CN1125714A - 制备新的2,2-二甲基环丙烷甲酸衍生物的方法 - Google Patents
制备新的2,2-二甲基环丙烷甲酸衍生物的方法 Download PDFInfo
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- CN1125714A CN1125714A CN95115659A CN95115659A CN1125714A CN 1125714 A CN1125714 A CN 1125714A CN 95115659 A CN95115659 A CN 95115659A CN 95115659 A CN95115659 A CN 95115659A CN 1125714 A CN1125714 A CN 1125714A
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- Prior art keywords
- compound
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- carboxylic acid
- cyclopropane
- dimethyl
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- 238000004519 manufacturing process Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 230000002829 reductive effect Effects 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 6
- GPTFURBXHJWNHR-UHFFFAOYSA-N protopine Chemical compound C1=C2C(=O)CC3=CC=C4OCOC4=C3CN(C)CCC2=CC2=C1OCO2 GPTFURBXHJWNHR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
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- MOTRZVVGCFFABN-UHFFFAOYSA-N hexane;2-propan-2-yloxypropane Chemical compound CCCCCC.CC(C)OC(C)C MOTRZVVGCFFABN-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 6
- 239000005645 nematicide Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
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- A—HUMAN NECESSITIES
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- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- A—HUMAN NECESSITIES
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- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- A—HUMAN NECESSITIES
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- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
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- A—HUMAN NECESSITIES
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- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/40—Unsaturated compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/117—Esters of phosphoric acids with cycloaliphatic alcohols
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- 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
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- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/177—Esters of thiophosphoric acids with cycloaliphatic alcohols
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- 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
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- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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Abstract
Description
本发明的主题是制备式(I)化合物的方法:其中X1和X2彼此相同或不同,代表卤原子;R1代表卤原子、含8个以下碳原子的烷基、含14个以下碳原子的芳基(可任意取代)、含8个以下碳原子的全氟烷基、—C≡N基团、
基团(其中R′代表含8以下碳原子的烷基);Y代表选自下列一组基团的基团:-SO2alk1基团,其中alk1代表被一个或多个官能团任意取代的、饱和或不饱和的直链或分枝的烃基基团;-SO2Ar基团,其中Ar代表含14个以下碳原子、由一个或多个官能团任意取代的芳基;-基团
或
其中alk2和alk3彼此相同或不同,代表直链或分枝的烃基基团,可以是饱和的或不饱和的,含8个以下的碳原子,并由一个或多个官能团任意取代;或者,alk2和alk3能与自由基形成一个环其中A代表一个直链或分枝的碳链,可以是饱和的或不饱和的,由一个或多个官能团任意取代,并含有6个以下的碳原子;-基团其中alk2′和alk3′代表与alk2和alk3相同的意义;-基团其中R″代表由一个或多个官能团任意取代的烷基或芳基,R代表氢原子、含8个以下碳原子的烷基,或用于拟除虫菊酯合成的醇的残基。
X1和X2相同或不同,最好代表氯、溴或碘原子。
R1代表卤原子时,最好是溴、氯或氟原子。
R1代表烷基时,最好是下列基团之一:甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基。
R1代表芳基时,最好是苯基。
R1代表取代的芳基时,最好是由卤原子如氯原子取代的苯基。
R1代表全氟烷基时,最好是CF3基团。
alk1、alk2、alk3、alk2′和alk3′最好代表下列基团之一:甲基、乙基、正丙基、异丙基、正丁基、异丁基和叔丁基。
Ar最好代表苯基。
当alk1、alk2、alk3、alk2′、alk3′及Ar被取代时,最好是由一个或多个下列取代基取代:卤原子、CF3、羟基、羧基、氨基及铵基,含4个以下碳原子的烷基和烷氧基,例如甲基及甲氧基。
A最好代表含1—4个碳原子的饱和碳链,并且被一个或多个下列基团任意取代:含1—5个碳原子的烷基、卤原子、CF3基团或羟基。
当R代表烷基时,最好是下列基团之一:甲基、乙基、正丙基、异丙基、丁基、异丁基或叔丁基。
用于拟除虫菊酯合成的醇的结构将在后面指出。
本发明的主题更特别地是制备X1和X2代表氯、溴或碘原子的那些化合物,如X1和X2代表溴原子的那些化合物的方法,以及制备R1代表溴、氯或氟原子的那些化合物的方法,或者还有制备R1代表三氟甲基的那些化合物的方法。
在由本发明的方法获得的较好的化合物中,可以举出的有:化合物中Y代表SO2alk1基团(alk1代表含8个以下碳原子的烷基或链烯基),例如SO2CH3基团;化合物中Y代表SO2Ar基团,Ar与前述意义相同;以及式(I)化合物中,R代表下列基团中的任一基团:-氢原子;-任意取代的含1—8个碳原子的直链或分枝的烷基;-由一个或多个基团任意取代的苄基,取代基从下列一组基团中选择:
含1—4个碳原子的烷基,
含2—6个碳原子的链烯基,
含2—6个碳原子的链烯氧基,
含4—8个碳原子的链二烯基,
甲二氧基和卤原子;基团其中取代基R″代表氢原子或甲基,取代基R2代表单环芳基或-CH=CH2基团;特别是5-苄基3-呋喃基甲基基团;-基团其中a代表氢原子或甲基,R3代表含有2—6个碳原子及一个或多个碳-碳不饱和键的脂肪族有机基团,特别是下列基团之一:-CH2-CH=CH2,-CH2-CH=CH-CH3,-CH2-CH=CH-CH=CH2,-CH2-CH=CH-CH2-CH3-CH2-C≡CH;基团其中a代表氢原子或甲基,R3与前述意义相同,R1′和R2′相同或不同,代表氢原子、卤原子、含1—6个碳原子的烷基、含6—10个碳原子的芳基、含2—5个碳原子的烷氧羰基基团或氰基;-基团其中B′代表氧或硫原子、-C-或-CH2-基团或亚砜基团或砜基团,R4代表氢原子、-C≡N基团、甲基、-CONH2基团、-CSNH2基团或-C≡CH基团,R5代表卤原子或甲基,n代表数字0、1或2;特别是下列基团之一:3-苯氧基苄基、α-氰基-3-苯氧基苄基、α-乙炔基-3-苯氧基苄基、3-苯甲酰基苄基、1-(3-苯氧基苯基)乙基或α-硫代酰胺基3-苯氧基苄基;-基团-基团其中取代基R6、R7、R8和R9代表氢原子、氯原子、或甲基,S/I表示芳香环或类似的二氢化的或四氢化的环;-基团-基团其中R10代表氢原子或CN基,R12代表-CH2-基或氧原子,R11代表噻唑基或噻二唑基,它可以任一个可能的位置与键合,R12连于R11上的处在硫原子和氮原子之间的碳原子上;-基团-基团其中R13代表氢原子或CN基;-基团其中R13定义如上,苯甲酰基在3位或4位;-基团其中R14代表氢原子、甲基、乙炔基或氰基,R15和R16不同,代表氢、氟或溴原子;-基团其中R14定义如上,每个R17分别代表含1—4个碳原子的烷基基团,含1—4个碳原子的烷氧基基团,含1—4个碳原子的烷硫基基团,含1—4个碳原子的烷基磺酰基基团,三氟甲基,3,4-甲二氧基,氯、氟或溴基团,P代表数字0、1或2,B″代表氧原子或硫原子;-基团其中R18代表氢原子、甲基、乙炔基或氰基,R19不同,代表氢、氟或溴原子,Ar代表含14个以下碳原子的芳基;-基团或
本发明的主题是一种更特别地制备具有下列结构的化合物的方法:
-1R-[1-α-(S)-3-α-(R)]2,2-二甲基-3-[1-(甲磺酰氧基)-2,2,2-三溴乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯,
-1R-[1-α-(S)-3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯,
-1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-[(3-苯氧基-4-氟)苯基]乙基酯,
-1R-[1-α,3-α(RS,RS)]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲磺酰氧基乙基]环丙烷甲酸[(2-甲基-3-苯基)苯基]甲基酯,
-1R-[1-α,3-α(RS*,RS*)]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯。
本发明的主题也是一种制备方法,其特征在于,式(II)化合物与式(V)化合物在碱存在下作用以得到式(IV)化合物,其中R与前述意义相同其中X1、X2和R1与前述意义相同式(IV)化合物与磺酰化、膦酰化、硫代磷酰化或酰化试剂作用以得到式(I)的相应化合物,该化合物可随意转变为相应的酸,该酸与酯化试剂作用以得到一种新的式(I)化合物。
在一个较好的实现本发明方法的办法中:-式(II)化合物与式(V)化合物反应时所用的碱最好从这样一组碱中选择:强碱性醇化物、强碱性氢化物和强碱性氢氧化物。可以举出的特别好的碱有:氢氧化钾、甲醇钾或叔丁醇钾;-磺酰化试剂相应于式(A):其中Z=卤素COalk(alk为1—8C)OSO2alk(alk为1—8C)咪唑基-膦酰化试剂相应于式(B):其中Z=卤素OSO2R咪唑基X代表氧或硫原子,alk2和alk3与式(I)产物的定义中的意义相同;-酰化试剂相应于式
其中Z=OCOalk
卤素
咪唑基-式(I)的试剂可由式(I)的酯与一种酸水解试剂反应来制备,酸水解试剂如对甲苯磺酸、硫酸或乙酸;-酯化试剂是一种醇,酯化按常规方法进行。
当用此方法进行操作时,所得式(IV)的产物除X1、X2和R1各代表卤原子的产物外,都是新产物。
式(I)化合物具备一些有用的性质,使得它们可用于防治寄生虫,例如可防治植物寄生虫、室内寄生虫和温血动物寄生虫。因此,由本发明方法获得的产物可用来防治昆虫、植物和动物的寄生线虫和寄生螨。
这样,式(I)产物尤其可用于在农业区防治昆虫,例如防治蚜虫、磷翅目幼虫和鞘翅目昆虫。它们以每公顷10g至300g活性物质的剂量来使用。
式(I)产物还可用于防治室内昆虫,特别是防治蝇、蚊和蟑螂。
由本发明方法获得的化合物具有非常显著的杀虫剂特性,尤其是非常好的“击倒”效力。
式(I)产物还可用于防治植物的寄生蜱螨。
式(I)化合物还可用于防治植物的寄生线虫。
式(I)化合物还可用于防治动物的寄生蜱螨,例如防治蜱,特别是牛蜱属(Boophilus)、璃眼蜱属(Hyalomma)、花蜱属(Amblyomma)和扇头蜱属(Rhipicephalus)的蜱,或防治所有类型的螨,特别是疥螨(sarcoptic mites)、啮虫目的螨(psoropticmites)和牛皮痒螨(chorioptic mites)。
因此,式(I)化合物可用于制备用来防治温血动物寄生虫、房屋寄生虫和植物寄生虫的组合物,这些组合物含有式(I)化合物作为活性要素。
因此,式(I)化合物可用于制备特别是杀虫剂组合物。
根据本发明获得的尤为良好的杀虫剂组合物中,可以具体地举出的是,含有实施例中所描述的化合物的组合物,特别是:
-1R-[1-α-(S)3-α-(R)]2,2-二甲基-1-[1-(甲磺酰氧基)-2,2,2-三溴乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯,
-1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯,
-1R-[1-α-(S)3-α-(R)] 2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-[(3-苯氧基-4-氟)苯基]乙基酯,
-1R-[1-α,3-α(RS,RS)]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲磺酰氧基乙基]环丙烷甲酸[(2-甲基-3-苯基)苯基]甲基酯,
-1R-[1-α,3-α(RS*,RS*)]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯。
根据本发明的组合物依照农药工业或兽药工业、或动物饲料工业的通常方法来制备。
这些组合物可以下列形式存在:粉剂、颗粒、悬浮液、乳剂、溶液、气溶胶溶液、可燃性带剂(bands)、毒饵以及其它为使用这类化合物而采用的传统制剂。
除活性要素外,这些组合物一般还含有表面活性介质和/或非离子型试剂,进一步使该混合物的组成物质均一分散。所用介质可以是液体如水、醇、碳氢化合物或其它有机溶剂;矿物油、动物油或植物油;粉末如滑石、粘土、硅酸盐、硅藻土或可燃性固体。
根据本发明的杀虫剂组合物最好含0.005%至10%重量的活性物质。
根据本发明的组合物,可依照一种方便的用于室内的操作方法,以熏蒸组合物的形式使用。
这样,可以很方便地组成根据本发明的组合物,用可燃性杀虫剂盘卷或非可燃性的纤维基质作非活性部分。在后一种情况下,掺入活性物质后所得到的熏蒸剂,置于一个加热装置如电子驱蚊器(electro-mosquito destroyer)上。
使用杀虫剂盘卷时,惰性载体可以是例如除虫菊果渣复合物(Pyrethrum marc compound)、Tabu粉(或MachilusThumbergii叶粉)、除虫菊茎粉、雪松叶粉、木屑(如松木屑)、淀粉和椰粉。活性物质的剂量可以是例如0.03至1%(重量)。
当使用不可燃的纤维素作载体时,活性物质的剂量例如按重量计为0.03%到95%。
根据本发明的用于室内的组合物也可如下获得:以活性要素作为基剂制备一种可涂抹的油,用此油浸透灯芯,点燃灯芯。
掺入油中的活性要素的浓度最好是0.03至95%(重量)。
式(I)化合物也可用于制备杀螨剂组合物及杀线虫剂组合物,这些组合物含有式(I)化合物作为活性要素。
根据本发明的杀虫剂组合物如杀螨剂和杀线虫剂组合物,也可加入一种或几种其它的杀虫剂试剂。杀螨剂和杀线虫剂组合物特别可以粉剂、颗粒、悬浮液、乳剂和溶液的形式存在。
使用杀螨剂时,最好用含1—80%活性要素的可湿性粉剂涂抹叶片,或用含1—500g/l活性要素的液体涂抹叶片。也可用含0.05—3%活性物质的粉剂对叶片施粉。
使用杀线虫剂时,最好用含300—500g/l活性要素的液体施用于土壤。
根据本发明的杀螨剂和杀线虫剂化合物,最好以每公顷1—100g活性物质的剂量使用。
式(I)化合物也可用于制备含有该化合物作为活性要素的杀螨剂组合物,这些组合物用来防治温血动物的寄生螨,尤其是蜱和螨。
为防治动物寄生虫,组合物可以喷雾、喷淋的形式使用,或也可依照“灌注法”(“pour-on”method)使用。
使用灌注法时,最好用每100cm3溶液含0.5g至4g活性要素的溶液。
为防治动物寄生螨,常常将根据本发明方法获得的产物与适于作动物饲料的营养混合物结合而掺入到营养组合物中。该营养混合物可依动物类型不同,可含有谷类、糖和谷粒、豆饼、花生饼和葵花饼,用动物作的饲料如鱼肉,合成氨基酸、无机盐、维生素和抗氧化剂。
式(I)化合物可用来制备用于动物饲料的组合物。
还可以指出,由本发明方法获得的产物可用作杀生物剂或生长调节剂。
式(I)化合物还可用于制备具有杀虫剂、杀螨剂或杀线虫剂活性的结合物,其特征在于,它们一方面至少含有一种通式(I)的化合物,另一方面至少含有一种选自下列一组化合物的拟除虫菊酯:allethrolone、3,4,5,6-四氢化苯二甲酰亚胺基甲基醇、5-苄基3-呋喃甲基醇、3-苯氧基苄醇、 α-氰基3-苯氧基苄醇与菊酸形成的酯,5-苄基3-呋喃甲基醇与2,2-二甲基3-(2-氧代-3,4,5,6-四氢硫代亚环己二烯基甲基)环丙烷-1-甲酸形成的酯,3-苯氧基苄醇和α-氰基-3-苯氧基苄醇与2,2-二甲基3-(2,2-二氯乙烯基)环丙烷-1-甲酸形成的酯,α-氰基3-苯氧基苄醇与2,2-二甲基3-(2,2-二溴乙烯基)环丙烷-1-甲酸形成的酯,3-苯氧基苄醇与2-对氯苯基2-异丙基乙酸形成的酯,allethrolones、3,4,5,6-四氢化苯二甲酰亚胺基甲基醇、5-苄基3-呋喃甲基醇、3-苯氧基苄醇、α-氰基3-苯氧基苄醇与2,2-二甲基3-(1,2,2,2-四卤乙基)环丙烷-1-甲酸形成的酯,其中“卤”代表氟、氯或溴原子。应当理解,化合物I可以其所有可能的立体异构形式存在,组成上述拟除虫菊酯的酸和醇也是如此。
上述结合物的重要性特别在于,它们可使得所防治的寄生虫的范围更宽(由于其作用的多效性),以及在某些情况下可表现出增效作用。
根据本发明的各种杀虫性组合物,还另外含有一种常规增效剂。可以举出的在类似情况下使用的常规增效剂有:1-(2,5,8-三氧杂十二烷基)-2-丙基-4,5-甲二氧基苯(或胡椒基丁醚)或N-(2-乙基庚基)-二环-[2,2,1]-5-庚烯-2,3-二羧酸酰亚胺,或胡椒基-双-2-(2′-正丁氧基乙氧基)乙基乙缩醛(或增效醛)。
本发明的主题也包括式(I)化合物的使用,其特征在于,式(I)化合物与一种还原剂作用以获得相应的式(III)化合物:其中X1、R1和R与前述意义相同。
在一种较好的实施方法中,所用还原剂是氢,并有氢反应催化剂如钯存在。此还原反应还可用锌在酸的存在下进行。也可在醇中用锌-铜组合物,或可用任何其它方法使卤原子和OY基团同时消除。
可以举出一种特别重要的使用方法,该方法的特征是,式(I)化合物相应于式(I′):其中Y和R与前述意义相同,而且式(III)化合物相应于式(III′)或同样的使用,其特征在于,式(I)化合物相应于式(I″):其中Y和R与前述意义相同,并且所得到的化合物(III)相应于式(III″):
下述实例阐述本发明,但并不限制本发明。实例1:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-(1-羟基-2,2,2-三溴乙基)环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R-[1-α-3-α-(R)]2,2-二甲基-3-[1-(三甲硅烷氧基)2,2,2-三溴乙基]环丙烷甲酸
于-60℃下,在30分钟内,将18.5g叔丁醇钾、40cm3四氢呋喃和80cm3叔丁醇加入含30.25g1R-[1-α-3-α-(R)2,2-二甲基-3-[1-羟基-2,2,2-三溴乙基]环丙烷甲酸(在法国专利2396006中描述)和300cm3四氢呋喃的溶液中。整个体系于-60℃搅拌10分钟,一滴一滴地加入80cm3三甲基氯硅烷和60cm3四氢呋喃。整个体系于-60℃搅拌10分钟,然后使环境温度升至-20℃。在-20℃搅拌半小时。将反应混合物倾入饱和碳酸氢钠溶液中。用氯仿进行萃取,萃取液脱水并在减压下进行干燥。加入100cm31%乙酸水溶液。整个体系搅拌15分钟,分离所获产物,将其溶于氯仿,脱水并进行减压干燥。于是得到16g产物,熔点为147℃。步骤B:1R-[1-α-(S)3-α-(R)2,2-二甲基-3-[1-(三甲硅烷氧基)2,2,2-三溴乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在含有32g步骤A所制备的产物、300cm3二氯甲烷和15g(S)α-氰基3-苯氧基苄醇的溶液中,加入14g二环己基碳化二亚胺和140cm3二氯甲烷的溶液。整个体系于20—25℃搅拌3小时,然后分离并进行减压干燥。用层析法进行纯化,用己烷-异丙醚混合液(8—2)洗脱。得到34g所要的产物,熔点为98℃。步骤C:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-(1-羟基-2,2,2-三溴乙基)-环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在含有8g实例1的步骤B中所获产物和150cm3甲醇的溶液中,加入3cm32N盐酸。于20—25℃搅拌30分钟后,弃去甲醇,余者用二氯甲烷导出,脱水并进行减压干燥。得到产物并在基质上进行层析,用己烷-乙酸乙酯混和液(7—3)洗脱。于是得到6.5g所要的产物。NMR光谱CDCl3ppm实例2:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[1-(甲磺酰氧基)2,2,2-三溴乙基)环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
于0°±5℃下,在3g实例1中制备的产物、30cm3四氢呋喃和0.5cm3甲磺酰氯的混合物中,加入0.91cm3三乙胺。整个体系于0±5℃搅拌2小时。再加入0.5cm3甲磺酰氯和0.91cm3三乙胺。分离形成的沉淀;有机相用水洗涤,脱水并进行减压干燥。在硅石上进行层析,用己烷-乙酸乙酯混合液(7—3)洗脱。得到2.6g所要的产物。NMR光谱CDCl3ppm实例3:1R-[1-α-(S*)3-α-(R*)]2,2-二甲基-3-(2,2,2-三溴-1-乙磺酰氧基乙基)环丙烷甲酸氰基-1-(3-苯氧基苯基)甲基酯
如前一实例操作,从实例1中制备的产物和乙磺酰氯起始,得到所要的产物,熔点为113℃。[α]D=+43°C=1%CHCl3实例4:1R-[1-α-(S)3-α-(R)]3-(2,2,2-三溴-1-甲基乙磺酰氧基乙基)2,2-二甲基环丙烷甲酸氰基-1-(3-苯氧基苯基)甲基酯
于0±5℃温度下,在含有1.5g实例1中所获产物、15cm3四氢呋喃和0.32g异丙基亚磺酰氯的溶液中,加入0.35cm3三乙胺。整个体系于0-5℃搅拌30分钟。将反应混合物倾入pH5的盐酸水溶液中,然后用二氯甲烷萃取,萃取液进行脱水、过滤并蒸发至干。加入1.5g对硝基过苯甲酸。整个体系于20—25℃下搅拌至干30分钟,使其干燥。得到3.2g所要的粗产物,在硅石上进行层析,用己烷-乙酸(8—2)混和液洗脱。得到1.43g所要的产物。[α]D=+42°±1.5 C=0.7%实例5:1R-[1-α-(S)3-α-(R)]3-[2,2,2-三溴-1-(2-甲基-2-丙烯-1-磺酰氧基]2,2-二甲基环丙烷甲酸氰基-1-(3-苯氧基苯基)甲基酯以实例1中所获产物和(1-磺酰氧基2-甲基)2-丙烯氯起始,如实例2进行操作,得到所要的产物。m.p.=107℃。实例6:1R-[1-α-(R,S)3-α-(R*)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸α-(R,S)氰基-1-(6-苯氧基2-吡啶基)甲基酯步骤A:1R-[1-α-(R,S)3-α-(R*)]2,2-二甲基-3-[2,2,2-三溴-1-三甲硅烷氧基乙基]环丙烷甲酸α-(R,S)氰基-1-(6-苯氧基2-吡啶基)甲基酯
如实例1的步骤B进行操作,以实例1的步骤A中得到的1R-[1-α,3-α(R)]2,2-二甲基-3-[三甲硅烷氧基2,2,2-三溴乙基]环丙烷甲酸和α-(R,S)氰基1-(6-苯氧基-2-吡啶基)甲醇起始,得到所要的产物,熔点为160℃。步骤B:1R-[1-α-(R,S)3-α-(R*)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸α-(R,S)氰基-1-(6-苯氧基2-吡啶基)甲基酯
如实例1步骤C进行操作,以本实例的步骤A中所获得产物起始,得到所要的产物,用于下述步骤。步骤C:1R-[1-α-(R,S)3-α-(R*)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸α-(R,S)氰基-1-(6-苯氧基2-吡啶基)甲基酯
如实例2进行操作,以步骤B中所获得产物和甲磺酰氧起始,得到所要的产物。[α]D=+6°±1.5°C=0.3%CHCl3。实例7:1R-[1-α,3-β-(R)]2,2-二甲基-3-(2,2,2-三溴-1-甲磺酰氧基乙基)-环丙烷甲酸(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-三甲硅烷氧基乙基)-环丙烷甲酸(3-苯氧基苯基)甲基酯
如前一实例进行操作,以实例1的步骤A中所获产物和间苯氧基苄醇起始,得到所要的产物。步骤B:1R-[1-α,3-α-(R*)]2,2-二甲基-3-[2,2,2-三溴-1-羟乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯
如前一实例的步骤B进行操作,以步骤A中所获得产物起始,得到所要的产物,用于下述步骤。步骤C:1R-[1-α,3-α(R)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸(3-苯氧基苯基)甲基酯
如前一实例的步骤C进行操作,以本实例的步骤B中所获产物起始,得到所要的产物,熔点为72℃。实例8:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-(2,2,2-三溴-1-甲磺酰氧基乙基)环丙烷甲酸(S)氰基[(3-苯氧基--氟)苯基)甲基酯步骤A:1R-[1-α-(S)3-α-(R)]3-[2,2,2-三溴-1-三甲硅烷氧基乙基]2,2-二甲基环丙烷甲酸氰基[(3-苯氧基-4-氟)苯基]甲基酯
如实例7进行操作,以1R-[1-α,3-α(R)]2,2-二甲基-3-[1-三甲硅烷氧基2,2,2-三溴乙基]环丙烷甲酸和(S)氰基[(3-苯氧基-5-氟)苯基)甲醇起始,得到所要的产物。m.p.=133℃。步骤B:1R-[1-α-(S)3-α-(R)]3-[2,2,2-三溴-1-羟乙基]2.2-二甲基环丙烷甲酸(S)氰基[(3-苯氧基-4-氟)苯基]甲基酯
如实例7进行操作,水解步骤A中所获得产物,得到所要的产物,用于下述步骤。步骤C:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸(S)氰基[(3-苯氧基-4-氟)苯基)甲基酯
如实例7进行操作,以本实例的步骤B中所获得产物和甲磺酰氯起始,得到所要的产物。[α]D=+34°±1°C=1%CHCl3实例9:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-(2-丙烯1-磺酰氧基)乙基]环丙烷甲酸氰基(3-苯氧基苯基)甲基酯
用1-磺酰氧基2-氯丙烯酯化实例1的产物,得到所要的产物,熔点为96℃。实例10:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-三氟甲基羰氧基乙基]环丙烷甲酸(S)氰基(3-苯氧基苯基)甲基酯步骤A:1R-[1-α-(S)3-α-(R)]2,2-二甲基3-[2,2,2-三溴-1-三氟甲基羰氧基乙基]环丙烷甲酸1,1-二甲基乙基酯
于10/15℃,在5g 2,2-二甲基-3-[2,2,2-三溴-1-羟乙基]环丙烷甲酸叔丁酯和20cm吡啶的混和物中,加入16cm3三氟乙酸。使反应混和物回温至20°/25℃,搅拌一个半小时。将反应混和物倾入冰水混和物中。用乙醚进行萃取,萃取液脱水并进行减压干燥。所获产物加己烷进行冷却,脱水并进行干燥。得到5.09g所要的产物。熔点为102℃。步骤B:1R-[1-α,3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-三氟甲基羰氧基乙基]环丙烷甲酸
如实例(?)的步骤B进行操作,以本实例的步骤A中所获的酸起始,得到所要的产物:m.p.=178℃。步骤C:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[2,2,2-三溴-1-(三氟甲基羰氧基乙基)]环丙烷甲酸(S)氰基(3-苯氧基苯基)甲基酯
如实例(?)的步骤C进行操作,以本实例的步骤B中所获的酸及(S)α-氰基3-苯氧基苄醇起始,得到所要的产物,熔点为79℃。实例11:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[(1-二乙氧基磷酰氧基)-2,2,2-三溴乙基]环丙烷甲酸氰基(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R)]3-[2,2,2-三溴-(二乙氧基磷酰氧基)乙基]2,2-二甲基环丙烷甲酸二甲基乙基酯
于-60℃,在含有4g酮[1-α,3-α(R)]环丙烷甲酸二甲基乙基酯和40cm3四氢呋喃的悬浮液中,加入5.05g溴仿、35g叔丁醇钾和20cm3四氢呋喃。整个体系于-60℃搅拌15分钟,然后加入3.6g二乙氧基磷酰氧基氯。混合物于-60℃搅拌一个半小时后,倾入当量盐酸溶液中。用乙醚进行萃取,萃取液用水洗涤,脱水后进行减压干燥。得到7.09g所要的产物,熔点为79℃。步骤B:1R-[1-α,3-α-(R)]3-[2,2,2-三溴-1-二乙氧基磷酰氧基)乙基]2,2-二甲基环丙烷甲酸
将含有5g步骤A所制备的产物,50cm3苯和0.5g对甲苯磺酸的溶液回流1小时。将反应混和物冷却至20/20℃,倾入水中。倾析出有机相,脱水后进行减压干燥。用己烷提取残渣,分离所获的产物。得到3g产物,熔点为146℃。步骤C:1R-[1-α-(S)3-α-(R)]2,2-二甲基-3-[(1-二乙氧基磷酰氧基)2,2,2-三溴乙基]环丙烷甲酸氰基(3-苯氧基苯基)甲基酯
在含有3g步骤B中所制备的酸、1.34g(S)α-氰基3-苯氧基苄醇、50mg二甲氨基吡啶和30cm3二氯甲烷的混合物中,加入1.22g环己基碳化二亚胺和5cm3二氯甲烷。使反应混合物升至室温,持续搅拌一个半小时。分离所获产物并进行干燥,然后用硅石进行层析,用己烷-乙酸乙酯混和液(6—4)进行洗脱。得到3.3g所要的产物。实例12:1R-[1-α-(S)3-α-(R)]3-[2,2,2-三溴-1-(2-氧代-1,3,2-二氧-磷六环基氧基)乙基]2,2-二甲基环丙烷甲酸氰基(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R)]3-[2,2,2-三溴-1-(2-氧代-1,3,2-二氧-磷六环基氧基)乙基]2,2-二甲基环丙烷甲酸1,1-二甲基乙基酯
于-60℃,在9.9g 2,2-二甲基3-酮(1R,3-α)环丙烷甲酸1,1-二甲基乙基酯在100cm3四氢呋喃中的溶液中,加入4.6cm3溴仿。然后于-60℃加入6.05g叔丁醇钾和25cm3四氢呋喃。然后于-60℃在15分钟内加入7.5g 2-氧代1,3,2-二氧磷烷氯和25cm3四氢呋喃。整个体系于-60℃搅拌15分钟,然后倾入盐酸水溶液中,用二氯甲烷萃取;用水洗涤有机相,脱水并进行减压干燥。,得到27g产物并用100cm3乙醚研制。所获产物进行过滤和干燥。得到18.4g所要的产物,熔点为210℃。步骤B:1R-[1-α,3-α-(R)]3-[2,2,2-三溴-1-(2-氧代1,3,2-二氧磷六环烷基氧基)乙基]2,2-二甲基环丙烷甲酸
于回流下,在500cm3苯和对甲苯磺酸的溶液中,加入12.9g步骤A中所制备的产物。整个体系持续回流30分钟。所获产物进行干燥,并用乙酸乙酯导出,搅拌15分钟后过滤。得到5.5g所要的产物,熔点为225℃。步骤C:1R-[1-α-(S)3-α-(R)]3-[2,2,2-三溴-1-(2-氧代1,3,2-二氧磷六环烷基氧基)乙基]2,2-二甲基环丙烷甲酸(S)氰基(3-苯氧基苯基)甲基酯
如实例1步骤B进行操作,以2.5g上述获得的产物和1.07g(S)α-氰基3-苯氧基苄醇起始,得到所期望的产物。m.p.=155℃。[α]D=+42°±1.5°(C=1%,CHCl3)实例13:1R-[1-α,3-α(R)]3-[2,2,2-三溴-1-(2-氧代-1,3,2-二氧磷六环烷基氧基)乙基]2,2-二甲基环丙烷甲酸(2-甲基3-苯基苯基)甲基酯
以实例6的步骤B中所制备的酸和(2-甲基2-苯基苯基)甲醇起始,得到所要的产物。m.p.=182℃。实例14:1R-[1-α-(S)3-α-(R或S)]3-[2,2,2-三氯-1-(二乙氧基硫代磷酰氧基)乙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R+S)]3-[2,2,2-三氯-1-(二乙氧基磷酰氧基)乙基]2,2-二甲基环丙烷甲酸二甲基乙基酯
于-60℃,在含有1.98g2,2-二甲基3-酮(1-α-3-α)环丙烷甲酸1,1-二甲基乙基酯在10cm3四氢呋喃中的溶液中,加入0.84cm3氯仿和1.21g叔丁醇钾在10cm3四氢呋喃中的溶液。整个体系于-60℃搅拌30分钟,然后加入1.88g氯硫代磷酸O,O-二乙基酯。使温度升至20/25℃。搅拌5小时。将反应混和物倾入当量盐酸溶液中,用乙醚萃取,分离萃取液并进行减压干燥,然后在硅胶上进行层析,用己烷-异丙醚混和液(9—1)洗脱。于是得到2.15g所要的产物。步骤B:1R-[1-α,3-α-(R+S)]3-[2,2,2-三氯-1-(二乙基硫代磷酰氧基)乙基]2,2-二甲基环丙烷甲酸
如前一实例的步骤B进行操作,以本实例的步骤A中所获产物起始,得到所要的产物。步骤C:1R-[1-α-(S)3-α-(R或S]3-[2,2,2-三氯-1-二乙氧基硫代磷酰氧基)乙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
如前一实例的步骤C进行操作,以本实例的步骤B中所获产物的起始,得到产物在硅胶上进行柱层析,用己烷-乙酸乙酯混和液(7—3)洗脱。得到0.850g异构体A和0.800g产物B。NMR光谱(A)成对CH3 73-74HzH环丙基 110-116HzCH-O-P 312-342Hz-CH-402CN芳香氢416-457NMR光谱(B)成对CH3 73-75Hz-CH- 384HzCN芳香氢 425或452Hz实例15:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-甲磺酰基乙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-羟乙基]2,2-二甲基环丙烷甲酸二甲基乙基酯
在搅拌和氮气氛下,于-60,-55℃,在4.95g3-甲酰1R,3 R2,2-二甲基环丙烷甲酸叔丁酯和50cm3四氢呋喃的混和物中,先加入2.2cm3氯仿,再加入2.95g叔丁醇钾和25cm3四氢呋喃。反应混和物持续搅拌2小时30分钟。用乙醚进行萃取;洗涤有机相,脱水并进行减压干燥。所获产物进行层析,用己烷-乙酸乙酯和液(7—1)洗脱。于是得到6.45g产物。m.p.=50℃。步骤B:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-甲磺酰氧基乙基]环丙烷甲酸二甲基乙基酯
于0—5℃,在6.35g步骤A中制备的产物、65cm3四氢呋喃和3.2cm3甲磺酰氯的混和物中,加5.6cm3三乙胺和6cm3四氢呋喃。将反应混和物倾入水中,用乙醚萃取,萃取液用硫酸钠干燥,过滤后进行干燥。得到8.1g产物,熔点为106℃。步骤C:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-甲磺酰氧基乙基]环丙烷甲酸
将6.5g前一步骤中制备的产物、65cm3苯和150mg对甲苯磺酸回流1小时。将反应混和物倾入水中,用二氯甲烷萃取并进行干燥。得到5.15g结晶,熔点为148℃。步骤D:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-甲磺酰氧基乙基)2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
如实例1进行操作,将前一步骤中得到的酸用(S)α-氰基3-苯氧基苄醇进行酯化,得到所要的产物。[α]D=+33°±1°,C=1%CHCl3实例16:1R-[1-α-(S)3-α-(R)]3-(2,2,2-三氯-1-甲磺酰氧基乙基)2,2-二甲基环丙烷甲酸(S)氰基-(3-苯氧基-4-氟)苯基甲基酯
用实例15的步骤C中得到的酸与S-α氰基4-氟3-苯氧基苄醇进行酯化,制备该产物。[α]D=+38°±1°,C=1.5%CHCl3。实例17:1R-[1-α,3-α-(R)]3-[2,2,2-三氯-1-甲磺酰氧基乙基)2,2-二甲基环丙烷甲酸氰基1-(6-苯氧基-2-吡啶基)甲基酯
用实例15的步骤C中得到的酸与、RS-氰基-1-(6-苯氧基--吡啶基)甲醇进行酯化,制备该产物。[α]D=2°±1°,C=0.8%CHCl3。实例18:1R-[1-α,3-α(R)]3-[2,2,2-三氯-1-甲磺酰氧基乙基]环丙烷甲酸(2-甲基3-苯基苯基)甲基酯
用实例15的步骤C中得到的酸与(2-甲基3-苯基苄基)醇进行酯化,制备该产物。[α]D =20°±1°,C=1%CHCl3实例19:1R-[1-α-(S*)3-α-(R*)]2,2-二甲基3-[2,2,2-三氯-1-(4-甲苯磺酰氧基)乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(R*)]3-[2,2,2-三氯-1-(4-甲基苯基)磺酰氧基]乙基2,2-二甲基环丙烷甲酸二甲基乙基酯
于-60℃,在3.96g(1R,3R)3-甲酰环丙烷甲酸叔丁酯和20cm3四氢呋喃的悬浮液中,先加入1.7cm3氯仿,再加入2.42g叔丁醇钾和20cm3四氢呋喃。于-60℃搅拌30分钟。于-60℃,在15分钟内加入4g甲苯磺酰氯和10cm3四氢呋喃。整个体系于-60℃搅拌30分钟,然后倾入200cm3当量盐酸溶液中。用乙醚进行萃取,萃取液进行洗涤、分离及减压干燥。于是得到5.3g所要的产物。步骤B:1R-[1-α,3-α-(R*)]3-[2,2,2-三氯-1-(4-甲基苯磺酰氧基)乙基]2,2-二甲基环丙烷甲酸
在对甲苯磺酸的存在下,将前面的酯在苯中加热至回流,即得到该化合物。m.p.=190℃。步骤C:1R-[1-α-(S*)3-α-(R*)]2,2-二甲基3-[2,2,2-三氯-1-(4-甲基-苯磺酰氧基)乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在实例1的步骤C的条件下,与S-α氰基-3-苯氧基苄醇进行酯化。得到所要的化合物。[α]D=77.5°+±1.5°C=1.1%CHCl3。实例20:1R-[1-α-(S)3-α-(S)]2,2-二甲基3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R-[1-α,3-α-(S)]2,2-二甲基3-[2,2,2-三溴-1-羟乙基]环丙烷甲酸1,1-二甲基乙基酯
在39.6g1,1-二甲基乙基1R,3R,2,2-二甲基3-酮环丙烷在200cm3四氢呋喃的溶液中,加入26cm3溴仿。在所得到的溶液中加入17.5g甲醇钾、100cm3叔丁醇、60cm3四氢呋喃和60cm3二甲基甲酰胺。整个体系于-10℃搅拌1小时,然后于+10℃搅拌1小时,然后倾入水中。用异丙醚进行萃取。萃取液脱水后进行真空干燥。得到两种非对映异构体,用色谱法进行分离。步骤B:1R-[1-α,3-α-(S)]2,2-二甲基3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸1,1-二甲基乙基酯
将含有4g前一步骤中所制备的产物、40cm3四氢呋喃和2.03g甲磺酰氯的混和物冷却至0°±5℃。于0°±5℃加入1.78g三乙胺和5cm3四氢呋喃。整个体系于0°±5℃搅拌2小时,然后倾入水中,用二氯甲烷萃取;萃取液脱水并进行减压干燥。所获产物进行纯化,先用己烷、再用异丙醚进行重结晶。得到2.9g产物,熔点为159℃。步骤C:1R-[1-α,3-α-(S)]2,2-二甲基3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸
将2.3g步骤B中制备的产物和25cm3苯的混和物进行回流。加入70mg对甲苯磺酸。整个体系进行冷却、水洗、脱水及减压干燥。得到1.8g所要的产物,熔点为168℃。步骤D:1R-[1-α(S)3-α(S)]2,2-二甲基-3-[2,2,2-三溴-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在含有1.8g上面得到的α-α酸、20cm3二氯甲烷、0.86g(S)α-氰基3-苯氧基苄醇和0.1g二甲氨基吡啶的溶液中,加入0.78g二环己基碳化二亚胺和3cm3二氯甲烷。整个体系于20—25℃搅拌2小时。所形成的产物进行脱水,滤液进行减压干燥。进行层析,用己烷-乙酸乙酯混和液(7—3)洗脱。于是得到2g所要的产物。[α]D=1°±1°,C=1%,CHCl3。实例21:[1R-(1-α-S*,3-α-RS*,RS*)]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基-3-[2-三氟甲基-2-溴-2-氯-1-甲基羟乙基]环丙烷甲酸
于-70℃,在5g1 R,顺2,2-二甲基-3-甲酰环丙烷甲酸1,1-二甲基乙基酯在50cm3 THF和3cm3卤乙烷(halothene)(CF3CHClBr)的溶液中,慢慢加入3.1g叔丁醇钾在20cm3THF中的溶液。在此温度下充分接触后,将该介质倾入PO4H2Na水溶液中。用二氯甲烷进行萃取,萃取液用水及饱和氯化钠溶液洗涤,脱水后进行减压干燥。所得产物在硅胶上进行层析,用己烷-异丙醚混和液(8—2)洗脱。于是得到6.83g所要的产物。步骤B:[1R-[1-α,3-α-(RS*RS*)]]2,2-二甲基-3-[2-三氟甲基-2-溴2-氯-1-甲磺酰氧基乙基]环丙烷甲酸1,1-二甲基乙基酯
于-10℃,在6.74g前一步骤中制备的产物、40cm3二氯甲烷的混和物中,加入8cm3三乙胺,在冰浴上加入4.3cm3甲磺酰氯并搅拌1小时。倾析后,用水和饱和氯化钠溶液洗涤有机相,脱水后进行减压干燥。于是得到9g产物,在硅胶上进行层析,用己烷-异丙醚混和液(8—2)洗脱。于是得到5.67g所要的产物,熔点为100℃。步骤C:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基-3-[2-三氟甲基-2-溴2-氯1-甲磺酰氧基乙基]环丙烷甲酸
于40℃,在含有1g前一步骤中制备的产物和10cm3二氯甲烷的溶液中,加入30mg对甲苯磺酸。反应混和物于40℃加热5小时,然后倾入冰中,然后倾析。有机相用水洗涤,用硫酸钠脱水并进行减压干燥。得到860mg所要的产物,熔点为138℃。步骤D:[1R-[1-α-(S*)3-α-(RS*,RS*)]]2,2-二甲基-3-[2-三氟甲基-2-溴2-氯-1-甲磺酰氧基乙基]环丙烷甲酸(S)氰基-(3-苯氧基苯基)甲基酯
在实例1(步骤B)的条件下,将前一步骤中得到的酸用S-α氰基3-苯氧基苄醇酯化,制备该产物。NMR光谱CDCl3成对甲基=1.24-1.27ppm和1.22-1.27ppmH1和H3=1.88-2.03ppmHa=5.54-5.60ppmHg=6.62-6.64ppm芳香H6.99-7.42ppm实例22:[1R-1-α-(S*)3-α-(RS*,RS*)]]2,2-二甲基-3-[2-三氟甲基2-溴2-氯-1-甲磺酰氧基乙基]-环丙烷甲酸氰基-(3-苯氧基4-氟苯基)甲基酯
如实例21的酯进行制备,但使用S-α氰基4-氟3-苯氧基苄醇。NMR光谱CDCl3成对CH3=1.23-1.25ppmH1和H3=1.9-2.15ppmSO2CH3=3.1ppmH′=5.32-5.7ppm苄基H=6.5ppm芳香H=6.85-7.6ppm实例23:[1R-[1-α-(R,S*)3-α-(RS*)]]2,2-二甲基3-[2-三氟甲基2-溴2-氯-1-甲磺酰氧基乙基]环丙烷甲酸氰基-(3-苯氧基2-吡啶基)甲基酯
如实例21的酯制备该产物,但使用RS-α氰基1-(6-苯氧基2-吡啶基)甲醇。NMR光谱CDCl3CH3甲基=1.25 1.3 1.43ppmH1H3=1.93 2.03ppmSO3CH3=3.05-3.07 3.12-3.16ppmH1′=5.32 5.7ppm苄基H=6.36 6.55ppm芳香H=6.87-7.99ppm实例24:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基3-(2-三氟甲基2-溴2-氯-1-甲磺酰氧基乙基)环丙烷甲酸(五氟苯基)甲基酯
如实例21的酯制备该产物,但使用五氟苄醇。m.p.=101℃。NMR光谱CDCl3成对CH3=1.26-1.39ppmH1,H3=1.75-1.98ppmSO3CH3=3.12-3.15ppmCO2-CH2=5.27ppmHa=5.7ppm实例25:[1R-[1-α,3-α-(RS,RS)]]2,2-二甲基-3-(2-三氟甲基2-溴2-氯1-甲磺酰氧基乙基)环丙烷甲酸(2-甲基3-苯基苯基)甲基酯
如实例21的酯制备该产物,但使用2-甲基3-苯基苄醇。NMR光谱CDCl3主要的非对映异构体(2/3)成对CH3=1.22-1.37ppmCH3=2.22ppmCO2CH2=5.27ppm O2S CH3 3.04ppmHa(5.6/5.64ppm H1 1.8-2.06ppm
(5.7 ppm H3芳香H=6.92/7.35ppm实例26:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基3-(2-三氟甲基2-溴2-氯1-甲磺酰氧基乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯步骤A:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基3-(2-三氟甲基2-氯2-溴1-羟乙基]环丙烷甲酸(3-苯氧基苯基)甲基酯
如实例21的步骤A所述进行操作制备该醇,但以1R,顺2,2-二甲基3-甲酰环丙烷甲酸3-苯氧基苄基酯起始。NMR光谱CDCl3成对CH3=1.21ppmH1,H3=1.54-1.92ppmH1′=4.28ppmCH2=5.08ppmOH=3.22ppm步骤B:[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基-3-(2-三氟甲基2-溴2-氯1-甲磺酰氧基乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯
在实例21的步骤B所述的条件下进行甲磺酰化。NMR光谱CDCl3成对CH3=1.23/1.36ppmH1,H3=1.8-2.06ppmCH3SO2=3.08/3.11ppmCO2CH2=5.15ppmH1′=3.85ppm-5.78ppm芳香H,6.87-7.55ppm实例27:[1R-[1-α,3-α]]2,2-二甲基3-[2-三氟甲基2-氯乙烯基]环丙烷甲酸
2g[1R-[1-α,3-α-(RS*,RS*)]]2,2-二甲基3-[2-三氟甲基2-溴2-氯1-甲磺酰氧基乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯在200mg10%的钯催化剂存在下,在30cm3乙醇中进行氢化。过滤,滤液进行减压干燥。如此得到产物,将其溶于20cm3当量氢氧化钠溶液中。水相用二氯甲烷洗涤,用浓盐酸酸化,然后用二氯甲烷萃取。萃取液脱水并进行干燥。于是得到400mg所要的产物,熔点为103℃。NMR光谱CDCl3异构体ZHa=6.83 6.98ppm异构体DE=6.55 6.7ppm实例28:1R-[1-α,3-α-(RS*,RS*)]2,2-二甲基-3-[2-溴2-氯1-[[4-甲基苯磺酰基]氧基]-3,3,3-三氟丙基环丙烷甲酸[2-甲基(1,1′-联苯基)-3-基]甲基酯步骤A:1R(1-α,3-α)2,2-二甲基3-甲酰环丙烷甲酸[2-甲基(1,1′-联苯基)-3-基]甲基酯
于0/5℃,在3.5g1R(1-α,3-α)2,2-二甲基3-甲酰环丙烷甲酸在100cm3 THF的溶液中,慢慢加入0.55g氢化钠。于0℃搅拌1小时后,加入12.9g[2-甲基(1,1′-联苯基)-3-基]甲基溴在30cm3二甲基甲酰胺中的溶液,在室温下持续搅拌22小时。蒸发部分溶剂,将混和物倾入冰水中,用异丙醚萃取。将有机相脱水并进行干燥,残渣在硅胶上进行层析(洗脱液:己烷-异丙醚7—3)。所获纯产物重7.7g。步骤B:
于-60℃,在3.22g步骤A中制备的产物和1.6cm3卤乙烷(CF3CH Br Cl)在15cm3四氢呋喃中的溶液中,慢慢加入溶于10cm3四氢呋喃的1.3g叔丁醇钾。然后,仍在-60℃下,加入20cm3四氢呋喃中的3.8g甲苯磺酰氯和0.8g二甲基氨基吡啶。于-60℃接触1小时30分钟后,将反应介质倾入磷酸二氢钾溶液中。用二氯甲烷萃取后,用水洗涤,干燥有机相,将干燥的剩余物在硅胶上进行层析(洗脱液:己烷-异丙醚8—2),分离出3.58纯产物。NMR光谱(CDCl3)成对CH3=1.24-1.38ppm甲苯磺酰CH3=2.4ppmCH3=2.25ppmH1H3=1.83-2.1ppmH1′=5.73-5.9ppm实例29:1R-[1-α,3-α-(RS*,RS*)]]3-[2-溴2-氯1-[二乙氧基磷酰基)3,3,3-三氟丙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯步骤A:1R[1-α,3-α(RS*,RS*)3-[2-溴2-氯1-(二乙氧基磷酰氧基)3,3,3-三氟丙基]2,2-二甲基环丙烷甲酸1,1-二甲基乙基酯
于-60℃,在2g1R(1-α,3-α)3-甲酰2,2-二甲基环丙烷甲酸1,1-二甲基乙基酯和1.2cm3卤乙烷(CF3CH Br Cl)在20cm3四氢呋喃中的溶液中,慢慢加入溶于10cm3四氢呋喃中的1.3g叔丁醇钾。于-60℃下搅拌15分钟中,滴加1.6cm3氯化磷酸二乙酯在4cm3四氢呋喃中的溶液。于-60℃下接触30分钟后,将该混合物倾入磷酸二氢钾水溶液中。用二氯甲烷萃取,分离出一种油状物,将其在硅胶柱上层析进行纯化。于是分离出2.1g所期望的产物。步骤B:1R-[1-α(S)3-α(RS*,RS*)3-(2-溴2-氯1-二乙氧基磷酰氧基3,3,3-三氟丙基)2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在对甲苯磺酸(60mg)的存在下,将1.74g前一步骤中得到的产物在苯(15cm3)中加热回流48小时。将反应混合物倾入冰水混和物中,用二氯甲烷萃取;萃取液进行洗涤、脱水并浓缩至干。残渣在硅胶上进行层析(洗脱液:己烷-乙酸乙酯1—1),得到中间产物酸。在实例1的步骤B所述条件下,将全部的酸用S-α氰基3-苯氧基苄醇(0.46g)进行酯化。色谱法纯化得到0.6g所期望的产物。NMR光谱CDCl3成对CH3=1.17-1.23ppmEtO的CH3=1.36ppmEtO的CH2=4.17ppmH1-H3=1.93-1.96ppmH1′=5.21ppm苄基H=6.55ppm实例30:1R-[1-α(S)3-α(R)]2,2-二甲基-3-[2,2,2-三溴1-[(3-羟基2-甲基)丙磺酰氧基)乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
室温下,将125cm3四氢呋喃中的5g实例5中得到的产物和3.75gN-甲基吗啉N-氧化物与40cm3水一起混合。加入100mg四氧化锇,于20℃搅拌22小时。将反应介质用250cm3二氯甲烷稀释,冷却至0℃,然后慢慢加入6g亚硫酸氢钠在40cm3水中的溶液。使整个体系升至室温,脱水,并减压除去溶剂。得到的5.1g粗产物在硅胶上进行层析(洗脱液:己烷-乙酸乙酯85—15)。收集到1.7g所期望的产物,用乙醚处理后,得到1.4g无定形产物。[α]D=+38°±1°(C=1%氯仿)分析:C26H28Br3NO8S:754.306计算值:C% 41.40 H% 3.74 N% 1.86 Br% 31.78 S% 4.25分析值: 41.7 3.7 1.9 30.0 4.1实例31:1R-[1-α(S)3-α(R)]2,2-二甲基-3-[2,2,2-三溴-1-[(3-羟基2-羟基)丙磺酰氧基)乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
如实例30进行操作,以实例9中得到的产物起始。在硅胶上进行层析(洗脱液:二氯甲烷-乙酸乙酯1—1)并用乙醚导出残液后,得到2.6g所期望的产物。[α]D=+41°±1.5°(C=0.7%CHCl3)分析:C25H26Br3NO8S:754.306计算值:C% 40.56 H% 3.54 N% 1.89 Br% 32.38 S% 4.33分析值: 40.8 3.3 1.8 30.5 4.3实例32:1R-[1-α(S)3-α(R)]2,2-二甲基-3-[2,2,2-三溴1-[(2,2-二甲基3-二氧戊环-4-基)甲磺酰氧基]乙基]环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯
在130cm3丙酮中,将1.3g实例31中得到的产物和130mg对甲苯磺酸在20℃下搅拌2小时,然后用100cm3水稀释。脱水后减压除去溶剂。收集到1.25g粗产物,将其在硅胶上进行层析(洗脱液:己烷-乙酸乙酯3—1),得到1.15g所期望的产物。[α]D=+44°±1.5°(C=1%CHCl3)。
如前面这些实例进行操作,制备下列产物:实例33:(1R,顺)2,2-二甲基-3-(2,2,2-三溴1-三甲硅烷氧基乙基)-环丙烷甲酸(S)-α氰基-(3-苯氧基苯基)甲基酯m.p.=98℃。[α]D=+64°±1°(C=2%甲苯)实例34:[1-α(S),3-α(R)]3-[2,2,2-三溴1-(2-乙基磷酸吡啶鎓)乙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯[α]D=+13°±2°(C=0.65%氯仿)实例35:[1-α(S),3-α(R)]3-[2,2,2-三溴1-(2-乙基磷酸三甲铵)乙基]2,2-二甲基环丙烷甲酸氰基-(3-苯氧基苯基)甲基酯[α]D=+14°±1°(C=1%氯仿)实例36:(1R,顺)2,2-二甲基-3-(2,2,2-三氯1R-甲氧基乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯分析:C22H23Cl3O4计算值:C% 57.72 H% 5.06 Cl% 23.23分析值: 57.8 5.1 23.0实例37:(1R,顺)2,2-二甲基-3-(2,2,2-三氯1R-甲氧基乙基)环丙烷甲酸(R S)氰基-(3-苯氧基苯基)甲基酯分析:C23H22Cl3NO4计算值:C% 57.22 H% 4.59 Cl% 22.03 N% 2.9分析值: 57.5 4.7 21.9 2.8实例38:(1R,顺)2,2-二甲基-3-(2,2,2-三氯1R-乙酰氧基乙基)环丙烷甲酸(3-苯氧基苯基)甲基酯分析:C2H23Cl3O5计算值:C% 56.87 H% 4.77 Cl% 21.89分析值: 56.9 4.8 21.7实例39:(1R,顺)2,2-二甲基-3-(2,2,2-三氯1R-甲磺酰氧基乙基)环丙烷甲酸(R)或(S)氰基-(3-苯氧基苯基)甲基酯[α]D=+7°(C=0.75苯)实例40:可溶性浓缩剂的制备
由下列物质组成均一混合物:实例2的产物 0.25g胡椒基丁醚 1.00g吐温80 0.25gTopanol A 0.1g水 98.4g实例41:可乳化的浓缩剂的制备
准确混和下列物质:实例3的产物 0.015g胡椒基丁醚 0.5gTopanol A 0.1g吐温80 3.5g二甲苯 95.885g实例42:可乳化的浓缩剂的制备
由下列物质组成均一混和物:实例8的产物 1.5g吐温80 20.00gTopanol A 0.1g二甲苯 78.4g实例43:熏蒸制剂的制备
均一地混合下列物质:实例20的产物 0.25gTabu粉剂 25.00g雪松叶粉 40.00g松木屑 33.75g亮绿 0.5g对硝基苯酚 0.5g实例44:动物复合饲料实例
用含下列物质的饲料作为平衡基本饲料(balanced basicfood):玉米、脱水苜蓿、麦草、糖浆棕榈芯、脲、含维生素的无机调味品。
该饲料至少含11%粗蛋白物质(其中2.8%由脲提供),2.5%脂肪物质,最多含15%纤维素物质,6%无机物质和13%水份。
所用饲料相当于每100千克饲料为82饲料单位,并且,每100千克饲料维生素A910,000 I.U.,维生素D 91,000 I.U.,维生素E 150mg,维生素C150mg。
在此饲料中,每100kg全饲料掺入0.3kg实例1的化合物。实例45:动物复合饲料实例
使用与实例44相同的平衡基本饲料。在此饲料中,每100kg全饲料掺入0.04Kg实例2的化合物。
生物学研究1)对家蝇击倒活性的研究
受试昆虫为4—5日龄的雌性家蝇。用阿诺德显微操作器进行操作,将1微升丙酮溶液局部涂于昆虫的背胸部。
每次用50只家蝇进行处理。处理24小时后进行成活率测定。
所获结果以LD50即杀死50%的昆虫所需的剂量(毫微克/个体)表示如下:
结论:本发明的产物对家蝇具有极好的击倒作用。2)对德国蜚蠊的跗节接触活性的研究
实例化合物 | LDng/昆虫 |
2348202122303132 | 1.72.78.71.32.31.10.95.75.24.5 |
受试昆虫为雄性德国蜚蠊(Blatella germanica)。将已知浓度的丙酮溶液置于直径为20cm的平皿底部而进行操作。干燥后,每个浓度放20只雄性蜚蠊并保持1小时,然后将昆虫移至洁净基质中,分别在24小时、48小时、3天和5天后检查其成活率。
结果用致死浓度50(LC50)以mg/ml为单位表示。
3)对海灰翅夜蛾(Spodoptera Littoralis)幼虫的致死作用的研究
实例 | LC50(mg/ml) |
2345892021222325303132 | 1.20.222.50.070.060.30.020.0050.120.150.300.290.22 |
利用阿诺德显微操作器,将丙酮溶液局部施用于幼虫的背胸部而进行测试。产物的每个剂量用15只幼虫进行测试。所用幼虫为第四幼虫期的幼虫,即在24℃和65%相对湿度下饲养的约10日龄的幼虫。处理后,将幼虫个体置于人工营养基质(Poitout medium)上。
处理48小时后,进行成活率检查。所获实验结果总结于下表中:
对海灰翅夜蛾幼虫局部施药
研究活性
试验结果
实例 | LD50(ng/昆虫) |
23482021222325 | 1311252.86.523.592432 |
Claims (4)
2.式(I)化合物的使用方法,其中,X1和X2彼此相同或不同,代表卤原子,R1代表卤原子或三氟甲基,Y代表选自下列一组基团的基团:-SO2alk1基,alk1代表含有8个和以下碳原子的烷基或链烯基;-SO2Ar自由基,Ar代表苯基;-基团或
alk2和alk3彼此相同或不同,代表含有8个和以下碳原子的烷基或链烯基,或者,alk2和alk3可与
基形成环
,A代表饱和或不饱和的,由一个或多个功能团任意取代、含有6个和以下碳原子的直链或分枝的碳链;-基团
,alk2′和alk3′的含义与alk2和alk3相同;R代表氢原子、含8个和以下碳原子的烷基或R为下列自由基:或
或或
W-H,CH3,OCH3其特征在于,将式(I)化合物与一种还原剂作用,以得到相应的式(III)化合物:其中X1、R1和R具有前述意义。
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KR880007430A (ko) * | 1986-12-11 | 1988-08-27 | 허버트 프리텔 | 펜타플루오로페닐메틸 2,2-디메틸3-포밀 시클로프로판 카르복실레이트의 제조방법 |
AU610856B2 (en) * | 1987-02-24 | 1991-05-30 | Sandoz Ltd. | Alpha cyanobenzyl esters of cyclopropane carboxylic acids |
FR2636945B1 (fr) * | 1988-09-29 | 1991-04-19 | Roussel Uclaf | Nouveaux derives de l'acide 2,2-dimethyl 3-(1-hydroxy-2-sulfino-ethyl) cyclopropane carboxylique, leur procede de preparation et leur application comme pesticides |
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GB2099810A (en) * | 1981-06-09 | 1982-12-15 | Shell Int Research | Cyclopropanecarboxylate esters and their use as pesticides |
FR2534252A1 (fr) * | 1982-10-12 | 1984-04-13 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique substitues en 3 par une chaine vinylique elle-meme substituee, leur procede de preparation et leur application comme pesticides |
IT1206727B (it) * | 1985-01-11 | 1989-05-03 | Donegani Guido Ist | Processo per la preparazione di carbinoli polialogenati. |
JPH0674238B2 (ja) * | 1985-09-30 | 1994-09-21 | 財団法人相模中央化学研究所 | 2,2−ジメチルシクロプロパンカルボン酸誘導体 |
FR2607133B1 (fr) * | 1986-11-20 | 1989-05-05 | Roussel Uclaf | Nouveaux derives de l'acide 2,2-dimethyl cyclopropane carboxylique portant en 3 une chaine halogenee saturee, leur procede de preparation et leur application comme pesticides |
-
1986
- 1986-11-20 FR FR8616155A patent/FR2607133B1/fr not_active Expired
-
1987
- 1987-11-18 MX MX941287A patent/MX9412A/es unknown
- 1987-11-18 HU HU875123A patent/HU206075B/hu not_active IP Right Cessation
- 1987-11-19 DE DE3751149T patent/DE3751149T2/de not_active Expired - Fee Related
- 1987-11-19 DE DE8787402605T patent/DE3781383T2/de not_active Expired - Fee Related
- 1987-11-19 BR BR8706250A patent/BR8706250A/pt unknown
- 1987-11-19 EP EP91105956A patent/EP0445843B1/fr not_active Expired - Lifetime
- 1987-11-19 ES ES87402605T patent/ES2051762T3/es not_active Expired - Lifetime
- 1987-11-19 RU SU874203815A patent/RU1779242C/ru active
- 1987-11-19 AT AT91105958T patent/ATE119516T1/de not_active IP Right Cessation
- 1987-11-19 EP EP91105958A patent/EP0451873B1/fr not_active Expired - Lifetime
- 1987-11-19 EP EP87402605A patent/EP0269514B1/fr not_active Expired - Lifetime
- 1987-11-19 DE DE3789064T patent/DE3789064T2/de not_active Expired - Fee Related
- 1987-11-19 ES ES91105956T patent/ES2062598T3/es not_active Expired - Lifetime
- 1987-11-19 ES ES91105958T patent/ES2069765T3/es not_active Expired - Lifetime
- 1987-11-19 PT PT86171A patent/PT86171B/pt not_active IP Right Cessation
- 1987-11-19 ZA ZA878666A patent/ZA878666B/xx unknown
- 1987-11-20 AU AU81434/87A patent/AU593955B2/en not_active Ceased
- 1987-11-20 US US07/123,374 patent/US4925874A/en not_active Expired - Lifetime
- 1987-11-20 KR KR1019870013093A patent/KR960010787B1/ko active IP Right Grant
- 1987-11-20 OA OA59226A patent/OA08693A/xx unknown
- 1987-11-20 CN CN87101182A patent/CN1033028C/zh not_active Expired - Fee Related
- 1987-11-20 JP JP29224687A patent/JP2717787B2/ja not_active Expired - Fee Related
-
1989
- 1989-10-18 US US07/423,803 patent/US5082832A/en not_active Expired - Fee Related
-
1991
- 1991-04-15 AT AT91105956T patent/ATE101391T1/de active
-
1992
- 1992-08-27 GR GR920400799T patent/GR3005520T3/el unknown
-
1994
- 1994-11-18 JP JP30834994A patent/JP2710097B2/ja not_active Expired - Fee Related
-
1995
- 1995-10-07 CN CN95115659A patent/CN1125714A/zh active Pending
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