CA2207002C - The preparation of halomethylbenzoyl cyanides - Google Patents
The preparation of halomethylbenzoyl cyanides Download PDFInfo
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- CA2207002C CA2207002C CA002207002A CA2207002A CA2207002C CA 2207002 C CA2207002 C CA 2207002C CA 002207002 A CA002207002 A CA 002207002A CA 2207002 A CA2207002 A CA 2207002A CA 2207002 C CA2207002 C CA 2207002C
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- cyanide
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- alkyl
- halomethylbenzoyl
- cyanides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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Abstract
A process is disclosed for preparing halogenated methyl benzoyl cyanides having the formula (I): PH-CO-CN, in which Ph stands for a phenyl rest substituted by chloromethyl or bromomethyl that may optionally carry 1-4 other rests, from halogenated methyl benzoyl chlorides having the formula (II): PH-CO-Cl. The compound having the formula (II) is reacted with a cyanide-releasing compound in the presence of a Lewis acid, optionally in an inert organic solvent or diluent, and the product obtained by this process is then isolated. The halogenated methyl benzoyl cyanides having the formula (I) are important intermediate products for the synthesis of plant protective agents.
Description
UUSU/ 453yb CA 02207002 1997-OS-22 The preparation of halomethylbenzoyl cyanides The present invention relates to an improved process for preparing halomethylbenzoyl cyanides of the general formula I
PH-CO-CN (I) where PH is phenyl which is substituted by chloromethyl or bromomethyl and which can, if required, also carry from 1 to 4 further radicals which are inert in the reaction, from halomethylbenzoyl chlorides of the general formula II
PH-CO-C1 (II).
DE-C 43 11 722 has disclosed that 2-halomethylbenzoyl chlorides II can be converted by reaction with alkali metal or transition metal cyanides into the corresponding 2-halomethylbenzoyl cyanides I, and that the progress of the process can~be beneficially influenced by adding a catalyst. Catalysts said to be suitable are the halides, cyanides, hydroxides, bisulfates, C1-C4-alkyl sulfates and tetrafluoroborates of quaternary nitrogen compounds, and aryl- and alkylphosphonium halides. However, the reactions indicated in the examples reveal that the yields are not entirely satisfactory for a reaction on the industrial scale.
It is an object of the present invention to remedy this deficiency.
We have found that this object is achieved by the gresent improved process for preparing the halomethylbenzoyl cyanides I, which comprises reacting II with a cyanide-donating compound in the presence of a Lewis acid, if required in an inert organic solvent or diluent, and then isolating the product.
The halomethylbenzoyl chlorides II can be prepared by known halogenation methods from the corresponding methyl-substituted benzene derivatives (cf. for example, DE-A 28 35 440) or from the corresponding benzoic acids (cf., for example, DE-A 40 42 282).
The process according to the invention is normally carried out under atmospheric pressure or slightly reduced pressure, generally at from -20 to 100°C, preferably 0 to 80°C, in particular 20 to 80°C.
PH-CO-CN (I) where PH is phenyl which is substituted by chloromethyl or bromomethyl and which can, if required, also carry from 1 to 4 further radicals which are inert in the reaction, from halomethylbenzoyl chlorides of the general formula II
PH-CO-C1 (II).
DE-C 43 11 722 has disclosed that 2-halomethylbenzoyl chlorides II can be converted by reaction with alkali metal or transition metal cyanides into the corresponding 2-halomethylbenzoyl cyanides I, and that the progress of the process can~be beneficially influenced by adding a catalyst. Catalysts said to be suitable are the halides, cyanides, hydroxides, bisulfates, C1-C4-alkyl sulfates and tetrafluoroborates of quaternary nitrogen compounds, and aryl- and alkylphosphonium halides. However, the reactions indicated in the examples reveal that the yields are not entirely satisfactory for a reaction on the industrial scale.
It is an object of the present invention to remedy this deficiency.
We have found that this object is achieved by the gresent improved process for preparing the halomethylbenzoyl cyanides I, which comprises reacting II with a cyanide-donating compound in the presence of a Lewis acid, if required in an inert organic solvent or diluent, and then isolating the product.
The halomethylbenzoyl chlorides II can be prepared by known halogenation methods from the corresponding methyl-substituted benzene derivatives (cf. for example, DE-A 28 35 440) or from the corresponding benzoic acids (cf., for example, DE-A 40 42 282).
The process according to the invention is normally carried out under atmospheric pressure or slightly reduced pressure, generally at from -20 to 100°C, preferably 0 to 80°C, in particular 20 to 80°C.
Cyanide-donating compounds are, preferably, hydrogen cyanide, cyanohydrin, alkali metal cyanides such as sodium and potassium cyanides or transition metal cyanides such as mercury(I) cyanide, silver cyanide and copper(I) cyanide. Sodium cyanide is particularly expedient.
In general, the halomethylbenzoyl chloride II and the cyanide-donating compound are used in approximately stoichiometric amounts. However, an excess of cyanide, up to a 2-fold quantity, in particular a 1.05-1.5-fold quantity, based on the amount of II, is preferred.
Concerning the use of Lewis acids, reference may be made to Jerry March, Advanced Organic Chemistry, Fourth Edition 1992, pages 539-552, and the literature cited therein.
According to findings to date, particularly particularly [sic) suitable catalysts are tin tetrachloride, aluminum chloride, iron(II) chloride, iron(III) chloride, zinc chloride, titanium tetrachloride, boron trifluoride and antimony pentachloride, and tin tetrachloride and titanium tetrachloride are very particularly suitable.
The catalyst is preferably used in amounts of from 0.01 to 5 mold, in particular from 0.1 to 3 mold, based on the amount of II.
Where the halomethylbenzoyl chloride II is not in liquid form, it is advisable to add an inert organic solvent or diluent, in which case aprotic dipolar and non-polar solvents are particularly suitable.
Aprotic dipolar solvents are solvents in which a solvent molecule has a pronounced dipole moment but carries no hydrogen atoms capable of hydrogen bonding. The dielectric constant of such solvents is. greater than 15. Concerning the definition of aprotic dipolar solvents, reference may be made to A. J. Parker, Chem.
Rev. ~~ (1969), 1 - 32, especially page 2.
Examples of suitable aprotic dipolar solvents are sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, methyl ethyl sulfone and tetramethylene sulfone;
nitriles such as acetonitrile, benzonitrile, butyronitrile, isobutyronitrile and m-chlorobenzonitrile; N,N-dialkyl-substituted carboxamides such as dimethylformamide, tetramethylurea, N,N-dimethylbenzamide, N,N-dimethylacetamide, N,N-dimethylphenylacetamide, N,N-dimethylcyclohexanecarboxamide, N,N-dimethylpropionamide and homologous pigeridide, morpholide and pyrrolidide of carboxylic acids, and the corresponding N,N-diethyl, N,N-dipropyl, N,N-diisopropyl, N,N-diisobutyl, N,N-dibenzyl, N,N-diphenyl, N-methyl-N-phenyl, N-cyclohexyl-N-methyl, N-ethyl-N-tert-butyl compounds of the abovementioned N,N-dimethyl compounds, furthermore N-methylformanilide, N-ethylpyrrolidone, N-butylpyrrolidone, N-ethyl-piperidone-(t) , N-methylpyrrolidone and hexamethylphosphoric triamide. Mixtures of said solvents are also suitable.
Dimethylacetamide, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, tetramethylene sulfone, acetone and acetonitrile are preferred.
Suitable non-polar solvents are preferably aromatic hydrocarbons such as benzene, toluene and o-, m- and p-xylenes, chlorinated hydrocarbons such as methylene chloride, and alcohols such as methanol and ethanol. Toluene is particularly preferred. The products I can be purified in a conventional way, eg. by distillation.
The process according to the invention can be carried out either batchwise or continuously. In the continuous procedure, the reactants are passed, for example, through a tubular reactor or cascades of stirred vessels. Solvents and catalysts can, if required, be circulated.
The halomethylbenzoyl cyanides I can be obtained by the present process with very good purity and in high yield in a technically straightforward manner. It is normally unnecessary to purify the crude products.
The halomethylbenzoyl cyanides I are valuable intermediates for preparing various crop protection agents, for example the herbicidal 4-phenylpyrazoles described in EP-A 352 543.
The products I can additionally be used to synthesize arylglyoxylic esters as disclosed in DE-A 40 42 271. A mixture of phenylglyoxylic esters and their ketals obtained from the Dinner reaction described therein can be converted as disclosed in DE-A 40 42 272 into the E oxime ethers of phenylglyoxylic esters of the formula III
In general, the halomethylbenzoyl chloride II and the cyanide-donating compound are used in approximately stoichiometric amounts. However, an excess of cyanide, up to a 2-fold quantity, in particular a 1.05-1.5-fold quantity, based on the amount of II, is preferred.
Concerning the use of Lewis acids, reference may be made to Jerry March, Advanced Organic Chemistry, Fourth Edition 1992, pages 539-552, and the literature cited therein.
According to findings to date, particularly particularly [sic) suitable catalysts are tin tetrachloride, aluminum chloride, iron(II) chloride, iron(III) chloride, zinc chloride, titanium tetrachloride, boron trifluoride and antimony pentachloride, and tin tetrachloride and titanium tetrachloride are very particularly suitable.
The catalyst is preferably used in amounts of from 0.01 to 5 mold, in particular from 0.1 to 3 mold, based on the amount of II.
Where the halomethylbenzoyl chloride II is not in liquid form, it is advisable to add an inert organic solvent or diluent, in which case aprotic dipolar and non-polar solvents are particularly suitable.
Aprotic dipolar solvents are solvents in which a solvent molecule has a pronounced dipole moment but carries no hydrogen atoms capable of hydrogen bonding. The dielectric constant of such solvents is. greater than 15. Concerning the definition of aprotic dipolar solvents, reference may be made to A. J. Parker, Chem.
Rev. ~~ (1969), 1 - 32, especially page 2.
Examples of suitable aprotic dipolar solvents are sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, methyl ethyl sulfone and tetramethylene sulfone;
nitriles such as acetonitrile, benzonitrile, butyronitrile, isobutyronitrile and m-chlorobenzonitrile; N,N-dialkyl-substituted carboxamides such as dimethylformamide, tetramethylurea, N,N-dimethylbenzamide, N,N-dimethylacetamide, N,N-dimethylphenylacetamide, N,N-dimethylcyclohexanecarboxamide, N,N-dimethylpropionamide and homologous pigeridide, morpholide and pyrrolidide of carboxylic acids, and the corresponding N,N-diethyl, N,N-dipropyl, N,N-diisopropyl, N,N-diisobutyl, N,N-dibenzyl, N,N-diphenyl, N-methyl-N-phenyl, N-cyclohexyl-N-methyl, N-ethyl-N-tert-butyl compounds of the abovementioned N,N-dimethyl compounds, furthermore N-methylformanilide, N-ethylpyrrolidone, N-butylpyrrolidone, N-ethyl-piperidone-(t) , N-methylpyrrolidone and hexamethylphosphoric triamide. Mixtures of said solvents are also suitable.
Dimethylacetamide, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, tetramethylene sulfone, acetone and acetonitrile are preferred.
Suitable non-polar solvents are preferably aromatic hydrocarbons such as benzene, toluene and o-, m- and p-xylenes, chlorinated hydrocarbons such as methylene chloride, and alcohols such as methanol and ethanol. Toluene is particularly preferred. The products I can be purified in a conventional way, eg. by distillation.
The process according to the invention can be carried out either batchwise or continuously. In the continuous procedure, the reactants are passed, for example, through a tubular reactor or cascades of stirred vessels. Solvents and catalysts can, if required, be circulated.
The halomethylbenzoyl cyanides I can be obtained by the present process with very good purity and in high yield in a technically straightforward manner. It is normally unnecessary to purify the crude products.
The halomethylbenzoyl cyanides I are valuable intermediates for preparing various crop protection agents, for example the herbicidal 4-phenylpyrazoles described in EP-A 352 543.
The products I can additionally be used to synthesize arylglyoxylic esters as disclosed in DE-A 40 42 271. A mixture of phenylglyoxylic esters and their ketals obtained from the Dinner reaction described therein can be converted as disclosed in DE-A 40 42 272 into the E oxime ethers of phenylglyoxylic esters of the formula III
(X)m N - OCH3 C
(III) CHZ-0- Ar where Ar is substituted or unsubstituted phenyl. Compounds of the type of III are used in crop protection, preferably as fungicides, acaricides or insecticides (cf., for example, EP-A
253 213 and EP-A 254 426).
With a view to the active substances III which can be prepared from the compounds I, Ph [sic] is, in particular, the radical (X)m Y
where X is in each case halogen, especially fluorine or chlorine, C1-C4-alkyl, especially methyl or ethyl, C1-C4-alkoxy, especially methoxy, ethoxy or isopropoxy, C1-C4-haloalkyl, especially trifluoromethyl, -C(C1-CS-alkyl)=N-O-(C1-C5-alkyl) or -C(C1-CS-alkyl)=N-O-(C2-C5-alkenyl), in particular methylhydroxylimino or -C(CH3)=N-OCH3;
particularly preferably halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C~-haloalkyl;
m is from 0 to 4, in particular 1, in which case X is preferably in position 3, 5 or 6, and Y is chloromethyl or bromomethyl, especially chloromethyl, and Y is preferably in position 2.
Ph is very particularly preferably chloromethylphenyl or bromomethylphenyl.
VVJV/ ~:.7JJU
c Preparation Examples Example 1 5 Preparation of 2-chloromethylbenzoyl cyanide in acetonitrile 7.8 g (3 molg) of tin tetrachloride are added to a suspension of 196 g (4 mol) of sodium cyanide in 1000 ml of acetonitrile. The mixture was then heated to 60°C and, over the course of 30 minutes, 378 g (2 mol) of 2-chloromethylbenzoyl chloride were added dropwise. The mixture was stirred at about 60°C for 6 hours and then cooled. The undissolved catalyst was then removed by filtration through silica gel. Alternatively, the catalyst can also be washed out of the reaction mixture after adding toluene using 200 ml of a dilute mineral acid three times.
The clear solution remaining after removal of the catalyst was subjected to fractional distillation. Yield: 345.8 g (97~);
boiling point (0.5) = 105°C.
Example 2 Preparation of 2-chloromethylbenzoyl cyanide in toluene The preparation took place as in Example 1 but using 1000 ml of toluene which contained up to 200 ml of acetonitrile and, after the addition of the 2-chloromethylbenzoyl chloride, stirring for 8 hours. Yield: 317.3 g (89~); boiling point (0.3) = 100°C.
(III) CHZ-0- Ar where Ar is substituted or unsubstituted phenyl. Compounds of the type of III are used in crop protection, preferably as fungicides, acaricides or insecticides (cf., for example, EP-A
253 213 and EP-A 254 426).
With a view to the active substances III which can be prepared from the compounds I, Ph [sic] is, in particular, the radical (X)m Y
where X is in each case halogen, especially fluorine or chlorine, C1-C4-alkyl, especially methyl or ethyl, C1-C4-alkoxy, especially methoxy, ethoxy or isopropoxy, C1-C4-haloalkyl, especially trifluoromethyl, -C(C1-CS-alkyl)=N-O-(C1-C5-alkyl) or -C(C1-CS-alkyl)=N-O-(C2-C5-alkenyl), in particular methylhydroxylimino or -C(CH3)=N-OCH3;
particularly preferably halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C~-haloalkyl;
m is from 0 to 4, in particular 1, in which case X is preferably in position 3, 5 or 6, and Y is chloromethyl or bromomethyl, especially chloromethyl, and Y is preferably in position 2.
Ph is very particularly preferably chloromethylphenyl or bromomethylphenyl.
VVJV/ ~:.7JJU
c Preparation Examples Example 1 5 Preparation of 2-chloromethylbenzoyl cyanide in acetonitrile 7.8 g (3 molg) of tin tetrachloride are added to a suspension of 196 g (4 mol) of sodium cyanide in 1000 ml of acetonitrile. The mixture was then heated to 60°C and, over the course of 30 minutes, 378 g (2 mol) of 2-chloromethylbenzoyl chloride were added dropwise. The mixture was stirred at about 60°C for 6 hours and then cooled. The undissolved catalyst was then removed by filtration through silica gel. Alternatively, the catalyst can also be washed out of the reaction mixture after adding toluene using 200 ml of a dilute mineral acid three times.
The clear solution remaining after removal of the catalyst was subjected to fractional distillation. Yield: 345.8 g (97~);
boiling point (0.5) = 105°C.
Example 2 Preparation of 2-chloromethylbenzoyl cyanide in toluene The preparation took place as in Example 1 but using 1000 ml of toluene which contained up to 200 ml of acetonitrile and, after the addition of the 2-chloromethylbenzoyl chloride, stirring for 8 hours. Yield: 317.3 g (89~); boiling point (0.3) = 100°C.
Claims (4)
1. A process for preparing a halomethylbenzoyl cyanide of the formula I
PH-CO-CN (I) where PH is phenyl which is substituted by chloromethyl or bromomethyl and which can also carry from 1 to 4 further radicals inert in the reaction, comprising the steps of reacting a halomethylbenzoyl chloride of the formula II
PH-CO-CL (II) with a cyanide-donating compound in the presence of a Lewis acid and then isolating the obtained product.
PH-CO-CN (I) where PH is phenyl which is substituted by chloromethyl or bromomethyl and which can also carry from 1 to 4 further radicals inert in the reaction, comprising the steps of reacting a halomethylbenzoyl chloride of the formula II
PH-CO-CL (II) with a cyanide-donating compound in the presence of a Lewis acid and then isolating the obtained product.
2. A process as claimed in claim 1, wherein the reaction is carried out in an inert organic solvent or diluent.
3. A process as claimed in claim 1 or 2, wherein the variable PH is the radical where X is in each case halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, -C(C1-C5-alkyl)=N-O-(C1-C5-alkyl) or -C(C1-C5-alkyl)=N-O-(C2-C5-alkenyl), m is 0 to 4 and Y is chloromethyl or bromomethyl.
4. A process as claimed in any one of claims 1 to 3, wherein the cyanide-donating compound is an alkali metal cyanide, a transition metal cyanide, a cyanohydrin or a hydrogen cyanide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4441824.8 | 1994-11-24 | ||
| DE4441824 | 1994-11-24 | ||
| PCT/EP1995/004463 WO1996016023A1 (en) | 1994-11-24 | 1995-11-14 | Process for preparing halogenated methyl benzoyl cyanides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2207002A1 CA2207002A1 (en) | 1996-05-30 |
| CA2207002C true CA2207002C (en) | 2007-01-23 |
Family
ID=37684359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002207002A Expired - Fee Related CA2207002C (en) | 1994-11-24 | 1995-11-14 | The preparation of halomethylbenzoyl cyanides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2207002C (en) |
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1995
- 1995-11-14 CA CA002207002A patent/CA2207002C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2207002A1 (en) | 1996-05-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20121114 |