinoclamine, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, sodium pentachlorophenol, spiroxamine, sulfur, tebuconazole, isobutyl ethoxyquinoline, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valeriamine, valifenalate, vinclozolin, zineb, ziram, zoxamide, Fusarium oxysporum, benodanil, benquinox, phenamacril, benzamorf, binapacryl, buthiobate, carbamorph, chlobenthiazone, chloraniformethan, phenyl imidazole bacteria, chlorquinox, cyflufenamid, cyanazin, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, plondrel, dodicin, drazoxolon, etaconazole, dexon, propanenitrile, fenitropane, fluotrimazole, furoxime, furconazole, furmecyclox, furophanate, griseofulvin, quinoline acrylate, cyclohexanol sulfur phosphorus, isopamphos, chlorphenicone, mepronil, mecarbinzid, mechlorobactone, methfuroxam, metsulfovax, milneb, mucochloric anhydride, myclozolin, natamycin, phosdiphen, prothiocarb, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol, quinazolamide, fluquinconazole, rabenzazole, salicylanilide, sultropen, thiadifluor, thicyofen, thiochlorfenphim, thioquinox, thiocyanin benzamide, triamiphos, triarimol, triazbutil, trichlamide, urbacid, fenoxanil, etc. The composition is a fungicidal and insecticidal composition, which refers to a composition prepared by the compound as shown in formula I and one or several other insecticides, and a formulation thereof, for expanding the prevention and control scope of the product. Said other insecticides include avermectin, acephate, acetamiprid, acethion, acetoprole, fenvalerate, alanycarb, aldicarb, aldicarb sulfone, allethrin, allosamidin, allyxycarb, a-cypermethrin, a-ecdysone, endosulfan, amidithion, aminocarb, amiton, phoxim, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinos, azinphos-methyl, azothoate, barthrin, bendiocarb, benfuracarb, bensultap, p-cyfluthrin, p-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, bromfenvinfos, bromocyclen, bromophos, bufencarb, buprofenzin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, toxaphene, carbanolate, carbaryl, mitarway, carbophenothion, benfuracarb, padan, chlorantraniliprole, borneol, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, butazone, chlormephos, nitrochloroform, chlorphoxim, clopidophos, chlorpyrifos, chlorpyrifos-methyl, phosphite, chromafenozide, cinerin, cismethrin, cloethocarb, closantel, clothianidin, coumaphos, toxicphos, crotamiton, ciodrin, crufomate, surecide, cyanophos, cyanthoate, cyantraniliprole, cypermethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, carbofuran, deltamethrin, demephion, demephion, thiotephos, systox, demeton-S-methyl, diafenthiuron, dialifos, diazinon, dicapthon, dichlofention, dichlorvos, phosphor, dicyclanil, dieldrin, diflubenzuron, dimefluthrin, dimefox, dimetan, dimethoate, pyrethrin, dimethylvinphos, dimetilan, phenol, propanol, dinosam, dinotefuran, diofenolan, salithion, dioxacarb, delnav, disulfoton, thiofuran, doramectin, ecdysterone, emamectin, empenthrin, endosulfan, endothion, endrin, epofenonane, eprinomectin, allethrin, fenvalerate, ethiofencarb, diethion, ethiprole, ethoprophos, ethofenprox, etrimfos, famphur, phenamiphos, phenylester, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, tau-fluvalinate, fonofos, formetanate, formothion, formparanate, fosmethilan, fosthietan, furathiocarb, furethrin, y-cyhalothrin, halfenprox, halofenozide, heptachlor, heptenophos, heterophos, hexaflumuron, hydramethylnon, hydroprene, quinoline, imidacloprid, imiprothrin, indoxacarb, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isoprocorb, isoprothiolane, isofenphos, isoxathio, ivermectin, jasmonate, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, pronoprotein, reomycin, leptophos, acetamiprid, lufenuron, quinazoline, malathion, mitaconitrile, mazidox, mecarbam, mecarphon, azidithion, mephosfolan, fenthionsulfoxide, metaflumizone, methacrifos, methamidopho, methidathion, mesurol, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, tsumacide, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, propylene phosphorus fluoride, mirex, monosultap, monocrotophos, phosphorodithioicacid, moxidectin, naftalofos, dibrom, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, penfluron, permethrin, henkapton, permethrin, phenthoate, thimet, phosalone, phosfolan, phosemet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, aphid resistant phosphorus, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, precocene I, precocene II, precocene III, amidopyrimiphos, profenofos, trifluralin, promacyl, phenol, propaphos, propetamphos, propoxur, ethyl thiazolium, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridalyl, pyridaphenthione, pyrifluquinazon, pyrimidifen, pirimiphos-ethyl, pyriprole, pymetrozine, pyripropoxyfen, mersosin, quinalphos, methyl quinalphos, quinothion, rafoxanidum, rotenone, ryanodine, sabadilla, schradan, selamectin, silafluofen, formocarbam, spinosad, spinetoram, spirodiclofen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulphurtap, tau-fluvalinate, tazimcarb, tebufenozide, tebufenpyrad, tebupirimfos, eflubenzuro, tefluthrin, temephos, methenthrin, tertap, insecticide, tetramethrin, meperfluthrin, beta-cypermethrin, thiacloprid, thiamethoxam, quinoline phosphorus, thiocarboxime, thiocyclam, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon, bisultap, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, triarathene, triaguron, triazophos, dipterex, trichlormetaphos-3, trichloronate, phosphorus oxychloride, triflumuron, trimethacarb, triprene, vamidothion, flurozole, xylylcarb, triazophos, etc. Further, use of the compound as shown in formula I and the composition comprising the compound as shown in formula I in the preparation of a fungicide also fall within the protection scope of the present invention. The compound as shown in formula I of the present invention has broad-spectrum and excellent fungicidal activity, and can be used for prevention and cure of diseases caused by four major pathogenic fungi, i.e., ascomycetes, basidiomycetes, deuteromycotina, and oomycetes, on a variety of crops. Good prevention and cure effects can be obtained at very low doses. At the same time, such compounds as shown in formula I have certain absorbability and can be used as leaf and soil fungicides to prevent and cure diseases on a variety of crops. The following diseases can be particularly prevented and cured: phytophthora blight of pepper, tomato early blight, tomato late blight, tomato gray mold, rice blastwheat leaf spot, ring spot, rice sheath blight, rice false smut, rice bakanae disease, wheat powdery mildew, wheat fusarium head blight, rape sclerotinia rot, cucumber downy mildew, cucumber blight, cucumber gray mold, cucumber powdery mildew, apple powdery mildew, watermelon anthracnose, cercospora brown spot of peanut, rot of melon and fruit, damping-off and cottony leak of melon, cotton blight, cotton verticillium wilt, cotton damping-off.
Brief Description of Drawings Fig. 1 is a flow chart for the preparation of the compound as shown in formula I.
Detailed Description of Embodiments In the following, the present invention will be described through specific examples. However, the present invention is not limited to this. Any amendment, equivalent replacement, improvement, and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, and the like used in the following examples can be obtained commercially unless otherwise specified. I. The preparation examples of the compounds as shown in formula I are provided as follows, and the corresponding preparation flow chart is shown in Fig. 1.
Example 1 Preparation of compound Ia8a-1 (i.e., compound as shown in formula Iana, wherein n=8, Y=Br, Qi=H, Ar=A/[(R2)m=H, (R3)o=H]) 1. Preparation of N-[(1,1'-biphenyl)-2-yl]-11-bromoundecylamide A 250 mL three-necked bottle was taken, into which 2 g (9.13 mmol) of 2-iodoaniline, 1.3 g (10.96 mmol) of phenylboronic acid, and 2.5 g (18.26 mmol) of potassium carbonate were added. 120 mL of a mixed solution with toluene: ethanol: water =10:1:1 was added, followed by stirring. 300 mg (0.26 mmol) of tetra(triphenylphosphine) palladium was then added. After full reaction under heat and reflux for 8 hours, 1.4 g of o-aminobiphenyl was obtained at a yield of 91%. 1 g (3.77 mmol) of I1-bromoundecanoic acid, EDCI (0.72 g, 3.77 mmol), and HOBT (0.5 g, 3.77 mmol) were added into a 100 mL round-bottom flask, and 40 mL of dichloromethane was added to react for 15 min. Then o-aminobiphenyl (0.61 g, 3.6 mmol) and NMM (0.77 g, 7.55 mmol) were added. After reactions for 4 hours, 1.35 g of N-[(1,1'-biphenyl)-2-yl]-11-bromoundecanoamide was obtained at a yield of 86% 1H NMR (300 MHz, CDC3) 6 8.21 (d, J=8.2 Hz, 1H), 7.45-7.24 (m, 6H), 7.17-7.13 (m, 1H), 7.12-7.04 (m, 2H), 3.32 (t, J=6.8 Hz, 2H), 2.10 (t, J=7.5 Hz, 2H), 1.84-1.68 (m, 2H), 1.54-1.42 (m, 2H), 1.38-1.28 (m, 2H), 1.18 (s, 10H). 13 C NMR (75 MHz, CDCl3) 6 170.86, 137.88, 134.45, 131.82, 129.65, 128.95, 128.72, 128.08, 127.63, 123.86, 121.24, 37.48, 33.66, 32.48, 29.01, 28.95, 28.91, 28.74, 28.39, 27.81, 25.10. 2. Preparation of compound Iaa-1 0.6 g (1.45 mmol) of N-[(1,1'-biphenyl)-2-yl]-11-bromoundecanoamide, 0.5 g (1.9 mmol) of triphenylphosphine, 12 mg (0.72 ummol) of potassium iodide and magneton were added into a 100 mL three-necked bottle, followed by vacuumization and nitrogen filling. 30 mL of acetonitrile was added under the protection of nitrogen, followed by stirring at room temperature for 5-10 min, and refluxing under heating at 90 °C for 12 h. Column chromatography was performed for separation to obtain 0.87 g of white solid powder at a yield of 90%. Confirmation data of structural formula were as follows. 'H NMR (300 MHz, CDC3) 6 8.11 (d, J=8.2 Hz, 1H), 7.78-7.59 (m, 15H), 7.43-7.30 (m, 3H), 7.27-7.18 (m, 4H), 7.14 (dd, J=7.6, 1.6 Hz, 1H), 7.06 (t, J=7.4 Hz, 1H), 3.47 (s, 2H), 2.08 (t, J=7.5 Hz, 2H), 1.61-1.37 (m, 6H), 1.21-1.04 (m,1OH). 13 C NMR (75 MHz, CDCl3) 6 170.94, 137.32, 134.74, 134.69, 134.48, 133.28, 133.14, 132.19, 130.25, 130.08, 129.63, 129.33, 128.62, 127.62, 123.81, 121.38, 118.42, 117.28, 37.25, 30.09, 29.89, 28.77, 28.74, 28.65, 28.57, 24.98, 22.74, 22.23, 22.18, 22.08. The compounds numbered Ia4-1a-1-a4-1b-1 to Ia4-lla-80~a4-llb-80 were each prepared with reference to the method in Example 1. The NMR data of some of the compounds were as follows. The 1H NMR and 13 C NMR of compound Ia8a-3 were as follows. 1H NMR (300 MHz, CDC3) 6 7.93 (d, J=8.0 Hz, 1H), 7.76-7.56 (m, 15H), 7.40-7.27 (m, 2H), 7.25-7.13 (m, 4H), 7.13-7.02 (m, 2H), 3.54-3.35 (m, 2H), 2.10 (t, J=7.5 Hz, 2H), 1.63-1.33 (m, 6H), 1.21-0.99 (m, 1OH). 13 C NMR (75 MHz, CDCl3) 6 171.22, 139.94, 134.85, 134.82, 134.23, 134.15, 133.27, 133.14, 130.33, 130.16, 129.89, 129.51, 128.77, 128.27, 127.49, 127.01, 124.47, 122.94, 118.19, 117.06, 37.12, 30.11,29.90,28.71,28.61,28.58,25.04,23.02,22.35,22.17,22.11. The 1H NMR and 13 C NMR of compound Ia8a-5 were as follows. 1H NMR (300 MHz, CDCl3) 6 7.79-7.57 (m, 15H), 7.37 (dd, J=8.3, 5.1 Hz, 2H), 7.24-7.15 (m, 2H), 7.13-7.06 (m, 2H), 3.51-3.30 (m, 2H), 2.15 (t, J=7.5 Hz, 2H), 1.62-1.33 (m, 6H), 1.24-0.97 (m, 1OH). 13 C NMR (75 MHz, CDCl3) 6 171.55, 138.69, 134.89, 134.85, 134.20, 133.26, 133.13, 132.35, 132.10, 131.17, 130.50, 130.34, 130.27, 130.18, 129.48, 128.46, 128.33, 125.03, 124.40, 118.18, 117.04, 36.87, 30.09, 29.88, 28.67, 28.59, 28.48, 25.08, 23.03, 22.36, 22.16, 22.10. The 1H NMR and 13 C NMR of compound Ia8a-21 were as follows. 1H NMR (300 MHz, CDCl3) 6 8.12 (s, 1H), 7.79-7.59 (m, 16H), 7.51 (dd, J=30.9, 8.3 Hz, 4H), 7.22 (dd, J=7.7, 4.0 Hz, 1H), 7.14 (d, J=4.2 Hz, 2H), 3.47-3.31 (m, 2H), 2.16 (t, J=7.4 Hz, 2H), 1.67-1.45 (m, 4H), 1.45-1.31 (m, 2H), 1.28-1.01 (m,1OH).
C NMR (75 MHz, CDCl3) 6 171.75, 144.03, 134.92, 134.88, 134.16, 133.26, 133.13, 131.84, 130.35, 130.18, 129.62, 129.44, 128.66, 125.41, 118.56, 118.18, 117.04, 110.37, 36.60, 30.09,29.89,28.67,28.64,28.54,28.41,25.01,22.98, 22.32,22.15,22.09. The 1 H NMR and 13 C NMR of compound Ia8a-26 were as follows. 'H NMR (300 MHz, DMSO) 6 8.80 (s, 1H), 7.78-7.57 (m, 15H), 7.47 (dd, J=8.7, 5.4 Hz, 1H), 7.37 (d, J=2.0 Hz, 1H), 7.35-7.28 (m, 1H), 7.25 (dd, J=8.3, 2.0 Hz, 1H), 6.84 (ddd, J=11.8, 8.4, 2.9 Hz, 2H), 3.54-3.25 (m, 2H), 2.18 (t, J=7.5 Hz, 2H), 1.65-1.45 (m, 4H), 1.45-1.29 (m, 2H), 1.26-1.00 (m, 1OH). 13 C NMR (75 MHz, CDCl3) 6 172.22, 161.45, 158.20, 138.26, 136.25, 134.85, 134.82, 133.18, 133.05, 131.81, 131.18, 130.61, 130.28, 130.11, 130.02, 128.15, 118.26, 117.12, 116.05, 115.75, 114.88, 114.59, 36.25, 30.00, 29.80, 28.57, 28.51, 28.33, 25.04, 22.78, 22.12. Example 2 Preparation of compound Ia8a-115 (i.e., compound as shown in formula Iana, wherein n=8, Y=Br, Ql=B, Ar=Al/[(R2)m=H, (R3)=4-Cl]) 1. Preparation of 2-chloro-N-(4-chlorobiphenyl-2-yl)-N-(11-bromoundecanoyl) nicotinamide 1 g (3.77 mmol) of 11-bromoundecanoic acid, EDCI (0.72 g, 3.77 mmol), and HoBt (0.5 g, 3.77 mmol) were added into a 100 mL round-bottom flask, and 40 mL of dichloromethane was then added to react for 15 min. 1.24 g (3.6 mmol) of Boscalid {2-chloro-N-(4'-chloro-[1,1'-biphenyl]-2-yl) nicotinamide} was then added. After reactions of 4 hours, 1.5 g of 2-Chloro-N-(4-chlorobiphenyl-2-yl)-N-(11-bromoundecanoyl) nicotinamide was obtained at a yield of 93%. Confirmation data of structural formula were as follows. 1H NMR (300 MHz, CDC3) 6 8.40 (dd, J=4.8, 1.9 Hz, 1H), 7.59-7.39 (m, 7H), 7.33-7.24 (m, 3H), 3.42 (t, J=6.8 Hz, 2H), 2.39-2.23 (m, 1H), 2.05 (d t, J=17.3, 7.2 Hz, 1H), 1.94-1.80 (m, 2H), 1.50-1.04 (m, 15H). 13 C NMR (75 MHz, CDCl3) 6 174.45, 168.36, 149.49, 145.31, 139.63, 136.13, 136.05, 135.08, 134.20, 133.52, 130.97, 129.69, 129.64, 129.21, 129.13, 128.60, 121.91, 36.58, 33.71, 32.46, 28.94, 28.84, 28.82, 28.46, 28.34, 27.78, 23.64. 2 Preparation of compound Iaa-115 0.78 g (1.32 mmol) of 2-chloro-N-(4'-chloro-[1,1'-biphenyl]-2-yl)-N-(11-bromondecanoyl)-nicotinamide, 0.53 g (2 mmol) of triphenylphosphine, 12 mg (72 ummol) of potassium iodide and magneton were added into a 100 mL three-necked bottle, followed by vacuumization and nitrogen filling. Under the protection of nitrogen, 30 mL of acetonitrile was added, followed by stirring at room temperature for 5-10 min, and reflux under heating at 90 °C for 10 h. Column chromatography was performed for separation to obtain 1 g of white solid powder at a yield of 88%. Structure confirmation data were as follows. 'H NMR (300 MHz, CDC3) 6 8.23 (dd, J=4.8, 1.9 Hz, 1H), 7.74-7.57 (m, 15H), 7.47-7.14 (m, 10H), 3.60-3.42 (m, 2H), 2.28-1.79 (m, 2H), 1.48 (4, 6H), 1.25-0.87 (m, 12H). 13 C NMR (75 MHz, CDCl3) 6 174.42, 168.27, 149.35, 145.29, 139.46, 136.01, 135.96, 134.90, 134.73, 134.69, 134.02, 133.47, 133.27, 133.13, 130.94, 130.24, 130.07, 129.66, 129.23, 129.05, 128.49, 121.96, 118.42, 117.29, 36.48, 30.06, 29.86, 28.65, 28.59, 28.29, 23.52,22.75,22.25,22.19,22.08. The compounds numbered Ia4-ia-81-a4-1ib-81 to Ia4-lia-184-a4-lib-184 were each prepared according to the method in Example 1; the compounds numbered Ia4-1a-185~a4-1b-185 to Ia4-ia-553~la4-bb-553 were each prepared with reference to the methods in Example 1 and Example 2. Example 3 Preparation of compound Ib6a-2 (i.e., compound as shown in formulaIbna, wherein n=6, Y=Br, Q2=Cib)
2.35 g (8.2 mmol) of methyl (E)-2-(2-bromomethyl)phenyl-2-methoxyiminoacetate, 8-bromo-octanol (1.8 g, 8.61 mmol), 30 mL of a THF solution were added into a 100 mL three-necked bottle, and cooled to below 5 °C. 3.91 g (12 mmol) of Cs2CO3 was added, followed by stirring for lh. The temperature was raised to room temperature (25 °C ) and reactions continued for 8 h. Vacuum spin drying and column chromatography were performed to obtain 2.7 g of the product, methyl (E)-2-[2-(8-bromooctoxy)methylene)phenyl-2-methoxyiminoacetate at a yield of 80%. 1H NMR (300 MHz, CDCl3) 6 7.49-7.32 (m, 3H), 7.21-7.14 (m, 1H), 4.38 (s, 2H), 4.04 (s, 3H), 3.87 (s, 3H), 3.39 (dt, J=13.6, 6.8 Hz, 4H), 1.93-1.79 (m, 2H), 1.49-1.38 (m, 2H), 1.32 (s, 6H). 1.07 g (2.59 mmol) of methyl (E)-2-[2-(8-bromooctoxy) methylene)phenyl-2-methoxyiminoacetate, 0.82 g (3.1 mmol) of triphenylphosphine, 18 mg (108 ummol) of potassium iodide and magneton were added to a 100 mL three-necked bottle, followed by vacuumization and nitrogen filling. 30 mL of acetonitrile was added under the protection of nitrogen, followed by stirring at room temperature for 5-10 min, and refluxing under heating at 90 °C for 10 h. Column chromatography was then performed for separation to obtain 0.74 g of a white solid powder at a yield of 42%.
H NMR (300 MHz, CDCl3) 6 7.81-7.59 (m, 15H), 7.36-7.20 (m, 3H), 7.09-7.02 (m, 1H), 4.26 (s, 2H), 3.92 (s, 3H), 3.73 (s, 3H), 3.57 (s, 2H), 3.24 (t, J=6.6 Hz, 2H), 1.58-1.47 (m, 2H), 1.45-1.34 (m, 2H), 1.24-1.10 (m, 6H). The series of compounds numbered Ib4-iia were each prepared according to the method in Example 3. Example 4 Preparation of compound Ib8b-2 (i.e. compound as shown in formula Ibub, wherein n=8, Y=Br, Q2=Cib) 30 mL of a THF solution comprising 2.4 g (9 mmol) of11-bromoundecanoic acid was added into a 100 mL three-necked bottle, and cooled to below 5 °C. 3.91 g (12 mmol) of Cs2CO3 as added. After stirring for 1 h, 2.35 g (8.2 mmol) of methyl (E)-2-(2-bromomethyl)phenyl-2-methoxyiminoacetate was added. The temperature was heated to room temperature (25 °C), and reactions continued for 8 h. After vacuum spin drying, a yellow viscous liquid was obtained. Column chromatography was performed to obtain 3.2 g of a pink viscous liquid at a yield of 83%. 1H NMR (300 MHz, CDCl3) 6 7.47-7.34 (m, 3H), 7.20-7.13 (m, 1H), 4.97 (s, 2H), 4.03 (s, 3H), 3.86 (s, 3H), 3.62 (t, J=6.5 Hz, 2H), 2.28 (td, J=7.6, 2.1 Hz, 2H), 1.69-1.50 (m, 6H), 1.27 (s, 1OH). 1.2 g (2.59 mmol) of methyl (E)-2-[2-(11-bromoundecanoyloxy) methylene)phenyl-2-methoxyiminoaceate, 0.82 g (3.1 mmol) of triphenylphosphine, 18 mg (108 ummol) of potassium iodide and magneton were added into a 100 mL three-necked bottle, followed by vacuumization and nitrogen filling. 30 mL of acetonitrile was added under the protection of nitrogen, followed by stirring at room temperature for 5-10 min, and refluxing under heating at 90 °C for 10 h. Column chromatography was then performed for separation to obtain 0.99 g of a white solid powder at a yield of 52%. 1H NMR (300 MHz, DMSO-d6) 6 7.96-7.85 (m, 3H), 7.86-7.71 (m, 12H), 7.48-7.35 (m, 3H), 7.25-7.18 (m, 1H), 4.87 (s, 2H), 3.92 (s, 3H), 3.74 (s, 3H), 3.56 (s, 2H), 2.22 (t, J=7.4 Hz, 2H), 1.46 (s, 6H), 1.33-1.12 (m, 1OH). 13 C NMR (75 MHz, DMSO-d6) 6 172.52, 162.77, 148.93, 134.98 (d, J=3.1 Hz), 133.69 (d, J=9.8 Hz), 130.34 (d, J=12.4 Hz), 129.33, 128.90, 128.65, 128.15, 119.28, 118.15, 63.92, 63.45, 52.69, 33.34, 30.00, 28.98-28.58 (m), 28.50, 28.16, 24.33. The compounds numbered Ib4-lb and Ib4-11c were each prepared according to the method in Example 4. Among the compounds, compound Ib2b-2 was a viscous liquid, with a yield of 53% and 1H NMR as follows.
'H NMR (300 MHz, Chloroform-d) 6 7.69-7.55 (m, 9H), 7.51 (td, J=7.6, 3.7 Hz, 6H), 7.23-7.13 (m, 3H), 6.97 (dq, J=5.3, 2.5 Hz, 1H), 4.71 (s, 2H), 3.79 (s, 3H), 3.61 (s, 3H), 3.59-3.41 (m, 2H), 2.19 (t, J=6.7 Hz, 2H), 1.80 (p, J=7.1 Hz, 2H), 1.54 (p, J=7.8, 7.3 Hz, 2H). II. The examples of the composition comprising the compound as shown in formula I are provided as follows (the following components are all calculated by mass percentages, and the active components are added after being calculated in percentages). Example 5 Preparation of a wettable powder comprising 50% the compound as shown in formula I The composition of the wettable powder: the compound as shown in formula I (50%), dispersant polycarboxylate (5%), wetting agent sodium dodecyl sulfate (3%), and solid carrier or disintegrator bentonite (42%). The components were mixed according to the proportions to obtain a mixture, which was crushed by air flow to obtain the wettable powder comprising 50% the compound of formula I. Example 6 Preparation of amissible oil comprising 30% the compound as shown in formula I The composition of the missible oil: the compound as shown in formula I (30%), emulsifier polyoxyalkenylenealkylaryl ether (12%), penetrant alkylaryl sulfonate (10%), and liquid carrier cyclohexanone (48%). The components were mixed according to the proportions to obtain a transparent solution comprising 30% the compound of formula I. Example 7 Preparation of a water dispersing granule comprising 60% the compound of formula I The composition of the water dispersing granule: the compound as shown in formula I (70%), dispersant calcium alkylbenzene sulfonate ( 3 %), dispersant lignosulfonate (3%), wetting agent sodium dodecyl sulfate (4%), and solid carrier or filler starch (20%). The components were mixed according to the proportions to prepare the water dispersing granule comprising 70% the compound of formula I. III. Bioassay Example 8 Assay of bactericidal activity The compound of formula I of the present invention was used to test various fungus diseases of plants. The test method was as follows. Mycelial growth rate assay method: according to the Agricultural Industry Standard of the People's Republic of China (NY/T 1156.2-2006), the mycelial growth rate method was used for the assay. On a super clean experimental platform, activated pathogens were drilled with a hole punch having a diameter of 5 mm under sterile conditions. A fungus cake was cut, inoculated in the center of a cooled medium containing medicine with a No.11 scalpel, covered with a dish cover, and then cultured at inversion in a 25 °C incubator. Three such fungus cakes were placed in parallel, and an average value was taken as a result. When the CK diameters each reached 6-8 cm, the diameters of treated colonies were each measured by the cross method. Growth diameters of the colonies were calculated by formula (1), and an average value was taken. Growth diameter of colony = Diameter of colony - Diameter of fungus cake (1) Assay results: the growth inhibition rate of each compound to the mycelium of a pathogen was calculated by the growth diameter of a blank control colony and the growth diameter of the treated colony, as shown in the formula (2) below. Growth inhibition rate for mycelium (%)= (Growth diameter of control colony - Growth diameter of drug treated colony)/ Growth diameter of control colony x 100 (2)
S '~ Cl CC Cl Cl ~1 Cl
Cl g ~ & o~ A ~. 5Cl V ~- Cl a. Cl - Cl Cl Cl Cl Cl Cl Cl
K
0 Cl CC N - ON ON ON Cl 't N ON ON N - C C ON Cl - Cl Cl ~Th Cl N fl CC N ON '~ N '~
~ N CC ON N Cl Cl Cl Cl Cl '~ fl 6 - ~Th rn ~Th C Cl - CC 'C 'N C : CC N: CC N ~Th N ~Th N N 'C ~Th 'C ~Th
Ct - ....................................................................... -0
o t - ON 'C fl Cl Cl N't 't WCl'C C-CC
'C 'C Cl t Cl
ON N N N N 'C N N N N N N cJ~ C) C) cJ~ c~ 0
- Cl Cl '~ 'C '~ ~ fl Cl 't ON o ~' 0 0 -~ ~t fl ~i- Cl n 'C CC N fl CC CC N ~ R . fl fl 'C Cl Cl 'C ON N N 'C N 'C 'C N 'C
0
-0 .~
~
CC C' Cl C Cl 0C CC 't Cl N: rn - 'C ' - C 'C 't Cl Cl C CC ,1 C,..., ~ C Cl - 't 'C 'C C CC ON Cl - tfl ~Th ON ON CC ON N CC ON ON N CC C-, o 0 C/i ~
cJ~ CJ - ----------------------------------------------------------------------
cj~
,-. C) 0 ~ ~t CC 't Cl Cl N - CC ON ON fl ~ N 'C N ON fl ON CC CC 'C Cl CC ON rn ON N & ON o~ fl CC N CC ~ N 'C 'C 'C N 'C 'C 'C ,~ ~
FC - ----------------------------------------------------------------------
- 0 ~ Cl Cl N ON fl - fl N - CC - N C) ~ t Cl ~Th Cl ~Th t Cl C Cl Cl t C - ~ o< 5 '6 -4 o~ 6 ~ c~i 6 ~ - - CC CC CC CC CC CC ON ON ON ON CC
~ 4 't Cl Cl N Cl 't Cl Cl 'C 't ON ON C ON Cl - Cl N fl CC Cl N 'C Cl fl - Cl 'C ON C - C o N fl fl 'C 'C 'C 'C CC N ON 'C 'C ~
0 ~ Cl fl fl Cl CC N Cl Cl Cl ON Cl C - - ON Cl N ~ N 4 N 0 ON Cl Cl 't fl 't Cl - Cl N C N ON ON ON fl ON ON ON ON ON CC ON CC
z s
~t fl CC C - Cl ~t fl - 'C - F - - - - - Cl Cl N '~ C ~ A 6 ~ - - -
According to the results of sterilization experiments, 11 compounds of formula I series each showed excellent broad-spectrum fungicidal activity at a concentration of 0.07 [M. Compared with the control agent Boscalid, each drug had similar or even better fungicidal activity. Especially, Iaa-3, Iaa-13, Iaa-14, Ia8a-15, and Ia8a-21 showed good fungicidal effect on Botrytis cinerea, Phytophthoracapsici, Colletotrichum lagenarium, and Phytophthora infestans.
00 C~0
r- 00
%C 00 N
cl 00-W-)
\00 00 C
o .c
The fungicidal experiment results showed that at a concentration of 0.07 [M, three lb series compounds Ib8b-2 and Ibb-2 showed excellent broad-spectrum fungicidal activity. Compared with the control agent kresoxim-methyl, Ib8b-2 and Ib5b-2 had similar or even better fungicidal activity. Especially, Ibb-2 had a good fungicidal effect on Pythium aphanidermatum, Botrytis cinerea, Phytophthora capsici, Botryospuaeria berengeriana,and Phytophthorainfestans.
Industrial Application
The triphenylphosphonium salt compound shown in formula I of the present
invention has broad-spectrum and excellent fungicidal activity, and can be used to
prevent and cure diseases caused by four major pathogenic fungi: i.e., ascomycetes, basidiomycetes, deuteromycotina, and oomycetes, on a variety of crops. Good prevention
and cure effects can be obtained at a low dose. The compound is widely used in plant
protectants.

Claims (19)

  1. THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A compound having a general structural formula as shown in formula I: Ph Ph X' Y- nz
    Formula I wherein in formula I, X is selected from the group consisting of CH 2, NH, S, and 0; z is an integer in the range of 1 to 2; when z is 1, Y is any one selected from the group consisting of halogen, CH 3 SO3 , CF3 CO 2 , CH 3 CO 2 , CF3 SO3 , PhCO2, HOC 6 H4 CO 2 and formula W; when z is 2, Y is either one selected from the group consisting of (CH 2 CO 2 ) 2 and (CHCO 2 ) 2 ; the halogen is any one selected from the group consisting of chlorine, bromine, and iodine; n is an integer in the range from 0 to 16; and Q is selected from formula Ia or formula lb below; O ,Ar /\ /uQ2 R1 SO 3 IU'2 Qi w Ia Ib
    wherein in formula W, Ri represents H or C-C12 alkyl; wherein in formula Ia, Ar is any one selected from the group consisting of A1 -A4 and A 6-A8below, andQi is anyone selected fromthe group consisting of H andB1-B 11; and (R 2)m (R4), IN /
    A,= A2= A3 -= n A4
    -(3) (R) 0
    N S A6= A7 A7= =IC / CN F3C NA8=FC C1
    0 0 0 0 00
    Bj= B3= B4 =KcI B2= B3=B4
    o R 0 C2 H 5 0
    B 5= N l B 6=NN Yo B F 0 B8= NY (N R8 C 2H 5 HN
    B9= Bio- N , B 11 wherein in formula Ib, U is any one selected from the group consisting of 0, NH, S, OC=, SC=, NHC=, and NHC=S, and Q2 is any one selected from the group consisting of C1-C4;
    1= IMCH3 ( 12=KOCH3 C3= MCH, & 14= KOCH 3
    H 3CO'Z OCH3 H 3CO' OCH3
    wherein, in formulas Ai and A2 among Ai-A, R2, R3, R4 and R 5 are each at least one selected from the group consisting of hydrogen, C1 -Cs alkyl, C-C8 alkoxy, C-Cs alkylthio, CI-C8 fluoroalkyl, C1 -C 8 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, methanesulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; o, q, and r are each integers in the range from 0 to 5; m is an integer in the range from 0 to 4; p is an integer in the range from 0 to 3; and the binding sites of R2, R3, R5 and R6 are at least one of remaining five binding sites, wherein, when m, o, q, and r > 1, R2, R3, R5 , and R6 are the same or different; and the binding sites of R4 are at least one of remaining three binding sites, wherein, when p > 1, R 4 are the same or different; in formula A 2 , N is at any site of sites 3, 4, 5, and 6; wherein in formula B 1 among Bi-Bio, R 7 is at least one selected from the group consisting of hydrogen, C 1 -C 5 alkyl, C 1 -C5 alkoxy, C 1 -C 5 fluoroalkyl, C1 -C 5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methylsulfonyl, and trifluoromethylsulfonyl, the halogen being any one selected from the group consisting of fluorine, chlorine, bromine, and iodine; s is an integer in the range from 0 to 5; the binding sites of R7 are at least one of remaining 5 binding sites, wherein R7 are the same or different when s > 1; in formula B 6, R8 and R 9 are each any one selected from the group consisting of hydrogen, C1 -C 5 alkyl, C1 -C5 alkoxy, C-C5 fluoroalkyl, C 1 -C 5 fluoroalkoxy, and halogen; and wherein in formulas C 1 and C3 among formulas C-C4, Z is N or CH, and M is NH or O.
  2. 2. The compound according to claim 1, wherein in formula I, X is CH 2 or 0; Y is any one selected from the group consisting of halogen, CH 3 CO2 , p-toluenesulfonyl, PhCO 2, and HOC 6 H4 CO 2 ; n is an integer in the range from 4 to 11.
  3. 3. The compound according to claim 1 or 2, wherein in formula Ia, Ar is any one selected from the group consisting of A 1, A 3, A 4 , and A 6, Qi is selected from H; in formula Ib, U is any one selected from the group consisting of 0, OCO, and SC=O, and Q2 is any one selected from the group consisting of C-C4.
  4. 4. A preparation method of the compound of formula I according to any one of claims 1-3, comprising the step of: carrying out a nucleophilic reaction between a compound of formula VII and triphenylphosphine, in the presence or absence of a catalyst, to obtain the compound of formula I; n formula VII wherein in formula VII, Y, Q, X, and n are each defined in the same way as in formula I.
  5. 5. The preparation method according to claim 4, wherein the catalyst is sodium iodide or potassium iodide; wherein the molar ratio of the catalyst to the compound as shown in formula VII is (0.01-0.1): 1; wherein the reaction temperature of the nucleophilic reaction is in the range from 25 to 180 °C, and the reaction time is in the range from 4 to 24 h; wherein the molar ratio of the compound as shown in formula VII to triphenylphosphine is 1: (1-2); and wherein the nucleophilic reaction is carried out in an organic solvent which is at least one selected from the group consisting of acetonitrile, glycol dimethyl ether, benzene, toluene, and 1,2-dichloroethane.
  6. 6. The preparation method according to claim 5, wherein the reaction temperature of the nucleophilic reaction is in the range from 80 to 115 °C.
  7. 7. The preparation method according to claim 5 or claim 6, wherein the reaction time is in the range from 8 to 12 h.
  8. 8. The preparation method according to any one of claims 4 to 7, wherein the nucleophilic reaction is carried out in the following steps: performing vacuumization and then nitrogen filling on the catalyst, triphenylphosphine, and the compound as shown in formula VII, and turning on a magnetic stirrer; adding the organic solvent under the protection of nitrogen, followed by stirring at room temperature for 5-10 min, and then reacting at temperatures in the range from 80 to 115 °C for 8 to 12 h, to obtain the compound as shown in formula I.
  9. 9. A compound with a general structural formula as shown in formula VII: n formula VII wherein in formula VII, Y, Q, X, and n are each defined in the same way as in formula I.
  10. 10. A preparation method of the compound of formula VII according to claim 9, comprising the steps of: reacting a compound of formula IV with a compound of formula VI in the presence of a catalyst, or reacting a compound of formula V with the compound of formula VI, in the presence of an acid binding agent, to obtain the compound of formula VII; H NN'Ar Q 2 -Br/SH Y H formula IV formula V formula VI wherein in formula IV, Qi and Ar are each defined in the same way as in formula Ia in claim 1; in formula V, Q2 is defined in the same way as in formula Ib in claim 1; in formula VI, X, Y, and n are each defined in the same way as in formula I, and U is defined in the same way as in formula lb in claim 1; when the compound of formula IV reacts with the compound of formula VI, U is OC=O group.
  11. 11. The preparation method according to claim 10, wherein: the acid binding agent is at least one selected from the group consisting of pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, N-methylmorpholine, and NaH; and the catalyst is at least one selected from the group consisting of EDCIHOBT, CDI, DMAP/DCC, HATU/DIPEA and DIC; the molar ratio of the acid binding agent to the compound as shown in formula IV is (2-5): 1; the molar ratio of the catalyst to the compound as shown in formula IV is (1-2.5): 1, wherein the molar ratio of the compound as shown in formula IV to the compound as shown in formula VI is 1: (1-2); the molar ratio of the acid binding agent to the compound as shown in formula V is (2-5): 1; the molar ratio of the catalyst to the compound as shown in formula V is (1-2.5): 1; wherein the molar ratio of the compound as shown in V to the compound as shown in formula VI is 1: (1-2); the reaction temperature is in a range from -20 °C to 35 °C, and the reaction time is 1-6 h; the reaction is carried out in an organic solvent, which is at least one selected from the group consisting of dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, 1,4-dioxane, and toluene.
  12. 12. A composition, comprising the compound as shown in formula I according to any one of claims 1-3 and an agriculturally acceptable carrier.
  13. 13. The composition according to claim 12, wherein the mass percentage content of the compound as shown in formula I in the composition is in the range from 0.1% to 99%.
  14. 14. The composition according to claim 13, wherein the mass percentage is in the range
    from 30% to 60%.
  15. 15. The composition according to any one of claims 12 to 14, wherein the composition
    further comprises at least another active compound, which is at least one selected from the group
    consisting of a known fungicide, acaricide, nematicide, insecticide, herbicide, fertilizer, growth regulator, safety agent, and chemical pheromone.
  16. 16. The composition according to claim 15, wherein the at least one active compound is
    selected from a group consisting of a bactericidal agent and a pesticide.
  17. 17. The composition according to any one of claims 12 to 16, wherein the agriculturally
    acceptable carrier is selected from the group consisting of a solid carrier and/or liquid carrier;
    wherein the solid carrier is at least one selected from the group consisting of a natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum silicate oxide, natural or
    synthetic resin, polychlorophenol, starch, bentonite, and wax, wherein the natural or
    synthetic silicate is at least one selected from the group consisting of attapulgite, talcum, aluminum silicate, diatomite, mica, montmorillonite, and calcium silicate; the natural or
    synthetic resin is at least one selected from the group consisting of phenylpropyl furan resin,
    styrene polymer, and styrene copolymer; and the wax is selected from the group consisting of beeswax and/or paraffin; and
    wherein the liquid carrier is at least one selected from the group consisting of water, a
    C1-C4 alcohol, a C 3 -C 8 ketone, an aromatic hydrocarbon, a petroleum fraction, and a C-CI2 chloroalkane, wherein the alcohol is ethanol and/or glycol; the ketone is at least one selected
    from the group consisting of acetophenone, acetone, methyl ethyl ketone, and
    cyclohexanone; the aromatic hydrocarbon is at least one selected from the group consisting of benzene, toluene, and xylene; the petroleum fraction is kerosene and/or mineral oil; and
    the chloroalkane is at least one selected from the group consisting of carbon tetrachloride,
    dichloromethane, and trichloroethane; wherein the composition further comprises a surfactant, which is at least one selected from the group consisting of an emulsifier, a dispersant, a wetting agent, and a penetrant; wherein the emulsifier is at least one selected from the group consisting of calcium alkylbenzenesulfonate, phenylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, phenylethyl phenol polyoxyethylene polypropylene ether, polyoxyalkenylenealkylaryl ether, and ethylene oxide propylene oxide block copolymer; wherein the dispersant is at least one selected from the group consisting of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, an alkylbenzene sulfonate calcium salt, a benzenesulfonate formaldehyde condensate sodium salt, sodium lauryl sulfate, sodium castor oil sulfate, sodium alkylaryl sulfonate, alkylphenol polyoxyethyleneether, polyoxyethylene fatty acid, and ester polyoxyethylene ether; and wherein the wetting agent is at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekai BX, saponin powder, silkworm sand, and sapindus powder; and wherein the composition further comprises other auxiliaries, which are at least one selected from the group consisting of a disintegrating agent, a defoamer, an antifreeze, and a thickener; wherein the disintegrating agent is at least one selected from the group consisting of bentonite, urea, ammonium sulfate, aluminum chloride, and glucose; wherein the defoamer is at least one selected from the group consisting of silicone oil, a silicone compound, a C10-C20 saturated fatty acid compound, and a C8-CI1 fatty alcohol compound; wherein the antifreeze is at least one selected from the group consisting of glycol, propylene glycol, glycerol, and polyethylene glycol; and wherein the thickener is at least one selected from the group consisting of xanthan gum, polyvinyl alcohol, and polyethylene glycol.
  18. 18. Use of the compound of formula I according to any one of claims 1 to 3 and/or the composition according to any one of claims 12 to 17 in the preparation of a plant fungicide and/or soil fungicide.
  19. 19. The use according to claim 18, wherein the plant fungicide and/or soil fungicide are used for prevention and cure of diseases caused by at least one fungi of Eumycetes selected from the group consisting of ascomycetes, basidiomycetes, deuteromycotina, and oomycetes
    Dated this 29th day of June 2022 Spruson & Ferguson Attorneys for: China Agricultural University
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