IE69053B1 - Process for the preparation of acyl cyanides in anhydrous medium - Google Patents
Process for the preparation of acyl cyanides in anhydrous mediumInfo
- Publication number
- IE69053B1 IE69053B1 IE180190A IE180190A IE69053B1 IE 69053 B1 IE69053 B1 IE 69053B1 IE 180190 A IE180190 A IE 180190A IE 180190 A IE180190 A IE 180190A IE 69053 B1 IE69053 B1 IE 69053B1
- Authority
- IE
- Ireland
- Prior art keywords
- process according
- acid halide
- per mole
- cyanide
- product
- Prior art date
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Saccharide Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
A process for the synthesis of acyl cyanides of formula: <IMAGE> in which R denotes an alkyl, cycloalkyl or aryl radical or a heterocyclic residue, consisting in reacting acyl halides of formula: <IMAGE> in which R has the above definition and X denotes a halogen, with alkali metal cyanides, characterised in that the reaction takes place: a) in an anhydrous solvent medium, b) in the presence of a product containing alkylene oxide units, c) in the presence of a polar product, water being excluded.
Description
The present invention relates to a process for the synthesis of acyl cyanides in anhydrous medium. This process consists in reacting acid halides vith an alkali metal cyanide. Acyl cyanides are intermediates in the organic synthesis of, for example, herbicides.
FR Patent 2,353,524 describes a synthesis of benzoyl cyanide CgH5COCN by reaction of benzoyl chloride with sodium cyanide in molar excess in the presence of a nitrile and of copper cyanide. FR Patent 2,346,323 describes a similar but much more general reaction, since the latter applies to a whole group of acyl cyanides and consists in reacting sodium cyanide with an acid halide in excess in the presence of copper or zinc cyanide. These processes have the disadvantage of requiring the presence of heavy metals and therefore impose complicated treatments to avoid their presence in the effluents. In Tetrahedron Letters (Pergamon Press) No. 26, pages 2275-2278 (1974) there is disclosed a process limited to the synthesis of benzoyl cyanide by reaction of sodium cyanide with benzoyl chloride in solution in methylene 2θ chloride and in the presence of tetrabutylammonium bromide; the CgHsCOCN yield on CgH5COCl does not exceed 60 %.
FR Patent 2,364,894 describes the synthesis of CcH=COCN bv reaction of C^KeCOCI with NaCN i« a «solvent· in J w * w·· ** o wee ew «e v·, w « we a w ^e e the presence of benzoic anhydride (CgHgCO-O-CO-CgHg) or of products which can generate benzoic anhydride under the reaction conditions. The preferred quantity of benzoic anhydride is between 0.03 and 0.1 mole per mole of benzoyl chloride. This presence of benzoic anhydride complicates the recovery of benzoyl cyanide. A process has now been found according to the present invention which makes it possible to convert benzoyl chloride into benzoyl cyanide and which does not form benzoic anhydride as byproduct.
The present invention provides a process for the synthesis of acyl cyanides of formula (I): O R-!l-CN (I) in which R is either an alkyl radical containing from 1 to 8 carbon atoms or a cycloalkyl radical containing from 3 to 12 carbon atoms, or an aryl radical, or a heterocyclic residue which may be condensed with a benzene nucleus, all these radicals R being optionally substituted, which comprises reacting acid halides of formula (II): R-^-X (II) in which R has the above definition and X denotes a halogen, with alkali metal cyanides, characterized in that the reaction takes place: a) in anhydrous solvent medium, b) in the presence of a product containing alkylene oxide units, , c) in the presence of a polar product, water being excluded.
The reaction of the invention takes place according to the formula: i ϊ R-C-CX + MCN ---> R-C-CN + MX in which M denotes an alkali metal. After the reaction the alkali metal halide and the optional excess of alkali metal cyanide can be removed by filtration and washing with solvent. The pure acyl cyanide can be obtained by distillation of the filtered reaction mixture.
The acid halides employed as starting materials are defined by the formula (II). In this formula R preferably denotes a linear or branched alkyl radical containing from 1 to 4 carbon atoms which can be substituted; R also preferably denotes a cycloalkyl radical containing or 6 carbons which can be substituted; R also preferably denotes a phenyl or a naphthyl radical which can be substituted; R also preferably denotes a 5 or 6 membered heterocyclic residue, optionally substituted.
In formula (II), X advantageously denotes chlorine or * bromine. > The alkali metal, preferably sodium or potassium, cyanide is generally employed in stoichiometric quantity or else in excess, typically in a proportion of 1 to 2 moles per mole of acid halide; the preferred quantity is from 1 to 1.25 moles per mole of acid halide.
The acid halide is generally added little by little to the reaction mixture. It can be added either pure or diluted with the reaction solvent. The addition period can be from, say, a few minutes to several hours. The preferred period is approximately 0.5 hours.
The reaction should take place in the presence of a solvent in sufficient quantity to permit good stirring of the solid and liquid reactants.
Any solvents which do not react with the acid halide or with the alkali metal cyanide under the reaction conditions can be employed. Solvents of very low polarity are preferred. Suitable solvents include: - aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene, and dichlorobenzene, - aliphatic hydrocarbons such as cyclohexane and ligroin, - halogenated aliphatic hydrocarbons such as trichloroethylene and tetrachloroethane.
The preferred solvents for the reaction are toluene and xylene.
The quantity of solvent can vary within wide limits. From 200 to 500 ml per mole of acid halide is generally sufficient. A larger quantity of solvent can be used, but it would be necessary to distil a larger quantity to recover the acyl cyanide.
The reaction is suitably performed at a temperature of 60 to 150°C, the preferred temperature being 80 to 120°C.
The reaction is advantageously performed at 5 atmospheric pressure, under solvent vapour pressure or under inert gas pressure.
The reaction is generally finished in 2 hours. However, it is advantageous to continue heating for a period of 2 to 8 hours in order to remove any trace of benzoyl chloride. For example, at 95°C the preferred reaction period is from 5 to 7 hours.
The product containing alkylene oxide units advantageously contains 2 to 200 units chosen from ethylene oxide and propylene oxide. It is, for example, a product containing one or more polyoxyethylene chains of formula: —O—(CH2-CH2-O)n-CH2-CH2-OH where the sum of the n or the n’s is from 2 to 200.
The ethylene oxide units can be replaced by propylene oxide units or a mixture of these two units.
Among the polyoxyalkylenated derivatives which are suitable there may be mentioned: - simple polyethylene glycols of formula: HO-(CH2-CH2O)n-CH2-CH2OH of molecular mass 100 to 4000, - polyethylene glycols condensed with stearic acid of formula CH3- (CH2 ) 16-coo- (CH2-CH2O) n-CH2-CH2-OH where n is from 20 to 150, - triglyceride derivatives of polyethylene glycols, - polyoxyethylenated alkylphenols of formula Rx <ζ O -O(CH2-CH2O)n-CH2-CH2OH where n is from 10 to 200 and Rx denotes an alkyl containing up to 20 carbons.
Thus suitable compounds include polyethylene glycol derivatives which have more than 10 ethylene units.
Products which are similar to the above products can be employed, in which the ethylene oxide unit is replaced by the propylene oxide unit or a mixture of ethylene oxide and propylene oxide units.
The quantity of this product is suitably from 0.1 to g per mole of acid halide, the preferred quantity being from 0.4 to 2 g (per mole).
The product is generally added to the reaction, solvent, but it can also be added wholly or partly to the pure or solvent-diluted acid halide.
When the reaction takes place in a strictly anhydrous medium with carefully dehydrated reactants, the degree of conversion and yield are very low; a very small quantity of a polar product, such as formamide, glycerol or ethylene glycol, must be added to the reactants to obtain a high yield and degree of conversion.
The polar product is preferably poorly soluble in the reaction solvent but must not give rise to the formation of anhydride or acid by reaction with the acid halide.
Products whose dielectric constant is higher than 30 are advantageously employed, except for water.
Among the polar derivatives which are particularly suitable there may be mentioned: - glycerol CH2OH-CHOH-CH2OH - ethylene glycol CH2OH-CH2OH - formamide and sugar derivatives.
The quantity of the polar product to be added is suitably 0.1 g to 10 g per 1 mole of acid halide.
The preferred quantity is 0.25 to 2 g per mole of acid halide.
The way in which the polar product is introduced must ensure good distribution thereof over the reactants.
After the reaction, any excess of cyanide and of alkali metal halide which is formed can be removed by filtration. Pure acyl cyanide can be obtained by distillation of the filtered reaction mixture.
In the Examples which follow, and which further illustrate the present invention, the degree of conversion expresses the quantity of acid halide which has disappeared, relative to the initial quantity, and the yield expresses the ratio of the number of moles of acyl cyanide obtained to the number of moles of acid halide which were originally present. The composition of the filtrate is given in moles relative to the benzoyl chloride used.
EXAMPLE 1 29.4 g of anhydrous sodium cyanide (0.6 moles) and 0.5 g of glycerol are added to a glass reactor fitted with a stirrer and a condenser, containing 150 cm3 of xylene and 0.5 g of polyoxyethylenated nonylphenol supplied by GAF under the name Antarox CO 990. These are heated to 95°C with stirring and 70.3 g of benzoyl chloride (0.5 moles) are then run in over 0.5 hours; the temperature is kept at 95°C for 6 hours and then, after cooling, filtration and washing with xylene are carried out; an inorganic precipitate weighing 34.5 g and 241.9 g of filtrate are obtained.
The organic filtrate is analysed by gas phase chromatography and determined using an internal standard.
Molar composition of the filtrate: Benzoyl chloride 0.4 * Benzoyl cyanide 93.3 % Benzoic anhydride 0.35 % Benzoic acid 0.0 % Dimer 2.6 * That is, a 93.3 % yield and a degree of conversion of benzoyl chloride of 99.6 %.
EXAMPLE 2 The procedure is exactly as in Example 1, but with glycerol being replaced with an equal weight of ethylene glycol. 229.1 g of organic filtrate are obtained, containing, in mol% relative to the initial benzoyl chloride: Benzoyl chloride 0.2 * Benzoyl cyanide 91.6 % Benzoic anhydride 0.45 % Benzoic acid 0.2 % Dimer 3.1 % That is, a 91.6 % yield and a degree of conversion of 99.8 %.
EXAMPLE 3 The procedure is as in Example 1, but with glycerol being replaced with 1.25 of formamide. After benzoyl chloride has been run in over 1 hour and heating has been continued for 2 hours, an inorganic precipitate of 33.4 g is obtained, and an organic filtrate of 274.5 g, containing: Benzoyl chloride 3.3 Benzoyl cyanide 76.0 Benzoic anhydride 1.0 Dimer 10.0 That is, a 76 % yield and a degree of conversion of 96.7 %.
EXAMPLE 4 The procedure is exactly as in Example 1, but with glycerol being replaced with 0.5 g of glucose. A degree of conversion of 92 %, a 73.4 % yield and a benzoic anhydride content of 0.65 % (molar) in the filtrate are obtained.
EXAMPLE 5 The procedure is exactly as in Example 1, but with the quantity of solvent being reduced: 75 cm3 of xylene instead of 150 cm3. 34.4 g of an organic precipitate are obtained and 182.2 g of an organic filtrate containing: Benzonitrile 0.1 % Benzoyl chloride 14.8 % Benzoyl cyanide 79.0 % Benzoic anhydride 0.8 % Dimer 3.2 % That is, a 79 % yield and a degree of conversion of 85.2 %.
EXAMPLE 6 (not in accordance with the invention) The procedure is exactly as in Example 2, but omitting the Antarox CO 990. 36.6 g of an inorganic precipitate are obtained and 243.4 g of an organic filtrate containing: Benzoyl chloride 57.8 % Benzoyl cyanide 39.5 % Benzoic acid 0.2 % Benzoic anhydride 0.8 % Dimer 2.5 % That is, a 39.5 % yield and a degree of conversion of 42.2 *.
EXAMPLE 7 (not in accordance with the invention) The procedure is exactly as in Example 1, but omitting the polar derivative. 30.8 g of an inorganic precipitate are obtained and 229 g of an organic filtrate containing (molt): Benzoyl chloride 68.2 % Benzoyl cyanide 23.8 % Benzoic acid 0.3 % Benzoic anhydride 0.5 % EXAMPLE 8 The procedure is exactly as in Example 1, but replacing the Antarox CO 990 with the same weight of polyethylene glycol triglyceride containing 150 ethylenated units, marketed by Atlas under the name of 6 1295. 34.9 g of an inorganic precipitate are obtained and an organic filtrate containing, in molt relative to the initial benzoyl chloride: Benzonitrile 0.2 t Benzoyl chloride 1.9 t Benzoyl cyanide 92.3 t Benzoic anhydride 0.45 t Dimer 2.5 t That is, a 92.3 t chemical yield for a degree of conversion of 98.1 t.
Claims (15)
1. Process for the synthesis of an acyl cyanide of formula (I): 5 R-t-CN (I) in which R is either an alkyl radical containing from 1 to 8 carbon atoms or a cycloalkyl radical containing from 3 to 12 carbon atoms, or an aryl radical, or a heterocyclic residue which may be condensed with a benzene nucleus, all these 10 radicals R being optionally substituted, which comprises reacting an acid halide of formula (II): R-Ϊ-Χ (II) in which R is as defined above and X denotes a halogen atom, 15 with an alkali metal cyanide, in anhydrous solvent medium in the presence of a product containing alkylene oxide units and a polar product other than water.
2. Process according to Claim 1, in which the alkali metal cyanide is employed in an amount from l to 2 20 moles per mole of acid halide.
3. Process according to claim 2 in which the alkali metal cyanide is employed in an amount from 1 to 1.25 moles per mole of acid halide.
4. Process according to any one of Claims 1 to 3, 25 in which sodium cyanide is employed.
5. Process according to any one of Claims 1 to 4, in which xylene or toluene is employed as solvent.
6. Process according to any one of Claims 1 to 5, in which the product containing alkylene oxide units contains 2 to 200 units which are ethylene oxide and/or propylene oxide units.
7. Process according to Claim 6 in which the quantity of said product is from 0.1 to '10 g, per mole of acid halide.
8. Process according to claim 6 in which the quantity of said product is from 0.4 to 2 g, per mole of acid halide.
9. Process according to any one of claims 1 to 8 in which the polar product is glycerol, ethylene glycol, formamide or a sugar derivative.
10. Process according to any one of Claims 1 to 9, in which the quantity of polar product is from 0.1 to 10 q per mole of acid halide.
11. Process according to claim 10 in which the quantity of polar product is 0.25 to 2 g per mole of acid halide.
12. Process according to any one of Claims 1 to 11, in which the acid halide is benzoyl chloride.
13. Process according to any one of Claims 1 to 12, in which the quantity of solvent is from 200 to 500 ml per mole of acid halide.
14. Process according to claim 1 substantially as described in any one of Examples 1 to 5 and 8. *J:
15. An acyl cyanide whenever synthesised by a , A, process as claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8906563A FR2647109B1 (en) | 1989-05-19 | 1989-05-19 | PROCESS FOR THE PREPARATION OF ACYLATE CYANIDES IN ANHYDROUS MEDIA |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE901801L IE901801L (en) | 1990-11-19 |
| IE69053B1 true IE69053B1 (en) | 1996-08-07 |
Family
ID=9381809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE180190A IE69053B1 (en) | 1989-05-19 | 1990-05-18 | Process for the preparation of acyl cyanides in anhydrous medium |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0398782B1 (en) |
| JP (1) | JPH0686414B2 (en) |
| KR (1) | KR940000062B1 (en) |
| CN (1) | CN1027260C (en) |
| AT (1) | ATE111442T1 (en) |
| CA (1) | CA2015998C (en) |
| DE (1) | DE69012424T2 (en) |
| DK (1) | DK0398782T3 (en) |
| ES (1) | ES2058839T3 (en) |
| FI (1) | FI103572B (en) |
| FR (1) | FR2647109B1 (en) |
| IE (1) | IE69053B1 (en) |
| NO (1) | NO172116C (en) |
| PT (1) | PT94087B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0718279B1 (en) * | 1990-12-31 | 1997-09-24 | Basf Aktiengesellschaft | Process for the preparation of o-substituted benzoylcyanides |
| EP0617005B1 (en) * | 1993-03-22 | 2001-06-13 | Fuji Xerox Co., Ltd. | Triarylamine compound, process for producing the same and electrophotographic photoreceptor using the same |
| BR9509751A (en) * | 1994-11-24 | 1998-06-16 | Basf Ag | Process for preparing halomethylbenzoyl cyanides |
| CN102642363A (en) * | 2012-04-28 | 2012-08-22 | 河南永威安防股份有限公司 | Production method of high-strength high-pressure decorating plate |
| CN109651193A (en) * | 2019-01-22 | 2019-04-19 | 江苏佳麦化工有限公司 | A kind of synthetic method of benzoyl cyanide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2614242C3 (en) * | 1976-04-02 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | Process for the production of acyl cyanides |
| DE2624891C2 (en) * | 1976-06-03 | 1982-11-18 | Degussa Ag, 6000 Frankfurt | Process for the production of benzoyl cyanide |
| DE2642140C2 (en) * | 1976-09-20 | 1982-10-28 | Degussa Ag, 6000 Frankfurt | Process for the production of benzoyl cyanide |
| DE3015587A1 (en) * | 1980-04-23 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING ACYLCYANIDES |
-
1989
- 1989-05-19 FR FR8906563A patent/FR2647109B1/en not_active Expired - Lifetime
-
1990
- 1990-05-03 CA CA002015998A patent/CA2015998C/en not_active Expired - Fee Related
- 1990-05-09 AT AT90401222T patent/ATE111442T1/en not_active IP Right Cessation
- 1990-05-09 DK DK90401222.6T patent/DK0398782T3/en active
- 1990-05-09 DE DE69012424T patent/DE69012424T2/en not_active Expired - Fee Related
- 1990-05-09 ES ES90401222T patent/ES2058839T3/en not_active Expired - Lifetime
- 1990-05-09 EP EP90401222A patent/EP0398782B1/en not_active Expired - Lifetime
- 1990-05-14 NO NO902140A patent/NO172116C/en not_active Application Discontinuation
- 1990-05-18 FI FI902473A patent/FI103572B/en active IP Right Grant
- 1990-05-18 IE IE180190A patent/IE69053B1/en not_active IP Right Cessation
- 1990-05-18 PT PT94087A patent/PT94087B/en not_active IP Right Cessation
- 1990-05-19 KR KR1019900007191A patent/KR940000062B1/en not_active IP Right Cessation
- 1990-05-19 CN CN90103730A patent/CN1027260C/en not_active Expired - Fee Related
- 1990-05-19 JP JP2130107A patent/JPH0686414B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0398782B1 (en) | 1994-09-14 |
| ES2058839T3 (en) | 1994-11-01 |
| NO172116C (en) | 1993-06-09 |
| PT94087B (en) | 1997-01-31 |
| FI103572B1 (en) | 1999-07-30 |
| NO902140D0 (en) | 1990-05-14 |
| CN1027260C (en) | 1995-01-04 |
| EP0398782A1 (en) | 1990-11-22 |
| KR940000062B1 (en) | 1994-01-05 |
| NO172116B (en) | 1993-03-01 |
| CA2015998A1 (en) | 1990-11-19 |
| ATE111442T1 (en) | 1994-09-15 |
| FR2647109B1 (en) | 1991-07-26 |
| NO902140L (en) | 1990-11-20 |
| PT94087A (en) | 1991-01-08 |
| DE69012424T2 (en) | 1995-04-20 |
| JPH0686414B2 (en) | 1994-11-02 |
| FI103572B (en) | 1999-07-30 |
| CN1047282A (en) | 1990-11-28 |
| JPH035448A (en) | 1991-01-11 |
| FI902473A0 (en) | 1990-05-18 |
| FR2647109A1 (en) | 1990-11-23 |
| KR900018011A (en) | 1990-12-20 |
| CA2015998C (en) | 1996-09-03 |
| DK0398782T3 (en) | 1995-02-13 |
| DE69012424D1 (en) | 1994-10-20 |
| IE901801L (en) | 1990-11-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |