CA2207572C - Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones - Google Patents
Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones Download PDFInfo
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- CA2207572C CA2207572C CA002207572A CA2207572A CA2207572C CA 2207572 C CA2207572 C CA 2207572C CA 002207572 A CA002207572 A CA 002207572A CA 2207572 A CA2207572 A CA 2207572A CA 2207572 C CA2207572 C CA 2207572C
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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Abstract
A process for preparing a compound of formula (I), where R1, R2, R3, R4, R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, NO2, C1-4 alkyl, C1- 4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl; R8, R9 and R10 independently are hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, phenoxy or substituted phenoxy; RbS(O)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-4 alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(O)- in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy; SO2NRgRh in which Rg and Rh independently are hydrogen or C1-4 alkyl; or any two of R8, R9 and R10 together with the carbon atoms to which they are attached form a 5 or 6 membered heterocyclic ring containing up to three heteroatoms selected from O N or S and which may be optionally substituted by C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, =NOC1-4 alkyl, or halogen; which process comprises the rearrangement of a compound of formula (II), where R1, R2. R3, R4. R5, R6, R7, R8, R9 and R10 are as defined in relation to formula (I), in the presence of a base and a polar aprotic solvent characterised in that the process is carried out in a reaction medium substantially free of hydrogen cyanide or cyanide anion.
Description
Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones The present invention relates to the production of 2-(substituted benzoyl)-1,3-cyclohexanedione compounds.
2-(substituted benzoyl)-1,3-cyclohexanediones are known as herbicides from for example US Patent No. 4,780,127, US Patent No. 4,806,146, US Patent No. 4,946,981, US Patent No. 5,006,158, WO 9408988 and 4J0 9404524. One method of producing these compounds is by re-arrangement of an enol ester. This method is described in US Patent No. 4,780,127 and US
Patent No. 4,695,673. In these rearrangement reactions the presence of hydrogen cyanide or cyanide anion is described as essential (generally in an amount of 1-10 mol percent with respect to the enol ester). In an industrial scale process it is desirable to avoid the use of such materials. Surprisingly it has now been found that in certain solvents it is possible to perform the rearrangement in the absence of hydrogen cyanide or cyanide anion.
According to the present invention there is provided a process for preparing a compound of formula (I) where R1, R2, R3, R4, R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, N02, C -4 alkyl, C -4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl;
R~, R9 and R1~ independently are hydrogen, halogen, C alk 1_4 yl~ C1_4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, N02, phenoxy or substituted phenoxy; RbS(0)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-4 alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(0)-in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy;
S02NRgRh in which Rg and Rh independently are hydrogen or C alkyl; or any two of R8, R9 and R10 together with the carbon atoms tolwhich they are attached form a 5 or 6 membered heterocyclic ring containing up to three heteroatoms selected from 0, N or S and which may be optionally substituted by C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, =NOC1-4 alkyl or halogen; which process comprises the rearrangement of a compound of formula (II) where R1, ' R2l R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in relation to formula (I), in the presence of a base and a polar aprotic solvent ! . characterised in that the process is carried out in a reaction medium substantially free of hydrogen cyanide or cyanide anion.
As used herein the term "alkyl", refers to straight or branched chains. The term "haloalkyl" refers to an alkyl group substituted by at least one halogen. Similarly the term "haloalkoxy" refers to an alkoxy group substituted by at least one halogen. As used herein the term , "halogen" refers to fluorine, chlorine, bromine and iodine.
Suitable optional substituents for phenoxy groups R8, Rg and RIO
include halogen such as fluorine and chlorine and CI-4 haloalkyl.
A preferred group of compounds of formula (I) are those where RI, R2, R3, R4, R5 and R6 are independently hydrogen or CI-6 alkyl; R~ is halogen, cyano, N02, C -4 alkyl, C -4 haloalkyl, CI-4 alkoxy or RaS in which Ra is CI-4 alkyl; R~, R9 and RI~ independently are hydrogen, halogen, CI-4 alkyl, CI-4 alkoxy, CI-4 haloalkyi, CI-4 haloalkoxy, CN, N02, phenoxy or substituted phenoxy; RbS(0)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is CI-4 alkyl, CI-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is CI-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or CI-4 alkyl;
RfC(0)- in which Rf is hydrogen, CI-4 alkyl, CI-4 haloalkyl or CI-4 alkoxy;
or S02NRgRh in which Rg and Rh independently are hydrogen or CI-4 alkyl.
Preferably RI, R2, R3, R4, R5 and R6 are independently hydrogen or CI-4 alkyl. More preferably RI, R2, R5 and R6 are hydrogen and R3 and R4 are independently hydrogen or methyl.
R~ is preferably halogen or NO2. A preferred value for R8 is hydrogen.
R9 is preferably hydrogen or CI-4 alkoxy, especially ethoxy. Most preferably R9 is hydrogen.
Preferably RIO is a group RbS(0)nOm where Rb, n and m are as defined above. More preferably m is zero, n is 2 and Rb is CH3 or CZH~. Most preferably RIO is a group CH3S02 attached to the benzoyl group at the 4-position.
Suitable bases include both organic bases such as trialkylamines and inorganic bases such as alkali metal carbonates and phosphates. The trialkylamines are preferably tri(lower alkyl) amines having from 1 to 6, preferably 1 to 4 carbon atoms per alkyl group. A particularly preferable amine is triethylamine. Suitable inorganic bases include sodium carbonate, potassium carbonate and trisodium phosphate. Even a bicarbonate such as potassium bicarbonate will function effectively in this reaction when used ' PCTlGB96/00081 in combination with a Bipolar aprotic solvent such as dimethylformamide.
Preferred bases are sodium carbonate and potassium carbonate.
T
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
As used herein the expressions "substantially free of hydrogen cyanide or cyanide anion" means that neither of these moieties is deliberately added to the reaction medium.
Preferred solvents for the process are acetonitrile, dimethylformamide, tetrahydrofuran and mixtures of these solvents with non-polar solvents such as toluene and xylene.
In general, depending on the nature of the reactants, the base and the solvent the rearrangements may be conducted at temperatures from 0°C, up to about 100°C. Preferably the temperature is at a maximum of about 80°C.
Most preferably the temperature is from about 20°C, to about 70°C. In some cases, for instance when there is a possible problem of excessive by-product formation (for instance, when using an orthonitro benzoyl halide) the temperature should be kept at about 40°C maximum.
The process may be carried out using the enol ester as the starting material, or with generation of the enol ester in situ, for instance by reaction of a compound of formula (III) where R1, R2, R3, R4, R5 and R6 are as defined in relation to formula (I) with a compound of formula (IV) where R~, R8, R9 and R10 are as defined in relation to formula (I) and Z is a halo, preferably chloro.
4Jhen the enol ester is utilised as a starting material it may be prepared by any of a number of known means, including acylation of a compound of formula (III) with, a compound of formula (IV).
ThA nrnr~~~..+,.. ..r _ ...,. r",4u,.,,",r~ "~ compounds of formula (I) according to this invention, may be advantageously carried out starting with compounds of formula (III) and formula (IV) may be carried out with or without isolation of the intermediate enol ester. When carried out in two steps, the compound of formula (III) and the compound of formula (IV) are reacted in the presence of a moderate base such as sodium carbonate or triethylamine.
The enol ester isolated from the resulting product mix by known techniques, for instance washing the resultant solution with acid and base, and with saturated sodium chloride solution, and drying. Such a technique is advantageous when a different solvent is preferred for the second step -_4_ the rearrangement of the enol ester to the compound of formula (I). The dried enol ester may be mixed with an appropriate solvent such. as acetonitrile, or tetrahydrofuran and contacted with the appropriate amounts ' of moderate base and heated to an temperature, to produce the final product.
Alternatively, the enol ester may be retained in the reaction product and the second stage may be carried out (using the same solvent) by adding additional base if necessary to produce the compound of formula (I).
Comparable yields can be obtained either with or without isolation of the enol ester.
The compound of formula (I) is obtained from this reaction in the form of its salt. The desired acylated compound of formula (I) may be obtained with acidification and extraction with an appropriate solvent.
The process of the invention is illustrated by the following example.
Acetonitrile (25g) was charged to a 4 necked 250m1 flamed dried round bottom flask previously purged with N2 and sealed to a Drierite guard tube and oil bubbler. 1,3 cyclohexanedione (5.0g) and sodium carbonate powder (12.0g) were charged to give a red slurry. This mass was heated to 55-57°C
and held for 20 minutes. 2-chloro-4-(methylsulphonyi) benzoyl chloride (ll.Og) was added to acetonitrile (25g) and warmed gently to obtain a complete solution. This solution was added to the mass dropwise over 20 minutes at 55-57°C to give a pale yellow slurry. The mass was held at 55-57°C for 17 hours. The required compound of formula (I) as the sodium salt was produced in 82% yield.
In a second example the acetronitriie in Example 1 was replaced by dimethylformamide and the sodium carbonate was replaced with an equimolar amount of potassium carbonate. Following the same procedures, the reaction was complete 20 minutes after the acid chloride additions was ended and the yield of the required compound of formula (I) as the potassium salt was 54%.
The procedure of Example 1 was repeated using triethylamine in place of sodium carbonate and DMF in place of acetonitrile. The reaction was complete after 4 hours with a yield of 45%.
CHEMICAL FORMULAE
(IN DESCRIPT10N) R~ R~ ~ Rio R; O Rv (I) R= ~ Ra Rv O R' Z
R~R
O
R
io / R
Ra v Rs R O-r ' (i1) e ~ ~ R
O
R~ Rz O
R
(III) ' R
Rs ' R O
Rio R°
Z-(I~
R'
Patent No. 4,695,673. In these rearrangement reactions the presence of hydrogen cyanide or cyanide anion is described as essential (generally in an amount of 1-10 mol percent with respect to the enol ester). In an industrial scale process it is desirable to avoid the use of such materials. Surprisingly it has now been found that in certain solvents it is possible to perform the rearrangement in the absence of hydrogen cyanide or cyanide anion.
According to the present invention there is provided a process for preparing a compound of formula (I) where R1, R2, R3, R4, R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, N02, C -4 alkyl, C -4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl;
R~, R9 and R1~ independently are hydrogen, halogen, C alk 1_4 yl~ C1_4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, N02, phenoxy or substituted phenoxy; RbS(0)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-4 alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(0)-in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy;
S02NRgRh in which Rg and Rh independently are hydrogen or C alkyl; or any two of R8, R9 and R10 together with the carbon atoms tolwhich they are attached form a 5 or 6 membered heterocyclic ring containing up to three heteroatoms selected from 0, N or S and which may be optionally substituted by C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, =NOC1-4 alkyl or halogen; which process comprises the rearrangement of a compound of formula (II) where R1, ' R2l R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in relation to formula (I), in the presence of a base and a polar aprotic solvent ! . characterised in that the process is carried out in a reaction medium substantially free of hydrogen cyanide or cyanide anion.
As used herein the term "alkyl", refers to straight or branched chains. The term "haloalkyl" refers to an alkyl group substituted by at least one halogen. Similarly the term "haloalkoxy" refers to an alkoxy group substituted by at least one halogen. As used herein the term , "halogen" refers to fluorine, chlorine, bromine and iodine.
Suitable optional substituents for phenoxy groups R8, Rg and RIO
include halogen such as fluorine and chlorine and CI-4 haloalkyl.
A preferred group of compounds of formula (I) are those where RI, R2, R3, R4, R5 and R6 are independently hydrogen or CI-6 alkyl; R~ is halogen, cyano, N02, C -4 alkyl, C -4 haloalkyl, CI-4 alkoxy or RaS in which Ra is CI-4 alkyl; R~, R9 and RI~ independently are hydrogen, halogen, CI-4 alkyl, CI-4 alkoxy, CI-4 haloalkyi, CI-4 haloalkoxy, CN, N02, phenoxy or substituted phenoxy; RbS(0)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is CI-4 alkyl, CI-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is CI-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or CI-4 alkyl;
RfC(0)- in which Rf is hydrogen, CI-4 alkyl, CI-4 haloalkyl or CI-4 alkoxy;
or S02NRgRh in which Rg and Rh independently are hydrogen or CI-4 alkyl.
Preferably RI, R2, R3, R4, R5 and R6 are independently hydrogen or CI-4 alkyl. More preferably RI, R2, R5 and R6 are hydrogen and R3 and R4 are independently hydrogen or methyl.
R~ is preferably halogen or NO2. A preferred value for R8 is hydrogen.
R9 is preferably hydrogen or CI-4 alkoxy, especially ethoxy. Most preferably R9 is hydrogen.
Preferably RIO is a group RbS(0)nOm where Rb, n and m are as defined above. More preferably m is zero, n is 2 and Rb is CH3 or CZH~. Most preferably RIO is a group CH3S02 attached to the benzoyl group at the 4-position.
Suitable bases include both organic bases such as trialkylamines and inorganic bases such as alkali metal carbonates and phosphates. The trialkylamines are preferably tri(lower alkyl) amines having from 1 to 6, preferably 1 to 4 carbon atoms per alkyl group. A particularly preferable amine is triethylamine. Suitable inorganic bases include sodium carbonate, potassium carbonate and trisodium phosphate. Even a bicarbonate such as potassium bicarbonate will function effectively in this reaction when used ' PCTlGB96/00081 in combination with a Bipolar aprotic solvent such as dimethylformamide.
Preferred bases are sodium carbonate and potassium carbonate.
T
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
As used herein the expressions "substantially free of hydrogen cyanide or cyanide anion" means that neither of these moieties is deliberately added to the reaction medium.
Preferred solvents for the process are acetonitrile, dimethylformamide, tetrahydrofuran and mixtures of these solvents with non-polar solvents such as toluene and xylene.
In general, depending on the nature of the reactants, the base and the solvent the rearrangements may be conducted at temperatures from 0°C, up to about 100°C. Preferably the temperature is at a maximum of about 80°C.
Most preferably the temperature is from about 20°C, to about 70°C. In some cases, for instance when there is a possible problem of excessive by-product formation (for instance, when using an orthonitro benzoyl halide) the temperature should be kept at about 40°C maximum.
The process may be carried out using the enol ester as the starting material, or with generation of the enol ester in situ, for instance by reaction of a compound of formula (III) where R1, R2, R3, R4, R5 and R6 are as defined in relation to formula (I) with a compound of formula (IV) where R~, R8, R9 and R10 are as defined in relation to formula (I) and Z is a halo, preferably chloro.
4Jhen the enol ester is utilised as a starting material it may be prepared by any of a number of known means, including acylation of a compound of formula (III) with, a compound of formula (IV).
ThA nrnr~~~..+,.. ..r _ ...,. r",4u,.,,",r~ "~ compounds of formula (I) according to this invention, may be advantageously carried out starting with compounds of formula (III) and formula (IV) may be carried out with or without isolation of the intermediate enol ester. When carried out in two steps, the compound of formula (III) and the compound of formula (IV) are reacted in the presence of a moderate base such as sodium carbonate or triethylamine.
The enol ester isolated from the resulting product mix by known techniques, for instance washing the resultant solution with acid and base, and with saturated sodium chloride solution, and drying. Such a technique is advantageous when a different solvent is preferred for the second step -_4_ the rearrangement of the enol ester to the compound of formula (I). The dried enol ester may be mixed with an appropriate solvent such. as acetonitrile, or tetrahydrofuran and contacted with the appropriate amounts ' of moderate base and heated to an temperature, to produce the final product.
Alternatively, the enol ester may be retained in the reaction product and the second stage may be carried out (using the same solvent) by adding additional base if necessary to produce the compound of formula (I).
Comparable yields can be obtained either with or without isolation of the enol ester.
The compound of formula (I) is obtained from this reaction in the form of its salt. The desired acylated compound of formula (I) may be obtained with acidification and extraction with an appropriate solvent.
The process of the invention is illustrated by the following example.
Acetonitrile (25g) was charged to a 4 necked 250m1 flamed dried round bottom flask previously purged with N2 and sealed to a Drierite guard tube and oil bubbler. 1,3 cyclohexanedione (5.0g) and sodium carbonate powder (12.0g) were charged to give a red slurry. This mass was heated to 55-57°C
and held for 20 minutes. 2-chloro-4-(methylsulphonyi) benzoyl chloride (ll.Og) was added to acetonitrile (25g) and warmed gently to obtain a complete solution. This solution was added to the mass dropwise over 20 minutes at 55-57°C to give a pale yellow slurry. The mass was held at 55-57°C for 17 hours. The required compound of formula (I) as the sodium salt was produced in 82% yield.
In a second example the acetronitriie in Example 1 was replaced by dimethylformamide and the sodium carbonate was replaced with an equimolar amount of potassium carbonate. Following the same procedures, the reaction was complete 20 minutes after the acid chloride additions was ended and the yield of the required compound of formula (I) as the potassium salt was 54%.
The procedure of Example 1 was repeated using triethylamine in place of sodium carbonate and DMF in place of acetonitrile. The reaction was complete after 4 hours with a yield of 45%.
CHEMICAL FORMULAE
(IN DESCRIPT10N) R~ R~ ~ Rio R; O Rv (I) R= ~ Ra Rv O R' Z
R~R
O
R
io / R
Ra v Rs R O-r ' (i1) e ~ ~ R
O
R~ Rz O
R
(III) ' R
Rs ' R O
Rio R°
Z-(I~
R'
Claims (9)
1. A process for preparing a compound of formula (I):
where R1, R2, R3, R4, R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, NO2, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl; R8, R9 and R10 independently are hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, phenoxy or substituted phenoxy; RbS(O)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-4 alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(O)-in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy;
SO2NRgRh in which Rg and Rh independently are hydrogen or C1-4 alkyl;
or any two of R8, R9 and R10 together with the carbon atoms to which they are attached form a 5 or 6 membered heterocyclic ring containing up to three heteroatoms selected from O, N or S and which may be optionally substituted by C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, =NOC1-4 alkyl, or halogen; which process comprises the rearrangement of a compound of formula (II):
where R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in relation to formula (I), in the presence of a base and a polar aprotic solvent characterised in that the process is carried out in a reaction medium substantially free of hydrogen cyanide or cyanide anion.
where R1, R2, R3, R4, R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, NO2, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl; R8, R9 and R10 independently are hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, phenoxy or substituted phenoxy; RbS(O)n Om in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-4 alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(O)-in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy;
SO2NRgRh in which Rg and Rh independently are hydrogen or C1-4 alkyl;
or any two of R8, R9 and R10 together with the carbon atoms to which they are attached form a 5 or 6 membered heterocyclic ring containing up to three heteroatoms selected from O, N or S and which may be optionally substituted by C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, =NOC1-4 alkyl, or halogen; which process comprises the rearrangement of a compound of formula (II):
where R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in relation to formula (I), in the presence of a base and a polar aprotic solvent characterised in that the process is carried out in a reaction medium substantially free of hydrogen cyanide or cyanide anion.
2. A process according to claim 1 where R1, R2, R3, R4. R5 and R6 are independently hydrogen or C1-6 alkyl; R7 is halogen, cyano, N0 2, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy or RaS in which Ra is C1-4 alkyl;
R8, R9 and R10 independently are hydrogen, halogen, Cl-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, N0 2, phenoxy or substituted phenoxy; R b S(0)n 0m in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-~ alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(0)- in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy; or S02NRgRh in which Rg and Rh independently are hydrogen or C1-4 alkyl.
R8, R9 and R10 independently are hydrogen, halogen, Cl-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, N0 2, phenoxy or substituted phenoxy; R b S(0)n 0m in which m is 0 or 1, n is 0, 1 or 2 and Rb is C1-~ alkyl, C1-4 haloalkyl, phenyl or benzyl, NHCORc in which Rc is C1-4 alkyl, NRdRe in which Rd and Re independently are hydrogen or C1-4 alkyl; RfC(0)- in which Rf is hydrogen, C1-4 alkyl, C1-4 haloalkyl or C1-4 alkoxy; or S02NRgRh in which Rg and Rh independently are hydrogen or C1-4 alkyl.
3. A process -according to claim 1 or claim 2 where R1, R2, R5 and R6 are hydrogen and R3 and R4 are independently hydrogen or methyl.
4. A process according to any one of the preceding claims where R7 is halogen or N02.
5. A process according to any one of the preceding claims where R8 is hydrogen.
6. A process according to any one of the preceding claims where R9 is hydrogen or C1-4 alkoxy.
7. A process according to any one of the preceding claims where R10 is a group CH3S02 attached to the benzoyl group at the 4- position.
8. A process according to any one of the preceding claims where the solvent is acetonitrile, dimethylformamide, tetrahydrofuran or mixtures of these solvents with toluene or xylene.
9. A process according to any one of the preceding claims where the base is triethylamine, sodium carbonate or potassium carbonate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9501433.8 | 1995-01-25 | ||
| GBGB9501433.8A GB9501433D0 (en) | 1995-01-25 | 1995-01-25 | Chemical process |
| PCT/GB1996/000081 WO1996022957A1 (en) | 1995-01-25 | 1996-01-16 | Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2207572A1 CA2207572A1 (en) | 1996-08-01 |
| CA2207572C true CA2207572C (en) | 2006-12-05 |
Family
ID=37560813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002207572A Expired - Fee Related CA2207572C (en) | 1995-01-25 | 1996-01-16 | Process for the production of 2-(substituted benzoyl)-1,3 cyclohexanediones |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2207572C (en) |
-
1996
- 1996-01-16 CA CA002207572A patent/CA2207572C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CA2207572A1 (en) | 1996-08-01 |
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