EP0367789A1 - Procede d'isomerisation de triazoles symetriques en triazoles asymetriques - Google Patents

Procede d'isomerisation de triazoles symetriques en triazoles asymetriques

Info

Publication number
EP0367789A1
EP0367789A1 EP88906344A EP88906344A EP0367789A1 EP 0367789 A1 EP0367789 A1 EP 0367789A1 EP 88906344 A EP88906344 A EP 88906344A EP 88906344 A EP88906344 A EP 88906344A EP 0367789 A1 EP0367789 A1 EP 0367789A1
Authority
EP
European Patent Office
Prior art keywords
triazole
alkyl
formula
isomerization
mole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP88906344A
Other languages
German (de)
English (en)
Inventor
Christopher Scott Barnum
William Karl Moberg
Richard Eric Olson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0367789A1 publication Critical patent/EP0367789A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • U.S. Patents 4,530,922 and 4,510,136 disclose the preparation of mixtures of isomeric 1,2,4-triazolyl methylsilanes in which the unsymmetrical isomer pre- dominates.
  • U.S. 4,639,527 discloses the production of ⁇ -hydroxyalkyl-1,2,4-triazoles from ⁇ -hydroxyalkyl- 1,3,4-triazoles by heating the symmetrical isomers with base in polar-aprotic solvents.
  • EP-A-143,379 (Bayer) discloses the production of a class of ⁇ -hydroxyalkyl-1,2,4-triazoles from appropriate oxiranes without concurrent symmetrical triazole formation in the presence of base and cyclic amides.
  • Q is an optionally substituted radical of up to about 35 carbon atoms bonded to the triazole or to X through a carbon atom; and X is Cl, Br or I; provided that
  • heteroatom substituents on the carbon atom of Q bonded to the nitrogen atom of the triazole or to X are limited to one oxygen radical so as to form an ether linkage or one silicon radical;
  • Q are the radicals of antifungal, antimycotic or microbicidal 1H-1,2,4- triazoles including the following:
  • R 1 is C 1 -C 4 alkyl, OR 11 or CN;
  • R 2 is H, C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 6
  • R 3 is halogen or phenyl
  • R 4 is H or halogen
  • R 5 is C 1 -C 4 alkyl
  • R 6 is C 5 -C 7 alkylcarbonyl or
  • R 7 is H or CH 3 ;
  • R 8 and R 9 are independently C 1 -C 4 alkyl
  • R 10 is H or C 1 -C 4 alkyl
  • R 11 is H, C 1 -C 4 alkyl or C 2 -C 4 alkenyl
  • R 12 and R 13 are independently H or C 1 -C 4 alkyl; n is 0, 1 or 2; and
  • Z is O or CH 2 .
  • Q is generally a radical of up to about 25 carbon atoms, usually up to about 20 carbon atoms, preferably between about 10 and about 20 carbon atoms.
  • Preferred O radicals include
  • Q is not substituted by a hydroxyl group.
  • the isomerizing agent should be present in a concentration of at least about 1 mole %, usually about 1-20 mole %, preferably about 2-10 mole %, especially, about 6 mole %.
  • reaction media include N,N-dimethyl- formamide, toluene, xylene, ortho-diehlorobenzene or methylethyl ketone, especially, xylene.
  • the iso- merizing agent of Formula III is formed in situ by initially introducing into the reaction media a compound of the Formulae IV, V or VI different from the compound of Formula III
  • R 14 and R 15 are independently H, C 1 -C 6 alkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl,.
  • R 16 , R 17 and R 18 are independently C 1 -C 8 alkyl, -
  • Y and Z are independently H, F, Cl, Br, I, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl S(O) m , C 1 -C 3 haloalkyl S(O) m , NO 2 , CN or phenyl; and m is 0, 1 or 2.
  • This invention also comprises a process (Equation 2) for the conversion of a symmetric 4H-1,2,4-triazole of Formula VII to an unsymmetric 1H-1,2,4-triazole of Formula VIII in the presence of an oxirane, L.
  • J is an optionally substituted radical of up to about 35 carbon atoms bonded to the triazole through a carbon atom; provided that
  • substituents on the carbinol radical are selected from the group consisting of hydrogen or a radical bonded through a carbon atom;
  • the remaining substituent on the carbon atom of J bonded to the nitrogen atom of the triazole is selected from either a second hydrogen atom or an optionally substituted radical bonded through a carbon atom; (d) when the remaining substituent on the carbon atom of J bonded to the nitrogen atom of the triazole is other than a second hydrogen atom, then at least one of the substituents of the carbinol carbon is a hydrogen atom; and
  • L is the corresponding oxirane derivative of the radical J where the epoxide ether linkage is formed between the carbinol hydroxyl group of
  • Nonlimiting examples of J are the radicals of antifungal, antimycotic or microbicidal 1H-1,2,4- triazole carbinols including the following: > ;f R
  • R 19 is H, C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl C 4 -C 6
  • R 20 is halogen or phenyl;
  • R 21 is H or halogen;
  • R 22 is C 1 -C 4 alkyl;
  • R 23 is or C 5 -C 7 alkylcarbonyl; and 21 p is 0, 1 or 2.
  • J is generally a radical of up to about 25 carbon atoms, usually up to about 20 carbon atoms, preferably between about 10 and about 20 carbon atoms.
  • Preferred J radicals and the corresponding oxiranes L include
  • the oxirane L is formed in situ by initially introducing into the reaction media a compound of Formula IX different from the oxirane L,
  • R 24 is H, C 1 -C 2 alkyl, C 2 -C 6 alkylcarbonyl; R 25 and R 26 are independently H, C 1 -C 6 alkyl, - R 27 and R 28 are independently H, F, Cl, Br, I,
  • R 25 or R 26 is hydrogen.
  • Equation A V. Kendal, J. Org. Chem. 35. 2246, 1970 and C. Temple and J. A. Montgomery, Triazoles. Vol. 37 of The Chemistry of Heterocyclic Compounds. A. Weissberger and E. C. Taylor, Eds., John Wiley and Sons, New York, 1981, page 5). While such alkylation reactions (Equations A and B) can be conveniently carried out by the treatment of a metal salt (M) of the 1,2,4-triazole (1) with an alkylating agent (RZ or an oxirane), mixtures of the unsymmetrical 1H-1,2,4-alkyltriazole (2ab) and symmetrical 4H-1,2,4-alkyltriazole (3ab result (see J. Org. Chem. 35. 2246, 1970). Equation A
  • the unsymmetrical 1H-1,2,4-triazole is the major product with the amounts of the symmetrical 4H-1,2,4-triazole by-product varying with the reaction conditions (solvent, temperature), nature of the metal ion, and nature of the alkylating agent.
  • Q or J represent the radicals of antifungal, antimycotic or microbicidal 1H-1,2,4-triazoles (compounds of Formula II or Formula VIII) are well known in the art.
  • German Patent Application 3,326,456 (published January 31, 1985). 12. European Patent Application 158,448 (published October 16, 1985).
  • German Patent Application 3,018,865 (published November 26, 1981).
  • the intermediate 4 can be prepared according to the teachings of the previously cited application.
  • the triazole of Formula II where Q is Q 7 and the triazole of Formula VIII where J is J 2 are disclosed in U.S. 4,217,129.
  • the halides of Formula III where Q is Q 7 and the oxirane L 2 can be prepared from the ⁇ , ⁇ -unsaturated ketone (5 ) by
  • Intermediate 5 can be prepared from diketone 6 and aldehyde 2 according to the methods described in K. Uchara, F. Kitamura, M. Tanaka, Bull. Chem. Soc. Jap. 49, 493 (1976). v
  • Diketone 6 can be prepared according to the teachings in R. Levine, J. A. Conroy, J. Adams, C. R. Hauser, J. Am. Chem. Soc. 67, 1510 (1945).
  • Aldehyde 7 is available through the oxidation of commercially available 3,3-dimethyl-1-butanol by known methods.
  • the triazoles of Formula II where Q is Q 8 and of Formula VIII where J is J 3 are disclosed in U.S. 4,243,405 and U.S. 4,205,075.
  • the halides of Formula III where Q is Q 8 can be prepared by metal hydride reductions of the ⁇ -haloketones 8 disclosed in the previously cited patents by methods described in H. O. House, Modern Synthetic Reactions, second edition, W. A. Benjamin, 1972, pages 474 to 476.
  • the epoxide L 3 can be prepared from the corresponding halohydrins of Formula III utilizing methodology also described in Modern Synthetic Reactions, pages 435 and 436.
  • halides of Formula III where Q is Q 10 can be prepared from the ketone 9 disclosed in the previously cited reference by reaction with methylene triphenylphosphorane followed by conversion of the resulting olefin 10 to a halohydrin (Formula III,
  • the triazoles of Formula II where Q is Q 11 , the triazole of Formula VIII where J is J 6 , and the oxirane L 6 are disclosed in EP-A-40,345.
  • the halides of Formula III where Q is Q 11 can be prepared from ketone 11 disclosed in the previously cited reference by reaction with methylenetriphenylphosphorane followed by conversion of the resulting olefin 12 to a halohydrin (Formula III, Q 11 ) as described in Modern Synthetic Reactions, pages 432 to 442.
  • Equation C treatment of the 4H-1,2,4-triazole I with the isomerizating agent QX results in the formation of the quaternary ammonium salt X which then undergoes fragmentation to the 1H-1,2,4-triazole II with the regeneration of QX.
  • This sequence is exemplified in Equation E by the isomerization of 1-[[bis(4-fluorophenyl)methylsilyl]- methyl]-4H-1,2,4-triazole (Q is Q 1 ) to 1-[[bis(4- fluorophenyl)methylsilyl]methyl]-1H-1,2,4-triazole.
  • Equation D The process of Equation D is exemplified by the isomerization of (RS)-2,4'-difluoro- ⁇ -(4H-1,2,4- triazol-1-ylmethyl)benzhydryl alcohol (J is J 1 ) to (RS)-2,4'-difluoro- ⁇ -(1H-1,2,4-triazol-1-ylmethyl)- benzhydryl alcohol (Equation F).
  • Q and J would not contain functional groups which themselves would be reactive with the isomerizing agents QX or L, for example, thiols or amines including amino groups, substituted amino groups or nitrogen containing heterocycles, or that such functionality would first have to be render- ed non reactive prior to carrying out the isomerization process, utilizing a molar excess of the isomerizing agent or "protecting groups" well known in the art. See for example, T. W. Greene, Protective Groups in Orqanic Synthesis, John Wiley and Sons, New York, 1981.
  • Suitable solvents include aliphatic and aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, esters, and amides.
  • Specific solvents include petroleum fractions, petroleum ethers, C 5 -C 8 aliphatic hydrocarbons, for example, pentane, hexane, heptane, octane, nonane, decane, cyclohexane or methylcyclohexane, benzene, toluene, xylenes, chlorobenzene, dichlorobenzene, trimethylbenzene, durene, p-ethyltoluene, ethylether, methyl-t-butyl ether, i-propylether, tetrahydrofuran, dioxane, ethyl acetate, dimethylacetamide, dimethylformamide and N-methylpyrrolidinone.
  • Preferred solvents include aromatic and halogenated aromatic
  • the rate and/or efficiency of the isomerization process is affected by moisture, the reaction temperature, the degree of. mixing of ingredients, and the concentrations, ratios and chemical structure of the reactants.
  • the present invention is conducted at elevated temperatures usually between about 100oC and about
  • 300°C preferably between about 100oC and about 250oC more preferably between about 140oC and about 200oC.
  • the main I'imitation is the solubility of the materials in the solvent at the reaction temperature if a solvent is to be used.
  • reactions can be carried out in the presence of less than stoichiometric (i.e., less than about 90%) amounts of these reactants (QX or L).
  • QX or L reactants
  • quantities of QX or epoxide L of about 0.1 mole % relative to the amount of the symmetrical triazoles I or VII can effect isomerization to the unsymmetrical isomer
  • the preferred range of these reactants is about 1 to 20 mole %, more preferred is about 2 to 10 mole % most preferred is about 4 to 8 mole %, especially preferred is about 6 mole %.
  • Factors to consider in the selection of the ratio of QX or L with respect to the triazoles I or VII is the desired rate of isomerization, reaction temperature, relative reactivity of QX or L and the ease of separ- ation of these reactants from the product unsymmetrical triazole in the reaction mixture.
  • the use of very high temperatures for the conversion can effect the decomposition of QX or L resulting in a decrease in the conversion rate and/or reduced yields of the product triazole, however.
  • the relative reaction rate is also affected by the reactivity of the isomerizing agents QX and L.
  • iodides are more reactive than the corresponding bromides which are more reactive than the chlorides.
  • Primary halides QX are more reactive than secondary halides.
  • Primary epox- ides L are more reactive than secondary epoxides.
  • the addition of pyri- dines, tertiary phosphines or tertiary amines may enhance the reactivity of these halides.
  • the isomerizing agents QX or L can also be conveniently generated in situ in the reaction mixture as described in Equations G and H.
  • RX represents a halide, silyl- halide or silylmethylhalide of Formula IV , V or VI. respectively different from QX.
  • Triazole substrates of Formula I bearing free hydroxyl groups may react with compounds of
  • halides of Formula IV are commercially available or can be prepared from commercially available alcohols by methods well known to one skilled in the art.
  • Silylhalides and silyl- methylhalides are also available from commercial sources or can be prepared, as described in V. Bazant, V. Chvalovsky, J. Rathousky, Qrganosilicon Compounds. Academic Press, New York, 1965 and C. Eaborn, Organosilicon Compounds. Butterworths Scientific Publications, London, 1960.
  • iodides are more reactive than the corresponding bromides which are more reactive than the chlorides.
  • Primary alkyl or arylalkyl halides are more reactive than secondary derivatives.
  • Suitable compounds of Formulae IV, V and VI include methyl iodide, ethyl iodide, benzyl iodide, benzyl bromide, benzyl chloride, trimethyl- silyl iodide, trimethylsilyl bromide, trimethylsilyl chloride, triethylsilyl chloride, triphenylsilyl bromide, triphenylsilyl chloride and trimethylsilyl- methyl iodide.
  • the epoxide L can be generated by initial reaction of an epoxide of Formula IX different from L with the triazole of Formula VII.
  • L then effects the isomerization of the symmetrical triazole VII to the unsymmetrical triazole VIII and is subsequently regenerated.
  • the reaction conditions for this sequence are as previously discussed where the isomerization is effected directly by L.
  • the process is again most useful the higher the ratio of the substrate triazole VII to the initiating epoxide IX. The higher this ratio, the lower the reduction in yield of the product triazole VIII resulting f rom the formation of the triazole XIII and the easier the separation of the product from the other species of the reaction mixture.
  • Many epoxides of Formula IX are commercially available or can be prepared from commercial olefins by epoxidation methods well known to one skilled in the art.
  • Suitable epoxides of Formula IX include 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxydecane, 1,2-epoxydodecane, styrene oxide, 1,2-e ⁇ oxyhexane, 1,2-epoxyoctane or 1,2-epoxypropane.
  • Equation I by the isomerization of the symmetrical triazole of Q 6 , conversion of a triazole of Formula I, where the carbon atom of Q bonded to the nitrogen atom of the triazole is also bonded to a carbinol group, to the corresponding triazole of Formula II, by reaction with a halide of Formula III can afford an epoxide XIV in addition to or instead of the reformation of halide III.
  • the epoxide XIV so formed can then effect the conversion of the triazole I as previously described in Equations D and F.
  • the epoxide XIV can also be formed utilizing a halide of Formulae IV, V or VI as described in Equation G.
  • xylene refers to a mixture of the ortho, meta and para isomers. All gas chromatographic analyses were performed on a Hewlett-Packard 5840A Gas Chromatograph equipped with an FID detector utilizing a HP17 flexible capillary column (50% phenyl sili- cone). The initial column temperature was 135oC and was programmed to rise 8oC/min. from 135-250oC.
  • the bis (4-fluorophenyl) (iodomethyl)methysilane utilized as the isomerizing agent in Examples 1 and 5 was prepared as follows:
  • the reaction mixture was heated and dried azeotropically by removal of solvent through the distilling head. The distillation was continued until the temperature of the reaction mixture reached 175oC at which point all of the sec-butanol had been removed. The distil- lation head was then removed and replaced with a stopper, a con denser was inserted between the flask and the gas inlet tube and the mixture refluxed at
  • reaction mixture indicated 97% conversion of the starting 4H-1,2,4-triazole to 1-[[bis(4-fluorophenyl)- methylsilyl]methyl]-1H-1,2,4-triazole by comparison to an authentic sample prepared according to U.S. 4,510,136.
  • the reaction mixture was diluted to a 25% concentration of the 1H-1,2,4-triazole product by addition of xylene/ethylacetate (9:1).
  • Aqueous 37% hydrochloric acid (12 g) was added at a rate such that the temperature of the mixture remained below 30oC.
  • the resulting hydrochloride salt of the product which precipitated was collected by filtration and washed with xylene (60 ml).
  • Example 3 isomerization of 1-[[bis(4-fluoro ⁇ henyl)methylsilyl]- methyl]-4H-1,2,4-triazole to 1-[[bis(4-fluorophenyl)- methylsilyl]methyl]-1H-1,2,4-triazole utilizing trimethylsilyl iodide - identification of bis (4-fluorophenyl)(iodomethyl)methylsilane in the reaction mixture 1-[[Bis(4-fluorophenyl)methylsilyl]methyl]-4H-
  • 1,2,4-triazole was dried in xylene/sec-butanol (1:1) by azeotropic removal of the sec-butanol from the mixture through distillation. Cooling of the resulting xylene solution resulted in precipitation of the dried 4H-1,2,4-triazole which was collected by filtration.
  • the compound (25 g, 79 mmole), trimethylsilyl iodide (1.4 g, 7 mmole) and xylene (25 ml) were combined, solvent was removed by distillation until the temperature of the reaction mixture reached 175oC and then heating was continued at 175°C under nitrogen for 20 hrs.
  • Example 5 Isomerization of 1-[[bis(4-fluorophenyl)methylsilyl]- methyl]-4H-1,2,4-triazole to 1-[[bis(4-fluorophenyl)-methylsilyllmethyll-1H-1.2.4-triazole 1-[[Bis(4-fluorophenyl)methylsilyl]methyl]-4H- 1,2,4-triazole was azeotropically dried as described in Examples 2 and 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Des 4H-1,2,4-triazoles symétriques sont isomérisés en 1H-1,2,4-triazoles correspondants en présence d'un agent d'isomérisation consistant en un époxyde ou un halogénure organique. Ce procédé est utile pour la récupération de 1H-1,2,4-triazole antifongicide, antimycotique ou microbicide par isomérisation du sous-produit 4H-1,2,4-triazole indésiré formé pendant leur préparation.
EP88906344A 1987-06-16 1988-06-13 Procede d'isomerisation de triazoles symetriques en triazoles asymetriques Pending EP0367789A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6261987A 1987-06-16 1987-06-16
US62619 1987-06-16

Publications (1)

Publication Number Publication Date
EP0367789A1 true EP0367789A1 (fr) 1990-05-16

Family

ID=22043686

Family Applications (2)

Application Number Title Priority Date Filing Date
EP88906344A Pending EP0367789A1 (fr) 1987-06-16 1988-06-13 Procede d'isomerisation de triazoles symetriques en triazoles asymetriques
EP88305372A Expired - Lifetime EP0296745B1 (fr) 1987-06-16 1988-06-13 Procédé pour l'isomérisation de triazoles symmétriques à triazoles assymétriques

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP88305372A Expired - Lifetime EP0296745B1 (fr) 1987-06-16 1988-06-13 Procédé pour l'isomérisation de triazoles symmétriques à triazoles assymétriques

Country Status (6)

Country Link
EP (2) EP0367789A1 (fr)
AT (1) ATE115140T1 (fr)
BR (1) BR8807554A (fr)
DE (1) DE3852344T2 (fr)
ES (1) ES2064351T3 (fr)
WO (1) WO1988010255A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ270418A (en) * 1994-02-07 1997-09-22 Eisai Co Ltd Polycyclic triazole & imidazole derivatives, antifungal compositions
CN102321035B (zh) * 2011-06-14 2013-07-03 江苏七洲绿色化工股份有限公司 一种从1,2,4-三氮唑取代物中除去1,3,4-三氮唑取代物的方法
CN113582979B (zh) * 2021-08-20 2023-02-24 浙江禾本科技股份有限公司 一种由异构体合成丙环唑的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1176258A (fr) * 1981-06-24 1984-10-16 William K. Moberg Derives de triazole-1,2,4 et d'imidazole fongicides
DE3202613A1 (de) * 1982-01-27 1983-08-04 Bayer Ag, 5090 Leverkusen Antimykotische mittel
DE3342692A1 (de) * 1983-11-25 1985-06-05 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von ss-hydroxyethyl-(1,2,4-triazol)-derivaten
DE3342693A1 (de) * 1983-11-25 1985-06-05 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von ss-hydroxy-ethyl-(1,2,4-triazol)- derivaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8810255A1 *

Also Published As

Publication number Publication date
BR8807554A (pt) 1990-05-22
WO1988010255A1 (fr) 1988-12-29
EP0296745A1 (fr) 1988-12-28
DE3852344T2 (de) 1995-05-18
DE3852344D1 (de) 1995-01-19
ES2064351T3 (es) 1995-02-01
ATE115140T1 (de) 1994-12-15
EP0296745B1 (fr) 1994-12-07

Similar Documents

Publication Publication Date Title
US20090069569A1 (en) Cycloaddition of azides and alkynes
KR880002863A (ko) 트리아졸 또는 이미다졸기를 함유하는 2,5- 디히드로푸란 유도체, 그의 제조방법 및 살균제로서의 용도
Murata et al. Synthesis of alkenylsilanes via palladium (0)-catalyzed silylation of alkenyl iodides with hydrosilane
EP0651748B1 (fr) Procede de preparation de derives d'indole contenant un substituant 1,2,4-triazol-1-yl
EP0734369B1 (fr) Procede d'elaboration d'intermedes pour la synthese de principes antimycosiques
Kira et al. Preparation and reactions of 1, 1, 4, 4-tetrakis (trimethylsilyl) butane-1, 4-diyl dianion
WO1988010255A1 (fr) Procede d'isomerisation de triazoles symetriques en triazoles asymetriques
US4992565A (en) Preparation of oxiranes
EP3186261B1 (fr) Préparation de composés de fluorosilicium
Shitov et al. Synthesis of 1-alkyl-1, 2, 4-triazolium 4-nitroimides by alkylation of 4-nitramino-1, 2, 4-triazole salts
EP0162265B1 (fr) Préparation de gamma butyrolactones substituées utiles comme intermédiaires dans la préparation d'imidazoles et de triazoles fongicides
US5294727A (en) Method for preparing tertiary hydrocarbon-silyl compounds
EP0031996B1 (fr) Hydantoinylsilanes et bis(hydantoinyl)silanes et procédé pour leur préparation
US4814474A (en) Method for the production of tertiary-alkyldimethylhalosilane
WO2007039912A1 (fr) Procede monotope permettant de preparer un 4-[1-cyanophenyl)-1-(1,2,4-triazol-1-yl)methyl]benzonitrile
KR940003295B1 (ko) 푸르푸릴 알코올류의 제조방법
US5159089A (en) Selective production of threo-epoxy compounds
US4988829A (en) Process for the preparation of 2-(4-chlorophenylethyl)-2-tert.-butyl-oxirane
US6160151A (en) Process for production of diphenyl-dialkoxysilane, phenylalkyl-dialkoxysilane, octaphenylcyclotetrasilozane and sym-tetraalkyltetraphenyl-cyclotetrasiloxane
EP0601380A1 (fr) Procédé de préparation de triorganochlorosilanes
US4772695A (en) Process for the preparation of vinyl carbamates
JPH06100487A (ja) エーテル化合物の製造方法
US5194636A (en) Preparation of benzyl ketones and an oxirane
KR100200246B1 (ko) 트리아졸 유도체의 제조방법
KR100209245B1 (ko) 트리아졸 유도체의 제조방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 19891207

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

XX Miscellaneous (additional remarks)

Free format text: VERFAHREN ABGESCHLOSSEN INFOLGE VERBINDUNG MIT 88305372.0/0296745 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) VOM 11.09.90.