CA1049541A - Process for the preparation of carboxylic amides - Google Patents
Process for the preparation of carboxylic amidesInfo
- Publication number
- CA1049541A CA1049541A CA237,128A CA237128A CA1049541A CA 1049541 A CA1049541 A CA 1049541A CA 237128 A CA237128 A CA 237128A CA 1049541 A CA1049541 A CA 1049541A
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- general formula
- same meanings
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
N,N-disubstituted carboxylic amides having the general formula:
(III) in which R1 and R2 each represents an optionally substituted aliphatic hydro-carbyl group or together with the adjacent nitrogen atom represent a hetero-cyclic group optionally containing one of more further hetero atoms, and R3 is an optionally substituted aliphatic, aromatic, araliphatic or cycloaliphatic group or saturated or aromatic heterocyclic group, are prepared by reacting a compound of the general formula:
(IV) with an adduct of the formula:
(R1R2N - CHO - X)+C1- (I) or (R1R2N = CHC1)+C1- (II) wherein X is a group selected from -SOC1, -POC12, -PC14, -PC12, -CO-CO-C1 and -CO-C1. The proccss operates with improved yield to give the amides III which are useful as herbicides, insecticides and in the dyestuff industry.
N,N-disubstituted carboxylic amides having the general formula:
(III) in which R1 and R2 each represents an optionally substituted aliphatic hydro-carbyl group or together with the adjacent nitrogen atom represent a hetero-cyclic group optionally containing one of more further hetero atoms, and R3 is an optionally substituted aliphatic, aromatic, araliphatic or cycloaliphatic group or saturated or aromatic heterocyclic group, are prepared by reacting a compound of the general formula:
(IV) with an adduct of the formula:
(R1R2N - CHO - X)+C1- (I) or (R1R2N = CHC1)+C1- (II) wherein X is a group selected from -SOC1, -POC12, -PC14, -PC12, -CO-CO-C1 and -CO-C1. The proccss operates with improved yield to give the amides III which are useful as herbicides, insecticides and in the dyestuff industry.
Description
l~C~S~ ' This invention relates to a novel process for the preparation of carboxylic amides.
N,N-Dialkyl carboxylic amides have extensive utilization in various fields. Thus, great amounts of N,N-dimethyl-~,a-diphenyl-acetamide are used in the agriculture as a herbicidal agent for plant protection purposes. Some other disubstituted carboxylic amides, having insecticidal properties, are also us~d as plant protecting agentsO Such compounds are also applied in the human therapyJ furthermore in the dyestuff industryO
According to the most widespread method, these compounds are p~epared by chlorinating the appropriate carboxylic acid derivatives, and reacting the thus-obtained acid chlorides with the appropriate dialkylamines.
In the majority of the synthesesstartin~ from carboxylic acid derivatives the carboxylic acid derivatives are reacted first with chlor m at-ing agents, and then the obtained acid chlorides are treated with a great excess of the appropriate dialkyl amine optionally in the presence of a solvent. The well-known disadvantages of this method are as follows: the acid chloride formation proceeds frequently with a low rate and with an inappropriate yield, the isolation of the acid chlorides is difficult, and, even when the reaction conditions are controlled very carefully, their
N,N-Dialkyl carboxylic amides have extensive utilization in various fields. Thus, great amounts of N,N-dimethyl-~,a-diphenyl-acetamide are used in the agriculture as a herbicidal agent for plant protection purposes. Some other disubstituted carboxylic amides, having insecticidal properties, are also us~d as plant protecting agentsO Such compounds are also applied in the human therapyJ furthermore in the dyestuff industryO
According to the most widespread method, these compounds are p~epared by chlorinating the appropriate carboxylic acid derivatives, and reacting the thus-obtained acid chlorides with the appropriate dialkylamines.
In the majority of the synthesesstartin~ from carboxylic acid derivatives the carboxylic acid derivatives are reacted first with chlor m at-ing agents, and then the obtained acid chlorides are treated with a great excess of the appropriate dialkyl amine optionally in the presence of a solvent. The well-known disadvantages of this method are as follows: the acid chloride formation proceeds frequently with a low rate and with an inappropriate yield, the isolation of the acid chlorides is difficult, and, even when the reaction conditions are controlled very carefully, their
2~ liability to hydrolysis decreases the yield of the amination procedure to a considerable extent.
Now it has been found that carboxylic acids can be converted I with very good yields into the appropriate N,N-disubstituted carboxylic I amides when an adduct formed from a ', :
.
.~ ~
. `' .
~ -2-. ' :
~4959~
:
disubstituted forma~ide and a chlorinating agent, such as thionyl chloride, is used as aminating agent.
Adducts of the above type are ~ell known in the literature and have known and identified structures. When contacting a disubstituted formamide (e.g. an N,N-dialkyl compound) with a chlorinating agent either in the presence of a solvent or in a solvent-free medium, an adduct of the general formula CI) ~RlR2N - C~10 - X) Cl (I) is obtained with quantitative yield. Upon hea~ing to higher temperatures, these compounds convert into the unsaturated derivatives having the general formula ~II) (RlR2N = CHCl) Cl ~II) The above-identified adducts, known in the literature as ; Vilsmeier complexes, have been applied so far as formylating agents`~ ~Ann. PharmO 24, 793 /1966/), isonitrile-forming agents ~J. Org. Chem. 37, ~; 187 /1972/), reactants for replacing alcoholic hydroxy groups by halogen atoms (Chem. and IndO 16, 664 /1974/), as well as for the conversion of carboxylic acids into acid chlorides ~Ann. Quim. 65 1167 /1969/).
~ Now it has been detected that these complexes can be used to a ;' 20 great advantage for the conversion of carboxylic acid derivatives into the respective N,N-disubstituted carboxylic amides. The reaction proceeds smoothly and provides the desired end-products with almost quantitative yields. When the reaction is performed at 110 to 150C, optionally in the presence of a solvent, both types of the above-men*ioned adducts can be used.
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.
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Accordingly, the invention relates to a novel process for the pre-paration of N,N-disubstituted carboxylic amides having the general formula (III), " ,1 :
R - C - N - R2 ~III) wherein Rl and R2 each represent an aliphatic hydrocarbyl group, or Rl and R2, ~ :
together with the adjacent nitrogen atom, form a heterocyclic group containing optionally further hetero atom(s), and R3 is an aliphatic, aromatic, araliphatic or cycloaliphatic hydrocarbyl group or a saturated or aromatic heterocyclic group, all of them optionally substituted by one or more halogen atoms and/or by a -CONRlR2 group, in which a compound of the general formula ~IV), 1 0 0 ,' ~ ' R3 - C - OH (IV) .
wherein R3 has the same meanings as defined above, is reacted, at a temperature :
not exceeding the boiling point of the reaction mixture, with an adduct of the general formula (I) or (II), (RlR2N - CHO - X) Cl (I) -.
(RlR2N = CHCl) Cl (II) wherein Rl and R2 each have the same meanings as defined above and X is a group of the formula -SOCl, ~POC12, _PC14J PC12, ~CO-CO-Cl or -CO-Cl, said adduc~s being prepared by ~, '~ ' '.
. .
' . . , 1(~4~\54~ :
mixing a compound of the general formula HC0NRlR2 (wheIein Rl and R2 each have the same meanings as defined above) with at least equimolar amount of thionyl chloride, phosphorous oxychloride, phosphorous pentachloride, phosphorous trichloride, oxalyl chloride or phosgene> and the obtained product of the general formula (III) is isolated from the reaction mixture.
One may proceed e~g. by preparing first an adduct of the general formula ~I) or (II) and reacting it in a further step with the appropriate acid derivative of the general formula ~IV), equally good results can be achieved, however, when the adduct is formed in the presence of the acid derivative. As solvent, preferably the disubstituted formamide used in the adduct ormation is appliedO
The process of the invention can be used for the conversion of the most diverse carboxylic acids, such as optionally substituted aliphatic, cycloaliphatic, heterocyclic aliphatic, aromatic, polycyclic aromatic, araliphatic or heteroaromatic mono- or dicarboxylic acids into their N,N-disubstituted amidesO Similarly, the most diverse N,N-disubsti~uted formamides containing aliphatic, cycloaliphatic, heterocyclic aliphatic or aromatic substituents can be applied in the preparation of the adducts.
As mentioned above, the novel reaction according to the invention - -2Q provides the aimed products with excellent yields. The reaction proceeds smoothly and quickly, and no difficult reaction or isolation conditions are to be met with.
Thus, for example, when 1 le of diphenylacetic acid is treated ;
at 130C for one hour with a complex prepared from l.l moles of thionyl chloride and 2 moles of dimethyl formamide, and then the reaction mixture is poured onto ice, the separated crystals are filtered off, washed with water, and dried, the aimed N,N-dimethyl-diphenylacetamide is obtained with a yield of 97 %.
Since the amidation according to the invention proceeds under -3Q far milder conditions than the known procedures, the side-reactions can be .; ., .~
r ~49S~
suppressed to a great extent, as a result of which the end-products are obtained with high yields or the non-reacted starting substances can be recovered with a good efficiency, respectively.
The process of the invention is elucidated in detail by the aid of the following non-limiting Examples.
Exam~le_l , N,N-Dimethyl-a, ~diphenyl=acetamide 21.2 g. of diphenylacetic acid and 14.1 g. of chloromethylene-dimethyl-ammonium chloride are dissolved in 10 ml. of dimethyl formamide, and the mixture is stirred at 130C for one hourO Thereafter the mixture is poured into 200 ml. of water under stirring, and the pH of the obtained mixture is adjusted to 8 using aqueous sodium hydroxide solution~ The separated white substance is filtered off, washed with water, and dried.
2302 g. ~96.9 %) of N,N dimethyl-~,~-diphenyl-acetamide are obtained; m.p.:
130-131.5C.
` Analysis:
calculated: C: 8Q.30 % H: 7.16 % N: 5.86 %
found: C: 8Q.27 % H: 7.19 % N: 5.84 %
ple 2 2a - N- ethyl-a,-diphenyl-acetamide A solution of 22.88 g. of phosphorous pentachloride in 14~6 g.
of dimethyl formamide is maintained at 90 to 100C for 5 minutes. Thereafter 21.2 g. of diphenylacetic acid are added to the solution, and the mixture is stirred at 130C for one hour. The mixture is poured into 200 ml. of water under stirring, and the pH of the obtained mixture is adjusted to 8 ~; using aqueous sodium hydroxide solution. The separated substance is filtered off, washed with water9 and dried. 23.3 g. (97.3 %) of N,N-dimethyl-a,~-diphenyl-acetamide are obtained; m.p.: 130-132C~
,, 1~9L95~L
21.9 g. of dimethyl formamide are treated with 14085 g. of phosgene at O to 5CJ and then the mixture is maintained at 40 ~o 45~C foT one hour. ~-21.2 g. of diphenylacetic acid are added, and the mixture is stirred at 130C
for one hour. Thereafter the mixture is processed as described in Example 1 to obtain 22.85 g. ~95.4 %) of N,N-dimethyl~ diphenyl-acetamide; mOp.:
130-132C.
Example 4 N N-Dimethyl-~,~-diphenyl-acetamide 13.09 g. of thionyl chloride are added to a stirred solution of a 21.2 g. of diphenylacetic acid in 14.6 g. of dimethyl formamide at 110C
within 10 minutes, and the mixture is stirred at 130C for one hour. There-after the mixture is processed as described in Example 1 to obtain 22.9 g.
C95.6 %) of N,N-dimethyl-~,~-diphenyl-acetamide; m.p.: 130-131C.
Example 5 N ~_ D ethyl~ henyl-acetamide One proceeds aS described in ~xample 4 with the difference tha~
16.88 g. of phosphorous oxychloride are substituted for the 13.09 g. of thionyl chloride. 23.0 g. (96.1 %~ of the title compound are obtained;
m.p.: 130-13105C.
2~ ~
N,N ~ -acetamide . _ One proceeds as described in Example 4 with the difference that 6.87 g. of phosphorous trichloride are substituted for the 13.09 g. of thionyl chloride. 23005 g. ~96.3 %) of the title compound are obtained;
m.p.: 130-132C.
Example 7 N N- methyl-p~ ylacetamide ~ _ _ 26018 g. of thionyl chloride are added, at 110C, to a stirred solution of 27.2 g. of phenylacetic acid in 29.2 g. of dimethyl formamide.
Now it has been found that carboxylic acids can be converted I with very good yields into the appropriate N,N-disubstituted carboxylic I amides when an adduct formed from a ', :
.
.~ ~
. `' .
~ -2-. ' :
~4959~
:
disubstituted forma~ide and a chlorinating agent, such as thionyl chloride, is used as aminating agent.
Adducts of the above type are ~ell known in the literature and have known and identified structures. When contacting a disubstituted formamide (e.g. an N,N-dialkyl compound) with a chlorinating agent either in the presence of a solvent or in a solvent-free medium, an adduct of the general formula CI) ~RlR2N - C~10 - X) Cl (I) is obtained with quantitative yield. Upon hea~ing to higher temperatures, these compounds convert into the unsaturated derivatives having the general formula ~II) (RlR2N = CHCl) Cl ~II) The above-identified adducts, known in the literature as ; Vilsmeier complexes, have been applied so far as formylating agents`~ ~Ann. PharmO 24, 793 /1966/), isonitrile-forming agents ~J. Org. Chem. 37, ~; 187 /1972/), reactants for replacing alcoholic hydroxy groups by halogen atoms (Chem. and IndO 16, 664 /1974/), as well as for the conversion of carboxylic acids into acid chlorides ~Ann. Quim. 65 1167 /1969/).
~ Now it has been detected that these complexes can be used to a ;' 20 great advantage for the conversion of carboxylic acid derivatives into the respective N,N-disubstituted carboxylic amides. The reaction proceeds smoothly and provides the desired end-products with almost quantitative yields. When the reaction is performed at 110 to 150C, optionally in the presence of a solvent, both types of the above-men*ioned adducts can be used.
, ' " .
,. .
~, , :
.
. ' .
; :
. ~ :
1~95~
Accordingly, the invention relates to a novel process for the pre-paration of N,N-disubstituted carboxylic amides having the general formula (III), " ,1 :
R - C - N - R2 ~III) wherein Rl and R2 each represent an aliphatic hydrocarbyl group, or Rl and R2, ~ :
together with the adjacent nitrogen atom, form a heterocyclic group containing optionally further hetero atom(s), and R3 is an aliphatic, aromatic, araliphatic or cycloaliphatic hydrocarbyl group or a saturated or aromatic heterocyclic group, all of them optionally substituted by one or more halogen atoms and/or by a -CONRlR2 group, in which a compound of the general formula ~IV), 1 0 0 ,' ~ ' R3 - C - OH (IV) .
wherein R3 has the same meanings as defined above, is reacted, at a temperature :
not exceeding the boiling point of the reaction mixture, with an adduct of the general formula (I) or (II), (RlR2N - CHO - X) Cl (I) -.
(RlR2N = CHCl) Cl (II) wherein Rl and R2 each have the same meanings as defined above and X is a group of the formula -SOCl, ~POC12, _PC14J PC12, ~CO-CO-Cl or -CO-Cl, said adduc~s being prepared by ~, '~ ' '.
. .
' . . , 1(~4~\54~ :
mixing a compound of the general formula HC0NRlR2 (wheIein Rl and R2 each have the same meanings as defined above) with at least equimolar amount of thionyl chloride, phosphorous oxychloride, phosphorous pentachloride, phosphorous trichloride, oxalyl chloride or phosgene> and the obtained product of the general formula (III) is isolated from the reaction mixture.
One may proceed e~g. by preparing first an adduct of the general formula ~I) or (II) and reacting it in a further step with the appropriate acid derivative of the general formula ~IV), equally good results can be achieved, however, when the adduct is formed in the presence of the acid derivative. As solvent, preferably the disubstituted formamide used in the adduct ormation is appliedO
The process of the invention can be used for the conversion of the most diverse carboxylic acids, such as optionally substituted aliphatic, cycloaliphatic, heterocyclic aliphatic, aromatic, polycyclic aromatic, araliphatic or heteroaromatic mono- or dicarboxylic acids into their N,N-disubstituted amidesO Similarly, the most diverse N,N-disubsti~uted formamides containing aliphatic, cycloaliphatic, heterocyclic aliphatic or aromatic substituents can be applied in the preparation of the adducts.
As mentioned above, the novel reaction according to the invention - -2Q provides the aimed products with excellent yields. The reaction proceeds smoothly and quickly, and no difficult reaction or isolation conditions are to be met with.
Thus, for example, when 1 le of diphenylacetic acid is treated ;
at 130C for one hour with a complex prepared from l.l moles of thionyl chloride and 2 moles of dimethyl formamide, and then the reaction mixture is poured onto ice, the separated crystals are filtered off, washed with water, and dried, the aimed N,N-dimethyl-diphenylacetamide is obtained with a yield of 97 %.
Since the amidation according to the invention proceeds under -3Q far milder conditions than the known procedures, the side-reactions can be .; ., .~
r ~49S~
suppressed to a great extent, as a result of which the end-products are obtained with high yields or the non-reacted starting substances can be recovered with a good efficiency, respectively.
The process of the invention is elucidated in detail by the aid of the following non-limiting Examples.
Exam~le_l , N,N-Dimethyl-a, ~diphenyl=acetamide 21.2 g. of diphenylacetic acid and 14.1 g. of chloromethylene-dimethyl-ammonium chloride are dissolved in 10 ml. of dimethyl formamide, and the mixture is stirred at 130C for one hourO Thereafter the mixture is poured into 200 ml. of water under stirring, and the pH of the obtained mixture is adjusted to 8 using aqueous sodium hydroxide solution~ The separated white substance is filtered off, washed with water, and dried.
2302 g. ~96.9 %) of N,N dimethyl-~,~-diphenyl-acetamide are obtained; m.p.:
130-131.5C.
` Analysis:
calculated: C: 8Q.30 % H: 7.16 % N: 5.86 %
found: C: 8Q.27 % H: 7.19 % N: 5.84 %
ple 2 2a - N- ethyl-a,-diphenyl-acetamide A solution of 22.88 g. of phosphorous pentachloride in 14~6 g.
of dimethyl formamide is maintained at 90 to 100C for 5 minutes. Thereafter 21.2 g. of diphenylacetic acid are added to the solution, and the mixture is stirred at 130C for one hour. The mixture is poured into 200 ml. of water under stirring, and the pH of the obtained mixture is adjusted to 8 ~; using aqueous sodium hydroxide solution. The separated substance is filtered off, washed with water9 and dried. 23.3 g. (97.3 %) of N,N-dimethyl-a,~-diphenyl-acetamide are obtained; m.p.: 130-132C~
,, 1~9L95~L
21.9 g. of dimethyl formamide are treated with 14085 g. of phosgene at O to 5CJ and then the mixture is maintained at 40 ~o 45~C foT one hour. ~-21.2 g. of diphenylacetic acid are added, and the mixture is stirred at 130C
for one hour. Thereafter the mixture is processed as described in Example 1 to obtain 22.85 g. ~95.4 %) of N,N-dimethyl~ diphenyl-acetamide; mOp.:
130-132C.
Example 4 N N-Dimethyl-~,~-diphenyl-acetamide 13.09 g. of thionyl chloride are added to a stirred solution of a 21.2 g. of diphenylacetic acid in 14.6 g. of dimethyl formamide at 110C
within 10 minutes, and the mixture is stirred at 130C for one hour. There-after the mixture is processed as described in Example 1 to obtain 22.9 g.
C95.6 %) of N,N-dimethyl-~,~-diphenyl-acetamide; m.p.: 130-131C.
Example 5 N ~_ D ethyl~ henyl-acetamide One proceeds aS described in ~xample 4 with the difference tha~
16.88 g. of phosphorous oxychloride are substituted for the 13.09 g. of thionyl chloride. 23.0 g. (96.1 %~ of the title compound are obtained;
m.p.: 130-13105C.
2~ ~
N,N ~ -acetamide . _ One proceeds as described in Example 4 with the difference that 6.87 g. of phosphorous trichloride are substituted for the 13.09 g. of thionyl chloride. 23005 g. ~96.3 %) of the title compound are obtained;
m.p.: 130-132C.
Example 7 N N- methyl-p~ ylacetamide ~ _ _ 26018 g. of thionyl chloride are added, at 110C, to a stirred solution of 27.2 g. of phenylacetic acid in 29.2 g. of dimethyl formamide.
3~ The~eafter the mixture is maintained at 130 to 140C for 1.5 hours~ The ` ' ' ,' . ' , ;' ' , ' . , ' ', ' . . ~ . '' . ~ , 10495~
reaction mixture is poured into 300 ml. of water, and the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous- ;
alkaline mixture is extracted with 3 x 50 ml. of dichloroethane, and the extract is fractionatedO 27.1 g. (83.5 %) of N,N-dimethyl-phenylacetamide are obtained; m.p.: 42-43C, b.p.: 162-165C/25 mm Hg.
Exa~æ e 8 N-~æeridyl~ diphenyl-acetamide _ _ 26018 g. of thionyl chloride are added, at llO~C, to a stirred mixture of 45.0 g. of N-formyl-piperidine and 42.4 g. of diphenylacetic acid, and the mixture is maintained at 135C for one hour. Thereafter the mixture is processed as described in Example 1 to obtain 50.3 g. ~90.0 %) of `
the title compound; m.p.: 116-117C.
Analysis:
calculated: C: 81.68 ~ ~: 7,58 % N: 5.01 %
found: C: 81.74 % H: 7.58 % N: 5.09 %
~9 N N- met~ ,o-dichloro-acetamide _~ _ _ _ _ _ _ 39.27 g. of thionyl chloride are added, at 110C, to a stirred solution of 38.7 g. of dichloroacetic acid in 44.4 g. of dimethyl formamide.
The reaction mixture is maintained at 135C for 2 hours, thereafter it is diluted with 150 ml. of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillation. 38.9 g. ~83.1 %) of N,N-dimethyl~ -dichloro-acetamide are obtained; b.p.: 78-80C/1.5-2 mm Hg; nD5 = 1.4946.
_xample 10 ~ _-Dieth ~
39.27 g. of thionyl chloride are added, at 110 C, to a stirred solution of 38.7 g. of dichloroacetic acid in 60.0 gO of diethyl formamide.
e reaction mixture is maintained at 135C for 2 hours, thereafter it is , ~(94954~
diluted with 150 ml. of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillation. 44.6 g. (80.8 %) of the title compound are obtained; b.p.: 100 C/4 mm Hg, nD = 1.4930.
E~ æle 11 N,N-Diallyl-a,a-dichloro-acetamide 39.27 g. of thionyl chloride are added, at 110C, to a stirred solution of 38.7 g. of dichloroacetic acid in 75.0 g. of diallyl formamide.
The mixture is maintained at 135C for 2 hours, thereafter it is diluted with 150 mlO of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillationO 31.2 g. ~52.8 %) of NJN-diallyl-a~a-dichlor acetamide are obtained; b.p.: 93C/2 mm Hg, nD5 = 1.5021.
le 12 N,N,N~,N'-Tetramethyl-adipic acid diamide 143.0 g. of thionyl chloride are added, at 110C, to a stirred solution of 73O0 g. of adipic acid in 146.0 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for 2 hours. The mixture is diluted with 300 ml. of water, and the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline mixture is extracted with 4 x 150 mlO of chloroform, and the extract is subjected to fractional distillation. 57.0 g. (56.9 %) of the title compound are obtained; b.p.: 190-192C/4 mm Hg; m.p.: 79-79.5C.
Exam~le 13 N~N-Dimethyl-ca~ryli _ amide 26.18 g. of thionyl chloride are added, at 110C, to a stirred suluticn of 28.2 g. of caprylic acid in 29.6 g. of dimethyl formamide, and 3Q the mixture is maintained at 135 C for 1.5 hours. The mixture is diluted _g_ I
:
with 200 ml. of water, the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution, and the aqueous-alkaline mixture is extracted with 3 x 50 ml. of chloroform. The extract is subjected to fractional distillation to obtain 27.7 g. (8Q~8 %) of N,N-dimethyl-caprylic amide; b.p.: 119-122C/60 mm Hg.
Analysis:
calculated: C: 70.12 % H: 12.36 % N: 8.18 %
found: C: 70.40 % H: 12.35 % N: 8.29 %
Ex~ple _14 ~N ___ ethyl-oleic a~ide 13.08 g. of thionyl chloride are added, at 110C, to a stirred solution of 28.2 g. of oleic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for 1.5 hours. The mixture is diluted with 100 ml. of water, and its pH is adjusted to 8 with aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 50 ml. of chloroform, and the extract is subjected to fractional distillation. 26.0 g. (84.0 %) of N,N-dimethyl-oleic amide are obtained;
n2D0 = 1.4644, m.p.: -8.5 C.
Example _15 2Q N,N-Dimethyl-benzoic amide ; 3~o27 g. of thionyl chloride are added~ at 110C, to a stirred solution o 36.6 g. of benzoic acid in 43.8 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for 3 hours. The mixture is diluted with 150 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline solution is extracted with `~ 3 x 80 ml. of chloroform. The extract is subjected to fractional distillation to obtain 36.1 g. (80.7 %) of N,N-dimethyl-benzoic amide; b~po 150-160C/35 mm Hg.
Analysis:
3Q calculated; C: 72.46 % H: 7.43 % N: 9.39 %
fo~nd: C: 72.36 % H: 7.47 % N: 9.38 %
'~' . , ' ' : ' ~ . : .
~ ' ' :, , ' . '' - . ' ' ':;.
~IL954~ :
Exam~l _ 16 N,N-Dimethyl-l-n~ yl-amide 13008 gO of thionyl chloride are added, at 110C, to a stirred solution of 17.2 g. of a naphthoic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for one hour. The mixture is diluted with 100 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline solution is extracted with 3 x 40 ml. of chloroform. The extract is subjected to fractional distillation to obtain 17.9 g. ~89.8 %~ of the title compound; b.p.: 134-136C/0.15 mm Hg; m.p.:
61-62C.
N N-Di-~tA~
13.08 g. of thionyl chloride are added, at 110C, to a stirred solution of 11.2 g. of a-furanecarboxylic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for 1.5 hours. Thereafter the mixture is diluted with 150 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline mixture is extracted with 3 x 50 mlO of chloroform. The extract is dried, the solvent is evaporated, and the residue is triturated with petroleum ether. 11.5 g.
2Q (82.6 %) of the title compound are obtained; m.p.: 43-45C.
Analysis: -~; calculated: C: 60.41 % H: 6.52 % N: 10.07 %
found: C: 60.40 % H: 6.39 % N 10.15 %
Exam~le 18 N-Dimethyl-2-chloro-nicotinic amide 26.2 g~ of thionyl chloride are added, at 110C, to a stirred i solution of 31.5 g. of 2-chloro-nicotinic acid in 29.2 g. of dimethyl formamide, and the mixture is maintained at 130 to 135C for one hour.
Thereafter the mixture is diluted with 150 ml. of water, its p~ is adjusted 3Q to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline `:`
' . ~ , .
. . .
.. , ,, ,, . , . . :
: `--954~L
mixture is extracted ~ith 3 x 100 ml. of chloroform. The extract is subjected to fractional distillation to obtain 28.0 g. ~75.6 %) of the title compound;
b.p.: 162-164 C/4 mm Hg; m.p.: 68-69C.
Example 19 N N- e~y~ _ ic inic amide ___ A suspension of 61.5 g. of nicotinic acid in 73.0 g. of dimethyl formamide is heated to 110C, and 71.5 g. of thionyl chloride are added with stirring to the obtained homogeneous solution. The mixture is maintained at 130 to 135C for 2 hours, thereafter it is diluted with 200 ml. of water, la and the pH of the mixture is adjusted to 8 with aqueous sodium hydroxide solution. The mixture is extracted with 3 x 200 ml. of chloroform, and the extract is subjected to fractional distillation. 52.5 g. ~69.9 %) of the title compound are obtained; b.p.: 162-165C/12 mm Hg, m.p.: 44-45C.
le 20 NJN-Dimethyl-cinnamic amide _ ___ _ ~
26.2 g. of thionyl chloride are added, at 110C, to a stirred solution of 29.6 g. of cinnamic acid in 29.2 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for one hour. The reaction mixture is poured into 200 ml. of water, and the pH of the obtained mixture 2a is adjusted to 8 using aqueous sodium hydroxide solution. The separated substance is filtered off, washed with water, and dried. 30.6 g. ~87.3 %) of the title compound are obtained; m.p.: 95-97C.
Analysis:
calculated: C: 75.40 % H: 7.48 % N: 7.99 %
found: C: 75.47 % H: 7.50 % N: 7.93 %
reaction mixture is poured into 300 ml. of water, and the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous- ;
alkaline mixture is extracted with 3 x 50 ml. of dichloroethane, and the extract is fractionatedO 27.1 g. (83.5 %) of N,N-dimethyl-phenylacetamide are obtained; m.p.: 42-43C, b.p.: 162-165C/25 mm Hg.
Exa~æ e 8 N-~æeridyl~ diphenyl-acetamide _ _ 26018 g. of thionyl chloride are added, at llO~C, to a stirred mixture of 45.0 g. of N-formyl-piperidine and 42.4 g. of diphenylacetic acid, and the mixture is maintained at 135C for one hour. Thereafter the mixture is processed as described in Example 1 to obtain 50.3 g. ~90.0 %) of `
the title compound; m.p.: 116-117C.
Analysis:
calculated: C: 81.68 ~ ~: 7,58 % N: 5.01 %
found: C: 81.74 % H: 7.58 % N: 5.09 %
~9 N N- met~ ,o-dichloro-acetamide _~ _ _ _ _ _ _ 39.27 g. of thionyl chloride are added, at 110C, to a stirred solution of 38.7 g. of dichloroacetic acid in 44.4 g. of dimethyl formamide.
The reaction mixture is maintained at 135C for 2 hours, thereafter it is diluted with 150 ml. of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillation. 38.9 g. ~83.1 %) of N,N-dimethyl~ -dichloro-acetamide are obtained; b.p.: 78-80C/1.5-2 mm Hg; nD5 = 1.4946.
_xample 10 ~ _-Dieth ~
39.27 g. of thionyl chloride are added, at 110 C, to a stirred solution of 38.7 g. of dichloroacetic acid in 60.0 gO of diethyl formamide.
e reaction mixture is maintained at 135C for 2 hours, thereafter it is , ~(94954~
diluted with 150 ml. of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillation. 44.6 g. (80.8 %) of the title compound are obtained; b.p.: 100 C/4 mm Hg, nD = 1.4930.
E~ æle 11 N,N-Diallyl-a,a-dichloro-acetamide 39.27 g. of thionyl chloride are added, at 110C, to a stirred solution of 38.7 g. of dichloroacetic acid in 75.0 g. of diallyl formamide.
The mixture is maintained at 135C for 2 hours, thereafter it is diluted with 150 mlO of water, and the pH of the mixture is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 100 ml. of chloroform, and the extract is subjected to fractional distillationO 31.2 g. ~52.8 %) of NJN-diallyl-a~a-dichlor acetamide are obtained; b.p.: 93C/2 mm Hg, nD5 = 1.5021.
le 12 N,N,N~,N'-Tetramethyl-adipic acid diamide 143.0 g. of thionyl chloride are added, at 110C, to a stirred solution of 73O0 g. of adipic acid in 146.0 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for 2 hours. The mixture is diluted with 300 ml. of water, and the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution. The aqueous-alkaline mixture is extracted with 4 x 150 mlO of chloroform, and the extract is subjected to fractional distillation. 57.0 g. (56.9 %) of the title compound are obtained; b.p.: 190-192C/4 mm Hg; m.p.: 79-79.5C.
Exam~le 13 N~N-Dimethyl-ca~ryli _ amide 26.18 g. of thionyl chloride are added, at 110C, to a stirred suluticn of 28.2 g. of caprylic acid in 29.6 g. of dimethyl formamide, and 3Q the mixture is maintained at 135 C for 1.5 hours. The mixture is diluted _g_ I
:
with 200 ml. of water, the pH of the solution is adjusted to 8 using aqueous sodium hydroxide solution, and the aqueous-alkaline mixture is extracted with 3 x 50 ml. of chloroform. The extract is subjected to fractional distillation to obtain 27.7 g. (8Q~8 %) of N,N-dimethyl-caprylic amide; b.p.: 119-122C/60 mm Hg.
Analysis:
calculated: C: 70.12 % H: 12.36 % N: 8.18 %
found: C: 70.40 % H: 12.35 % N: 8.29 %
Ex~ple _14 ~N ___ ethyl-oleic a~ide 13.08 g. of thionyl chloride are added, at 110C, to a stirred solution of 28.2 g. of oleic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for 1.5 hours. The mixture is diluted with 100 ml. of water, and its pH is adjusted to 8 with aqueous sodium hydroxide solution. The aqueous-alkaline solution is extracted with 3 x 50 ml. of chloroform, and the extract is subjected to fractional distillation. 26.0 g. (84.0 %) of N,N-dimethyl-oleic amide are obtained;
n2D0 = 1.4644, m.p.: -8.5 C.
Example _15 2Q N,N-Dimethyl-benzoic amide ; 3~o27 g. of thionyl chloride are added~ at 110C, to a stirred solution o 36.6 g. of benzoic acid in 43.8 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for 3 hours. The mixture is diluted with 150 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline solution is extracted with `~ 3 x 80 ml. of chloroform. The extract is subjected to fractional distillation to obtain 36.1 g. (80.7 %) of N,N-dimethyl-benzoic amide; b~po 150-160C/35 mm Hg.
Analysis:
3Q calculated; C: 72.46 % H: 7.43 % N: 9.39 %
fo~nd: C: 72.36 % H: 7.47 % N: 9.38 %
'~' . , ' ' : ' ~ . : .
~ ' ' :, , ' . '' - . ' ' ':;.
~IL954~ :
Exam~l _ 16 N,N-Dimethyl-l-n~ yl-amide 13008 gO of thionyl chloride are added, at 110C, to a stirred solution of 17.2 g. of a naphthoic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for one hour. The mixture is diluted with 100 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline solution is extracted with 3 x 40 ml. of chloroform. The extract is subjected to fractional distillation to obtain 17.9 g. ~89.8 %~ of the title compound; b.p.: 134-136C/0.15 mm Hg; m.p.:
61-62C.
N N-Di-~tA~
13.08 g. of thionyl chloride are added, at 110C, to a stirred solution of 11.2 g. of a-furanecarboxylic acid in 14.6 g. of dimethyl formamide, and the mixture is maintained at 135C for 1.5 hours. Thereafter the mixture is diluted with 150 ml. of water, its pH is adjusted to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline mixture is extracted with 3 x 50 mlO of chloroform. The extract is dried, the solvent is evaporated, and the residue is triturated with petroleum ether. 11.5 g.
2Q (82.6 %) of the title compound are obtained; m.p.: 43-45C.
Analysis: -~; calculated: C: 60.41 % H: 6.52 % N: 10.07 %
found: C: 60.40 % H: 6.39 % N 10.15 %
Exam~le 18 N-Dimethyl-2-chloro-nicotinic amide 26.2 g~ of thionyl chloride are added, at 110C, to a stirred i solution of 31.5 g. of 2-chloro-nicotinic acid in 29.2 g. of dimethyl formamide, and the mixture is maintained at 130 to 135C for one hour.
Thereafter the mixture is diluted with 150 ml. of water, its p~ is adjusted 3Q to 8 with aqueous sodium hydroxide solution, and the aqueous-alkaline `:`
' . ~ , .
. . .
.. , ,, ,, . , . . :
: `--954~L
mixture is extracted ~ith 3 x 100 ml. of chloroform. The extract is subjected to fractional distillation to obtain 28.0 g. ~75.6 %) of the title compound;
b.p.: 162-164 C/4 mm Hg; m.p.: 68-69C.
Example 19 N N- e~y~ _ ic inic amide ___ A suspension of 61.5 g. of nicotinic acid in 73.0 g. of dimethyl formamide is heated to 110C, and 71.5 g. of thionyl chloride are added with stirring to the obtained homogeneous solution. The mixture is maintained at 130 to 135C for 2 hours, thereafter it is diluted with 200 ml. of water, la and the pH of the mixture is adjusted to 8 with aqueous sodium hydroxide solution. The mixture is extracted with 3 x 200 ml. of chloroform, and the extract is subjected to fractional distillation. 52.5 g. ~69.9 %) of the title compound are obtained; b.p.: 162-165C/12 mm Hg, m.p.: 44-45C.
le 20 NJN-Dimethyl-cinnamic amide _ ___ _ ~
26.2 g. of thionyl chloride are added, at 110C, to a stirred solution of 29.6 g. of cinnamic acid in 29.2 g. of dimethyl formamide, and the mixture is maintained at 135 to 140C for one hour. The reaction mixture is poured into 200 ml. of water, and the pH of the obtained mixture 2a is adjusted to 8 using aqueous sodium hydroxide solution. The separated substance is filtered off, washed with water, and dried. 30.6 g. ~87.3 %) of the title compound are obtained; m.p.: 95-97C.
Analysis:
calculated: C: 75.40 % H: 7.48 % N: 7.99 %
found: C: 75.47 % H: 7.50 % N: 7.93 %
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of N,N-disubstituted carboxylic amides having the general formula (III), (III) wherein R1 and R2 each represent an aliphatic hydrocarbyl group, or R1 and R2, together with the adjacent nitrogen atom, form a heterocyclic group containing optionally further hetero atom(s), and R3 is an aliphatic, aromatic, araliphat-ic or cycloaliphatic hydrocarbyl group or a saturated or aromatic heterocyclic group, all of them optionally substituted by one or more halogen atoms and/or by a -CONR1R2 group, in which a compound of the general formula (IV), (IV) wherein R3 has the same meanings as defined above, is reacted, at a temperature not exceeding the boiling point of the reaction mixture, with an adduct of the general formula (I) or (II), (R1R2N - CHO - X)+ C1- (I) (R1R2N = CHC1)+ C1- (II) wherein R1 and R2 each have the same meanings as defined above and X is a group of the formula -SOC1, -POC12, -PC14, -PC12, -CO-CO-C1 or -CO-C1, said adducts being prepared by mixing a compound of the general formula HCONR1R2 (wherein R1 and R2 each have the same meanings as defined above) with at least equimolar amount of thionyl chloride, phosphorous oxychloride, phosphorous pentachloride, posphorous trichloride, oxalyl chloride or phosgene, and the obtained product of the general formula (III) is isolated from the reaction mixture.
2. A process as claimed in claim l, in which a compound of the general formula (IV), wherein R3 has the same meanings as defined in claim I
is reacted with a pre-formed adduct of the general formula (I) or (II), wherein R1, R2 and X each have the same meanings as defined in claim 1.
is reacted with a pre-formed adduct of the general formula (I) or (II), wherein R1, R2 and X each have the same meanings as defined in claim 1.
3. A process as claimed in claim 1, in which the adduct of the general formula (I) or (II), wherein R1, R2 and X each have the same meanings as defined in claim 1, is prepared in the presence of an acid derivative having the general formula (IV), wherein R3 has the same meanings as defined in claim 1.
4. A process as claimed in claim 1, in which the reaction is performed at a temperature not exceeding 150°C.
5. A process as claimed in claim 4, in which the reaction is performed at a temperature between 100 and 150°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HURI549A HU169760B (en) | 1974-10-07 | 1974-10-07 | Process for producing amides of carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049541A true CA1049541A (en) | 1979-02-27 |
Family
ID=11000960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA237,128A Expired CA1049541A (en) | 1974-10-07 | 1975-10-06 | Process for the preparation of carboxylic amides |
Country Status (10)
| Country | Link |
|---|---|
| CA (1) | CA1049541A (en) |
| CS (1) | CS193526B2 (en) |
| DD (1) | DD123454A5 (en) |
| ES (1) | ES441547A1 (en) |
| GB (1) | GB1521997A (en) |
| HU (1) | HU169760B (en) |
| IT (1) | IT1044638B (en) |
| NL (1) | NL7511771A (en) |
| PL (1) | PL98547B1 (en) |
| RO (1) | RO72874A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721873A (en) * | 2017-11-14 | 2018-02-23 | 湖北工业大学 | The preparation method of N, N dimethyl benzamide |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0462639A1 (en) * | 1990-06-05 | 1991-12-27 | Shell Internationale Researchmaatschappij B.V. | Preparation of 2-chloropyridine derivatives |
| CH697575B1 (en) | 2004-09-23 | 2008-12-15 | Ramachandran Radhakrishnan | A method of producing fatty acid amides substituted by N, N-dialkyl. |
| CN111320553A (en) * | 2018-12-17 | 2020-06-23 | 潘伟 | N, N-dimethyl benzamide purification device |
-
1974
- 1974-10-07 HU HURI549A patent/HU169760B/en unknown
-
1975
- 1975-10-03 CS CS671375A patent/CS193526B2/en unknown
- 1975-10-06 PL PL18380375A patent/PL98547B1/en unknown
- 1975-10-06 CA CA237,128A patent/CA1049541A/en not_active Expired
- 1975-10-07 IT IT2804175A patent/IT1044638B/en active
- 1975-10-07 ES ES441547A patent/ES441547A1/en not_active Expired
- 1975-10-07 RO RO7583540A patent/RO72874A/en unknown
- 1975-10-07 GB GB4104975A patent/GB1521997A/en not_active Expired
- 1975-10-07 NL NL7511771A patent/NL7511771A/en not_active Application Discontinuation
- 1975-10-08 DD DD18874575A patent/DD123454A5/xx unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721873A (en) * | 2017-11-14 | 2018-02-23 | 湖北工业大学 | The preparation method of N, N dimethyl benzamide |
| CN107721873B (en) * | 2017-11-14 | 2020-04-07 | 湖北工业大学 | Preparation method of N, N-dimethyl benzamide |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7511771A (en) | 1976-04-09 |
| GB1521997A (en) | 1978-08-23 |
| CS193526B2 (en) | 1979-10-31 |
| PL98547B1 (en) | 1978-05-31 |
| HU169760B (en) | 1977-01-28 |
| IT1044638B (en) | 1980-04-21 |
| DD123454A5 (en) | 1976-12-20 |
| RO72874A (en) | 1981-08-17 |
| ES441547A1 (en) | 1977-03-16 |
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