CA1246608A - Dichlorotrifluoropropion-aldehyde and a process for its preparation - Google Patents
Dichlorotrifluoropropion-aldehyde and a process for its preparationInfo
- Publication number
- CA1246608A CA1246608A CA000435310A CA435310A CA1246608A CA 1246608 A CA1246608 A CA 1246608A CA 000435310 A CA000435310 A CA 000435310A CA 435310 A CA435310 A CA 435310A CA 1246608 A CA1246608 A CA 1246608A
- Authority
- CA
- Canada
- Prior art keywords
- dichloro
- methyl
- preparation
- published
- aldehyde
- 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.)
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Abstract
ABSTRACT
The present invention relates to 2,2-dichloro-3,3,3-trifluoro-propionaldehyde of the formula III
CF3-CC12-CHO (III) and to a novel process for its production. 2,2-Dichloro-3,3,3-trifluoro-propionaldehyde is a valuable intermediate for the synthesis of 2,3-dichloro-5-trifluoromethylpyridine.
The present invention relates to 2,2-dichloro-3,3,3-trifluoro-propionaldehyde of the formula III
CF3-CC12-CHO (III) and to a novel process for its production. 2,2-Dichloro-3,3,3-trifluoro-propionaldehyde is a valuable intermediate for the synthesis of 2,3-dichloro-5-trifluoromethylpyridine.
Description
This is a divisional patent application to the Canadian Patent Application Patent Application No. 384 531.
Case 5-13034/ZF0/1+2/DIV
Case 5-13034/ZF0/1+2/DIV
2,2-Dichloro-3,3,3-trifluoropropionaldehyde and _ process for the preparation thereof -The present invention relates to 2,2-dichloro-3,3,3-trîfluoro-propionaldehyde of the formula III
CF3-CC12-CH0 (III) and to a novel process for its production.
2,2-Dichloro-3,3,3-trifluoropropionaldehyde is a valuable intermediate for the synthesis of 2,3-dichloro-5-triEluoromethylpyridine.
Up to now it was possible to obtain chloropyridines substituted by ~ethyl, trichloromethyl or trifluoromethyl groups only by means of complicated muLti-step processes. For example, 2,3-dichlorowS-methyl pyridine can be obtained by diazotising 2-chloro-3-amino-5-methyl-pyridine and replacing the diazo group with chlorine.
The above aminopyridine can be ob~tained by chlorinating 3-methyl-pyridine to 2-chloro-5-methylpyridine, nitrating this compound to 2-chloro-3-methyl-5-nitropyridine and reducing the nitro compounds.
When chlorinating 3-methylpyridine, several isomers are usually obtained in addition to the desired compound. Chlorination of 2,3-dichloro 5-methylpyridine gives ~,3-dichloro-5-trichloromethyl-pyridine, which can be converted into 2,3-dichloro-5-trifluoromethyl-, ~: :
A ~.. .
' ' pyridine by replacing the chlorine atoms of the trichloromethyl groupby fluorine atoms (q.~. for e~ample European patent publication 004414).
Chloropyridines of the ormula I, R\ ~-\ /R' 11 (I) ~/ \Cl wherein either R i8 chlorine and R' is methyl or trifluoromethyl, or R is methyl, trichloromethyl or trifluoromethyl and R' is chlorine, or R and R' are me~hyl, can be obtained by the addition of a) trichloroacetaldehyde to methaçrylonitrile or ~-trifluorometh-acrylonitrile, b) 2,2-dichloropropionaldehyde, pentachloropropionaldehyde or 2,2-dichloro-3,3,3-trifluoropropionaldehyde to acrylonitrile, or c) 2,2-dichloropropionaldehyde to methacrylonitrile, in the presence of a catalyst, and cyclising the intermediate of the formula II
Cl Cl I
OCH-C-GH -C-CN (II) : 1 2 1 R R"
:wherein either R is chlorine and R" is methyl or trifluoromethyl, or R ie methyl, trichloromethyl or trifluoromethyl and R" is hydrogen, or R and R" are methyl, to give a compound of the formula I.
., : :
, , .. .
`~
~ .
; : : .
~46~
According to ~he present invention 2,2-dichloro-3,3,3-trifluoro-propionaldehyde can be obtained by ~reating corresponding olefins with ozone and ~orking up the reaction mass by reduction. Suitable solvents which can be employed are: organic acids such as formic acid~ acetic acid, propionic acid; the esters of these acids, such as ethyl acetate, methyl ace~ate, ethyl formate, methyl formate; aliphatic hydrocarbons such as pcntane, hexane, heptane, octane, cyclopentane, cyclohexane; chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; or also water. Depending on the nature of the solvent 0mployed, the reaction temperatures are in the ~ange ~rom -90 to ~70C, preferably from -70 to ~30C.
The reduction oE the products of the ozonolysis can be effectecl either by direct catalytic hydrogenation w;th hydrogen and a noble metal catalyst such as platinum, palladium, or rhodium, which catalyst may, if desired, be applied to a carrier, or by addition of reducing agents such as zinc or dimethyl sulfide.
A prefe-rred embodiment of this ozonolysis comprises ozonising 4,4-dichloro-5,5,5-trifluoro-2-methyl-2-pentenecarboxylic acid methyl ester in acetic acid at 20CJ then adding an aqueous suspension of zinc powder to the reaction mixture, and distilling off 2,2-dichloro-3,3,3-trifl~loropropional-dehyde direct from the mixture.
The chloropyridines of the formula I can be used in manner known per se via one or more intermediate steps for the production of different compounds, especially insecticides and herbicides ~cf. for example S~iss patent 622 170 ~published 3I March 1981), European patent publications 00176 ~published 10 Janu~ry 1979) and 04414 ~published 3 October 1~79); German Offenlengungs-.....
6~
schrift specifications 2 812 649 (published 26 April 1979) and 2 748 636 ~published 3 May 1978); South African patent ~published 15 March 1979) 78.02440; Japanese patent publications 5 4115-380 ~published 1979), 5 5038-356 (published 1979), and 5 5079-369 (published 14 June 1980); and Canadian patent 1,120~480).
The process of the present invention is illustrated in more detail by the following Examples.
:: -3a-: ' ~
, ~2~
Example 1: Preparation of 2,2-dichloro-3~3,3-trifluoropropion-aldehyde 19.2 g of ozone (admixed with oxygen) are introduced at 20C into a solution of 100.4 g o 4,4-dichloro-5,5,5-trifluoro-2-methyl-2-pentenecarboxylic acid methyl ester in 800 ml of glacial acetic acid. Then a suspension of 15 g of zinc dust in 15 ml of water is added and 2,2-dichloro-3,3,3-trifluoropropionaldehyde is distilled off under normal pressure. Yield: 52.8 g of product in the form of a colourless li~uid with a pungent odour. Boiling point: 66-67C.
IR (CC14):~co 1770 cm H-NMR (CDC13): ~=9.3 (~, J = 2Hz) ppm-Analysis: C3HC12E'30 tl80.9) calculated: C 19.92~ H 0.56% F 31.50~ Cl 39.19 found: C 20.2% H 0.8% F 30,9% Cl 38.5 Example 2: Preparation of 4-formyl-2,4-dichloro-5,5,5-trifluoro~
valeronitrile A mixture of 36 g of 2,2-dichloro-3,3/3-trifluoropropionaldehyde, 80 ml of acetonitrile, 80 ml of acrylonitrile and 0.5 g of copper (I) chloride is heated in a tantalum autoclave for 12 hours to ; 120C. After the mixture has cooled, the solvent is distilled ofE, at about 40-50C in water jet vacuum. The residue is taken up in 50 ml of diethyl ether and the precipitated copper sludge is removed by filtration. The diethyl ether ls distilled off and the residue is rectified in a high vacuum. The 4-formyl-~,4-, ~`
;`
~,....
~Z'~6~
- 4a -dichloro-5,5,5-trifluorovaleronitrile is obtained as a colour-less oil; boiling point: 85-86C/900 Pa.
IR (CC14): ~CN 2550 cm , ~CO 1750 cm H-NMR (CDC13): ~ = 9.56 (m; lH, CHO); 4.7 (m, lH, C-2-3);
2.7-3.3 (m, 2H, C-3-H) ppm (m.ixture of diasteroisomers).
Analysis: C6H4C12F3NO (234.0) calculated: C 30.80% H 1.73% N 5.99% ~ 24.36%
found: C 31.5% H 2.0% N 5.9% F 23.8% .
::
~;
Example 3: Preparation of 2 7 3-dichloro-5-trifluoromethylpyridine _ 25 g of the 4-formyl-2~4-dichloro-5,595-trifluorovaleronitrile obtained in Example 2 and 0.1 g of copper powder are heated in a tantalum autoclave for 5 hours to 170C. Stea~ distillatiou of the contents of the autoclave yields 11.9 g of 2,3-dichloro-5-trifluoro-methylpyridine as a colourless oil with a pepp~rmint odour.
Boiling point: 80C/3325 Pa.
H-NMR SCDC13): ~= 8.63 (d, J = 2Hz, lH); 8.03 (d, J = 2Hz, lH) ppm.
Analysis C6~2C12F3N (216-0) calculated: C 33.36~ H 0.93% N 6.48% Cl 32.82~ F 26.38%
found: C 33.5% H 1.0% ~ 6.5% Cl 33.4~ F 25~9%o Example _ Single-step process for the preparation of 2,3-dichloro-5-trifluoromethylpyrldine The batch employed in Example 2 is heated in a tantalum autoclave for 2 hours to 150C and then for a further 2 hours to 180C. The solvent is then distilled off~ the residue is taken up in 50 ml of diethyl ether, and the ethereal solution is filtered. The diethyl ether is distilled off in a water jet vacuum and the residue is subjected to steam distillation. The product is identical with the compound of Example 3.
:`
CF3-CC12-CH0 (III) and to a novel process for its production.
2,2-Dichloro-3,3,3-trifluoropropionaldehyde is a valuable intermediate for the synthesis of 2,3-dichloro-5-triEluoromethylpyridine.
Up to now it was possible to obtain chloropyridines substituted by ~ethyl, trichloromethyl or trifluoromethyl groups only by means of complicated muLti-step processes. For example, 2,3-dichlorowS-methyl pyridine can be obtained by diazotising 2-chloro-3-amino-5-methyl-pyridine and replacing the diazo group with chlorine.
The above aminopyridine can be ob~tained by chlorinating 3-methyl-pyridine to 2-chloro-5-methylpyridine, nitrating this compound to 2-chloro-3-methyl-5-nitropyridine and reducing the nitro compounds.
When chlorinating 3-methylpyridine, several isomers are usually obtained in addition to the desired compound. Chlorination of 2,3-dichloro 5-methylpyridine gives ~,3-dichloro-5-trichloromethyl-pyridine, which can be converted into 2,3-dichloro-5-trifluoromethyl-, ~: :
A ~.. .
' ' pyridine by replacing the chlorine atoms of the trichloromethyl groupby fluorine atoms (q.~. for e~ample European patent publication 004414).
Chloropyridines of the ormula I, R\ ~-\ /R' 11 (I) ~/ \Cl wherein either R i8 chlorine and R' is methyl or trifluoromethyl, or R is methyl, trichloromethyl or trifluoromethyl and R' is chlorine, or R and R' are me~hyl, can be obtained by the addition of a) trichloroacetaldehyde to methaçrylonitrile or ~-trifluorometh-acrylonitrile, b) 2,2-dichloropropionaldehyde, pentachloropropionaldehyde or 2,2-dichloro-3,3,3-trifluoropropionaldehyde to acrylonitrile, or c) 2,2-dichloropropionaldehyde to methacrylonitrile, in the presence of a catalyst, and cyclising the intermediate of the formula II
Cl Cl I
OCH-C-GH -C-CN (II) : 1 2 1 R R"
:wherein either R is chlorine and R" is methyl or trifluoromethyl, or R ie methyl, trichloromethyl or trifluoromethyl and R" is hydrogen, or R and R" are methyl, to give a compound of the formula I.
., : :
, , .. .
`~
~ .
; : : .
~46~
According to ~he present invention 2,2-dichloro-3,3,3-trifluoro-propionaldehyde can be obtained by ~reating corresponding olefins with ozone and ~orking up the reaction mass by reduction. Suitable solvents which can be employed are: organic acids such as formic acid~ acetic acid, propionic acid; the esters of these acids, such as ethyl acetate, methyl ace~ate, ethyl formate, methyl formate; aliphatic hydrocarbons such as pcntane, hexane, heptane, octane, cyclopentane, cyclohexane; chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; or also water. Depending on the nature of the solvent 0mployed, the reaction temperatures are in the ~ange ~rom -90 to ~70C, preferably from -70 to ~30C.
The reduction oE the products of the ozonolysis can be effectecl either by direct catalytic hydrogenation w;th hydrogen and a noble metal catalyst such as platinum, palladium, or rhodium, which catalyst may, if desired, be applied to a carrier, or by addition of reducing agents such as zinc or dimethyl sulfide.
A prefe-rred embodiment of this ozonolysis comprises ozonising 4,4-dichloro-5,5,5-trifluoro-2-methyl-2-pentenecarboxylic acid methyl ester in acetic acid at 20CJ then adding an aqueous suspension of zinc powder to the reaction mixture, and distilling off 2,2-dichloro-3,3,3-trifl~loropropional-dehyde direct from the mixture.
The chloropyridines of the formula I can be used in manner known per se via one or more intermediate steps for the production of different compounds, especially insecticides and herbicides ~cf. for example S~iss patent 622 170 ~published 3I March 1981), European patent publications 00176 ~published 10 Janu~ry 1979) and 04414 ~published 3 October 1~79); German Offenlengungs-.....
6~
schrift specifications 2 812 649 (published 26 April 1979) and 2 748 636 ~published 3 May 1978); South African patent ~published 15 March 1979) 78.02440; Japanese patent publications 5 4115-380 ~published 1979), 5 5038-356 (published 1979), and 5 5079-369 (published 14 June 1980); and Canadian patent 1,120~480).
The process of the present invention is illustrated in more detail by the following Examples.
:: -3a-: ' ~
, ~2~
Example 1: Preparation of 2,2-dichloro-3~3,3-trifluoropropion-aldehyde 19.2 g of ozone (admixed with oxygen) are introduced at 20C into a solution of 100.4 g o 4,4-dichloro-5,5,5-trifluoro-2-methyl-2-pentenecarboxylic acid methyl ester in 800 ml of glacial acetic acid. Then a suspension of 15 g of zinc dust in 15 ml of water is added and 2,2-dichloro-3,3,3-trifluoropropionaldehyde is distilled off under normal pressure. Yield: 52.8 g of product in the form of a colourless li~uid with a pungent odour. Boiling point: 66-67C.
IR (CC14):~co 1770 cm H-NMR (CDC13): ~=9.3 (~, J = 2Hz) ppm-Analysis: C3HC12E'30 tl80.9) calculated: C 19.92~ H 0.56% F 31.50~ Cl 39.19 found: C 20.2% H 0.8% F 30,9% Cl 38.5 Example 2: Preparation of 4-formyl-2,4-dichloro-5,5,5-trifluoro~
valeronitrile A mixture of 36 g of 2,2-dichloro-3,3/3-trifluoropropionaldehyde, 80 ml of acetonitrile, 80 ml of acrylonitrile and 0.5 g of copper (I) chloride is heated in a tantalum autoclave for 12 hours to ; 120C. After the mixture has cooled, the solvent is distilled ofE, at about 40-50C in water jet vacuum. The residue is taken up in 50 ml of diethyl ether and the precipitated copper sludge is removed by filtration. The diethyl ether ls distilled off and the residue is rectified in a high vacuum. The 4-formyl-~,4-, ~`
;`
~,....
~Z'~6~
- 4a -dichloro-5,5,5-trifluorovaleronitrile is obtained as a colour-less oil; boiling point: 85-86C/900 Pa.
IR (CC14): ~CN 2550 cm , ~CO 1750 cm H-NMR (CDC13): ~ = 9.56 (m; lH, CHO); 4.7 (m, lH, C-2-3);
2.7-3.3 (m, 2H, C-3-H) ppm (m.ixture of diasteroisomers).
Analysis: C6H4C12F3NO (234.0) calculated: C 30.80% H 1.73% N 5.99% ~ 24.36%
found: C 31.5% H 2.0% N 5.9% F 23.8% .
::
~;
Example 3: Preparation of 2 7 3-dichloro-5-trifluoromethylpyridine _ 25 g of the 4-formyl-2~4-dichloro-5,595-trifluorovaleronitrile obtained in Example 2 and 0.1 g of copper powder are heated in a tantalum autoclave for 5 hours to 170C. Stea~ distillatiou of the contents of the autoclave yields 11.9 g of 2,3-dichloro-5-trifluoro-methylpyridine as a colourless oil with a pepp~rmint odour.
Boiling point: 80C/3325 Pa.
H-NMR SCDC13): ~= 8.63 (d, J = 2Hz, lH); 8.03 (d, J = 2Hz, lH) ppm.
Analysis C6~2C12F3N (216-0) calculated: C 33.36~ H 0.93% N 6.48% Cl 32.82~ F 26.38%
found: C 33.5% H 1.0% ~ 6.5% Cl 33.4~ F 25~9%o Example _ Single-step process for the preparation of 2,3-dichloro-5-trifluoromethylpyrldine The batch employed in Example 2 is heated in a tantalum autoclave for 2 hours to 150C and then for a further 2 hours to 180C. The solvent is then distilled off~ the residue is taken up in 50 ml of diethyl ether, and the ethereal solution is filtered. The diethyl ether is distilled off in a water jet vacuum and the residue is subjected to steam distillation. The product is identical with the compound of Example 3.
:`
Claims (2)
1. 2,2-dichloro-3,3,3-trifluoropropionaldehyde.
2. A process for the production of 2,2-dichloro-3,3,3-trifluoropropion-aldehyde, which comprises subjecting a corresponding olefin to ozonolysis and working up the reaction mass by reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000435310A CA1246608A (en) | 1980-08-27 | 1983-08-24 | Dichlorotrifluoropropion-aldehyde and a process for its preparation |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH644780 | 1980-08-27 | ||
| CH6447/80-0 | 1980-08-27 | ||
| CH3834/81-0 | 1981-06-11 | ||
| CH383481 | 1981-06-11 | ||
| CA000384531A CA1172638A (en) | 1980-08-27 | 1981-08-25 | Process for the production of chloropyridines substituted by methyl, trichloromethyl or trifluoromethyl groups |
| CA000435310A CA1246608A (en) | 1980-08-27 | 1983-08-24 | Dichlorotrifluoropropion-aldehyde and a process for its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246608A true CA1246608A (en) | 1988-12-13 |
Family
ID=27167120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000435310A Expired CA1246608A (en) | 1980-08-27 | 1983-08-24 | Dichlorotrifluoropropion-aldehyde and a process for its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1246608A (en) |
-
1983
- 1983-08-24 CA CA000435310A patent/CA1246608A/en not_active Expired
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| Date | Code | Title | Description |
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| MKEX | Expiry |