CA1073467A - Process for the production of diols and n,n-dialkyl carboxylic acid amides - Google Patents
Process for the production of diols and n,n-dialkyl carboxylic acid amidesInfo
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- CA1073467A CA1073467A CA241,880A CA241880A CA1073467A CA 1073467 A CA1073467 A CA 1073467A CA 241880 A CA241880 A CA 241880A CA 1073467 A CA1073467 A CA 1073467A
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- butanediol
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Abstract
Abstract of the Disclosure A process for producing diols and N,N-dialkyl carboxylic acid amides which comprises reacting diol carboxylic acid esters with dialkyl amines in the presence of lower alkanol and a transesterification-aminolysis catalyst.
Description
10"~3~6~;~
This invention relates to a process for producing diols and N,N-dialkyl carboxylic acid amides which comprises reacting carboxylic acid esters with dialkyl amines in the presence of a lower alkanol and a trans-esterification-aminolysis catalyst.
BACKGROUND OF THE INVENTION
The reaction of amines and esters to produce amides and alcohols has long been known. The practical applicability of this kind of process is somewhat restricted in scope, however. In particular, the reaction of secondary amines with esters derived from higher alcohols to produce the corresponding amides and the alcohols is not a facile process under ordinary conditions, and other methods are generally practiced. In production of N,N-dimethylacetamide, for example, dimethylamine and acetic acid are combined under conditions of elevated temperature and pressure as disclosed in U.S. Patents 2,667,511 and 3,006,956. Acetic anhydride may also be employed as the acylating agent as shown in U.S. Patent 3,006,956. In more recently described methods, N,N-dimethylacetamide is prepared from trimethyl- ~ -amine and carbon monoxide in the presence of a cobalt carbonyl catalyst as described in U.S. Patent 3,407,231, or by reaction of dimethylamine and ketene as disclosed in U.S.S.R. Patent 183,731.
N,N-dimethylacetamide has been produced in relatively low yield by reaction of dimethylamine and polyvinyl acetate in methanol solvent in absence of added catalyst as shown in U.S. Patent 3,197,450. N,N-dimethyl- -acetamide has also been produced by reaction of aqueous dimethylamine with allyl acetate or vinyl acetate as described in Netherlands Application 6,602,128. In the latter process, a substantial amount of acetic acid by-product is also formed.
N,N-dialkyl carboxylic acid amides have found important utility.
N,N-dimethylacetamide and N,N-dimethylformamide in particular are widely used in spinning of fibers and in other solvent applications.
-1- ~ -' ' ~ ~. - - . ' , , ' , ,, -: : . . -.
1073~67 Diols also constitute a class of valuable compounds. They have wide utility in manufacture of polyesters and polyurethanes and as solvents and synthetic intermediates. There are a number of methods known in the art by which diol esters may be converted to these more useful diols.
Aqueous base hydrolysis is unacceptable in that it involves the formation of salts which must be treated for recovery of their valuable components.
With esters of 1,4-butanediol especially, acidic conditions can be employed ;only with severe restrictionsj so as to avoid the cyclization reaction producing tetrahydrofuran.
In Canadian applications of Will Dockery Merritt, Jr., Ser.
No. 196,825, dated April 4, 1974, and John E. Corn et al, Ser.
No. 209,309 dated September 16, 1974, both assigned to the same assignee as this invention, processes involving alcoholysis of diol esters promoted by alkali metal hydroxides and acidic ion exchange resins, respectively, are disclosed. In a Canadian application of William Edward Smith, Serial No.
217,507 dated Jan/7/1975, and assigned to the same assignee -~
as this invention, the vapor phase alcoholysis of diol esters over magnesia catalysts is described.
DESCRIPTION OF THE INVENTION -~
It has been discovered that diols and N,N-dialkyl carboxylic ~ ~ -acid amides can be obtained from the corresponding carboxylic acid esters -~ -and dialkyl amines by a highly efficient method which involves the use of a lower alkanol mediating agent and a transesterification-aminolysis catalyst.
This invention has been found particularly useful for simultaneously producing diols and N,N-dimethyl carboxylic acid amides from the corresponding diol esters. In this case especially methanol solvent and a basic catalyst (such as sodium hydroxide) serve to bring about rapid reaction under mild conditions, -affording the desired products in excellent yield and to the virtually com-plete exclusion of any by-products. mè term "diol esters" refers to ~Oq346~
particular diol esters and mixtures of diol esters as well. The term is also meant to include both mono- and di-ester derivatives of diols.
The process is illustrated for the case of production of 1,4-butanediol and N,N-dimethylacetamide from 4-acetoxybutanol and dimethylamine in equation (1): -(1) , ,~ base catalyst ,.
HO(CH2)4 C CH3 + (CH3) NH ~ HO(CH2)4 OH ~ Me2 N C CH3 The process may be employed for conversion of a wide variety of diol carboxylic acid esters including aliphatic, cycloaliphatic and aromatic diol esters. Preferrably these are aliphatic diol esters. Most preferred ~
diol esters include acetates and formates of 1,4-butanediol, 2-methyl-1,3- -propanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol, ethylene gly-col, 1,6-hexanediol, 1,5-pentanediol, 2-methyl-1,4-butanediol and 1,4-di(hydro-xymethyl) cyclohexane. The method is particularly applicable to production of a mixture of 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol from a mixture of the corresponding acetate esters.
The dialkyl amines included within the scope of this invention are those wherein each alkyl group contains from 1 to 4 carbon atoms.
The lower alkanols that may be employed in this invention are those which contain one to six carbon atoms. The preferred alkanol is methanol. ~~
Since the lower alkanol is not consumed in the reaction, it may be used in amounts that vary widely. It may be used as the solvent or, alternatively, in amounts as small as one equivalent or less.
The transesterification-aminolysis catalysts that may be used within the scope of this invention are bases that are known in the art to promote transesterification reactions. These include alkali metal and .. , ~
1073~6q alkaline earth metal hydroxides, alkoxides and carboxylates, examples of which are sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium methoxide and lithium acetate. Strongly basic ion exchange resins may also be employed as catalyst; resins bearing the quaternary ammonium hydroxide function are very effective.
The temperature at which the process can be carried out varies widely and is not critical. Temperatures from room temperature to about 225C are found suitable. A preferred temperature range is from about 60C to about 180C.
A wide range of pressure may be used within the scope of this in-vention since pressure is not critical. Preferred pressure ranges are those that are required to contain the dialkyl amine at the operating tempera-ture.
The actual course by which this transformation proceeds is illustrated in equations 2 and 3 for the case of production of 1,4-butanediol and N,N-dimethylacetamide from 4-acetoxybutanol and dimethylamine in the presence of methanol and a basic catalyst. me net conversion is shown in equation 4. -
This invention relates to a process for producing diols and N,N-dialkyl carboxylic acid amides which comprises reacting carboxylic acid esters with dialkyl amines in the presence of a lower alkanol and a trans-esterification-aminolysis catalyst.
BACKGROUND OF THE INVENTION
The reaction of amines and esters to produce amides and alcohols has long been known. The practical applicability of this kind of process is somewhat restricted in scope, however. In particular, the reaction of secondary amines with esters derived from higher alcohols to produce the corresponding amides and the alcohols is not a facile process under ordinary conditions, and other methods are generally practiced. In production of N,N-dimethylacetamide, for example, dimethylamine and acetic acid are combined under conditions of elevated temperature and pressure as disclosed in U.S. Patents 2,667,511 and 3,006,956. Acetic anhydride may also be employed as the acylating agent as shown in U.S. Patent 3,006,956. In more recently described methods, N,N-dimethylacetamide is prepared from trimethyl- ~ -amine and carbon monoxide in the presence of a cobalt carbonyl catalyst as described in U.S. Patent 3,407,231, or by reaction of dimethylamine and ketene as disclosed in U.S.S.R. Patent 183,731.
N,N-dimethylacetamide has been produced in relatively low yield by reaction of dimethylamine and polyvinyl acetate in methanol solvent in absence of added catalyst as shown in U.S. Patent 3,197,450. N,N-dimethyl- -acetamide has also been produced by reaction of aqueous dimethylamine with allyl acetate or vinyl acetate as described in Netherlands Application 6,602,128. In the latter process, a substantial amount of acetic acid by-product is also formed.
N,N-dialkyl carboxylic acid amides have found important utility.
N,N-dimethylacetamide and N,N-dimethylformamide in particular are widely used in spinning of fibers and in other solvent applications.
-1- ~ -' ' ~ ~. - - . ' , , ' , ,, -: : . . -.
1073~67 Diols also constitute a class of valuable compounds. They have wide utility in manufacture of polyesters and polyurethanes and as solvents and synthetic intermediates. There are a number of methods known in the art by which diol esters may be converted to these more useful diols.
Aqueous base hydrolysis is unacceptable in that it involves the formation of salts which must be treated for recovery of their valuable components.
With esters of 1,4-butanediol especially, acidic conditions can be employed ;only with severe restrictionsj so as to avoid the cyclization reaction producing tetrahydrofuran.
In Canadian applications of Will Dockery Merritt, Jr., Ser.
No. 196,825, dated April 4, 1974, and John E. Corn et al, Ser.
No. 209,309 dated September 16, 1974, both assigned to the same assignee as this invention, processes involving alcoholysis of diol esters promoted by alkali metal hydroxides and acidic ion exchange resins, respectively, are disclosed. In a Canadian application of William Edward Smith, Serial No.
217,507 dated Jan/7/1975, and assigned to the same assignee -~
as this invention, the vapor phase alcoholysis of diol esters over magnesia catalysts is described.
DESCRIPTION OF THE INVENTION -~
It has been discovered that diols and N,N-dialkyl carboxylic ~ ~ -acid amides can be obtained from the corresponding carboxylic acid esters -~ -and dialkyl amines by a highly efficient method which involves the use of a lower alkanol mediating agent and a transesterification-aminolysis catalyst.
This invention has been found particularly useful for simultaneously producing diols and N,N-dimethyl carboxylic acid amides from the corresponding diol esters. In this case especially methanol solvent and a basic catalyst (such as sodium hydroxide) serve to bring about rapid reaction under mild conditions, -affording the desired products in excellent yield and to the virtually com-plete exclusion of any by-products. mè term "diol esters" refers to ~Oq346~
particular diol esters and mixtures of diol esters as well. The term is also meant to include both mono- and di-ester derivatives of diols.
The process is illustrated for the case of production of 1,4-butanediol and N,N-dimethylacetamide from 4-acetoxybutanol and dimethylamine in equation (1): -(1) , ,~ base catalyst ,.
HO(CH2)4 C CH3 + (CH3) NH ~ HO(CH2)4 OH ~ Me2 N C CH3 The process may be employed for conversion of a wide variety of diol carboxylic acid esters including aliphatic, cycloaliphatic and aromatic diol esters. Preferrably these are aliphatic diol esters. Most preferred ~
diol esters include acetates and formates of 1,4-butanediol, 2-methyl-1,3- -propanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol, ethylene gly-col, 1,6-hexanediol, 1,5-pentanediol, 2-methyl-1,4-butanediol and 1,4-di(hydro-xymethyl) cyclohexane. The method is particularly applicable to production of a mixture of 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol from a mixture of the corresponding acetate esters.
The dialkyl amines included within the scope of this invention are those wherein each alkyl group contains from 1 to 4 carbon atoms.
The lower alkanols that may be employed in this invention are those which contain one to six carbon atoms. The preferred alkanol is methanol. ~~
Since the lower alkanol is not consumed in the reaction, it may be used in amounts that vary widely. It may be used as the solvent or, alternatively, in amounts as small as one equivalent or less.
The transesterification-aminolysis catalysts that may be used within the scope of this invention are bases that are known in the art to promote transesterification reactions. These include alkali metal and .. , ~
1073~6q alkaline earth metal hydroxides, alkoxides and carboxylates, examples of which are sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium methoxide and lithium acetate. Strongly basic ion exchange resins may also be employed as catalyst; resins bearing the quaternary ammonium hydroxide function are very effective.
The temperature at which the process can be carried out varies widely and is not critical. Temperatures from room temperature to about 225C are found suitable. A preferred temperature range is from about 60C to about 180C.
A wide range of pressure may be used within the scope of this in-vention since pressure is not critical. Preferred pressure ranges are those that are required to contain the dialkyl amine at the operating tempera-ture.
The actual course by which this transformation proceeds is illustrated in equations 2 and 3 for the case of production of 1,4-butanediol and N,N-dimethylacetamide from 4-acetoxybutanol and dimethylamine in the presence of methanol and a basic catalyst. me net conversion is shown in equation 4. -
(2) " OH O .
HO(CH2)4 0 C CH3 + CH30H - ~ Ho(cH2)4oH + CH3 0 C CH3
HO(CH2)4 0 C CH3 + CH30H - ~ Ho(cH2)4oH + CH3 0 C CH3
(3) 0 .. -OH ..
CH3 0 C CH3 + (CH3)2NH > CH30H + (CH3)2 N C 3
CH3 0 C CH3 + (CH3)2NH > CH30H + (CH3)2 N C 3
(4) ~; -O O
20HO(CH2)4 0 C CH3 + (CH3)2 NH HO(CH2)4 OH + (CH3)2 N C C 3 As indicated, the methanol participates in the process by entering into a transesterification reaction with the ester starting material. me methyl acetate produced is a more efficient acylating agent than the diol esteri under the process conditions, it readily combines with dimethylamine 10~3~6q to form N,N-dimethylacetamide with regeneration of the methanol. (This reaction course was observed experimentally using gas-liquid partition chromotography (glpc) analysis.) Both the transesterification and aminolysis reactions are accelerated by the catalyst.
An important feature of this method is the facility with which the complete conversion of the diol ester to the diol is accomplished. The purification of that product is accordingly made considerably easier. Any incompletely converted lower alkanol carboxylate intermediate (for example, methyl acetate as in equations 1 and 2) can be recycled with the excess ,~
amine and lower alkanol, and can in that way be ultimately used in the amide formation.
The process can be efficiently carried out by heating the combined ester, amine, alkanol and catalyst in an autoclave until a satisfactory conversion to the diol and amide is attained. me products can be isolated by distillation, with recycle of the alkanol (and unconverted lower alkanol carboxylate as mentioned supra) to the reaction vessel. The catalyst can be recycled in the distillation residue.
PREFERRED EMBODIMENT OF THE INVENTION
The following examples are set forth to illustrate more clearly the principle and practice of this invention to those skilled in the art. -Unless otherwise specified, where parts or percents are mentioned, they are parts or percents by weight.
EXAMPLE I -Dimethylamine gas was bubbled into a solution of 25.0 grams of 1,4-butanediol diacetate in 100 ml of methanol. When about 15 grams had been absorbed, 0.5 grams of sodium hydroxide was added. The mixture warmed spontaneously; analysis by glpc within three minutes showed that the diace-tate had already reacted with the solvent to produce an equilibrium mixture of methyl acetate, butanediol and the monoacetate, with but a small amount ,: . , ~ 8CH-1993 1073~67 of residual diacetate. A small amount of N,N-dimethylacetamide had also appeared.
The mixture was heated at reflux (50C) for one hour while more of the amine was bubbled in (total of about 50 grams). During this time, the acetates were consumed and the diol and amide were produced as the exclusive products. Direct quantitative glpc analysis of the mixture (chlorobenzene as added internal standard) at that point revealed the presence of 12.9 grams of 1,4-butanediol (100% yield) and 25.1 grams of N,N-dimethylacetamide (100% yield). -EXAMPLE II
A solution of 25.0 grams of 1,4-butanediol diacetate and 100 ml :
of methanol was saturated with dimethylamine gas, then treated with 0.5 grams of sodium methoxide. The mixture was examined by glpc within a minute of the catalyst addition and was found to be more than halfway converted r ` 15 to the equilibrated methyl acetate-diol monoacetate-diol diacetate mixture.
It was heated at reflux while dimethylamine was slowly added. After three - -hours at 60C, the solution was cooled and subjected to quantitative glpc - analysis, which revealed the presence of 12.2 grams of 1,4-butanediol (95%
yield) and 19.6 grams of N,N-dimethylacetamide (78% yield). Distillation -~ -afforded the isolated products for spectral comparison with authentic ~ -samples.
EXAMPLE III
A solution of 9.0 grams of dimethylamine in 43.0 grams of methanol -~
was combined in a "Vitro 400" pressure bot.le with 0.3 grams of potassium hydroxide and 10.0 grams of crude butanediol acetate obtained from allyl acetate via the oxo process (containing, as determined by glpc analysis of a completely acetylated sample, 60 m mols of 1,4-butanediol derivatives, c 3.9 m ls of 2-methyl-1,3-propanediol derivatives and 9.6 m mols of 1,2-~ 8CH -1993 10~346~
butanediol derivatives). The mixture was heated at 85C for 30 minutes, then cooled and subjected to glpc analysis. me essentially complete con-version to N,N-dimethylacetamide and the diols (1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol are indicated.
S EXAMPLE IV
A mixture of 7.3 grams of ethylene glycol diacetate, 9.0 grams of dimethylamine, 44.7 grams of methanol and 0.2 grams of sodium hydroxide was heated in a pressure bottle at 110-130C for one hour. me product mixture was cooled and subjected to quantitative glpc analysis, which indicated the presence of 2.8 grams of ethylene glycol (90% yield), 6.6 -~
grams of N,N-dimethylacetamide (76% yield) and 1.8 grams of methyl acetate (24% yield). On the basis of 76% conversion of the methyl acetate inter- - -mediate, the yield of N,N-dimethylacetamide was 100~.
EXAMPLE V
A mixture of 7.4 grams of 1,4-butenediol diacetate, 9.0 grams of dimethylamine, 44.7 grams of methanol and 0.2 grams of sodium hydroxide was heated in a pressure bottle at 150C for two hours. The product solution was cooled and subjected to quantitative glpc analysis, which indicated the presence of 7.1 grams of N,N-dimethylacetamide (96% yield) and 1.7 grams of 1,4-butenediol (45% yield).
EXAMPLE VI
A mixture of 8.7 grams of 1,4-butanediol diacetate, 9.0 grams of dimethylamine, 43.0 grams of methanol and 0.5 grams of lithium acetate dihydrate was heated at 140C for 20 minutes in a pressure bottle, then cooled `
and subjected to glpc analysis. The substantial conversion to 1,4-butanediol and N,N-dimethylacetamide was indicated.
~. .
EXAMPLE VII
A mixture of 11.8 grams of ethylene glycol diformate, 13.0 grams of dimethylamine, 23.4 grams of methanol and 5.0 grams of Rexyn~ 201 basic + --ion exchange resin (R4N OH form) was stirred at 25C for 30 minutes.
20HO(CH2)4 0 C CH3 + (CH3)2 NH HO(CH2)4 OH + (CH3)2 N C C 3 As indicated, the methanol participates in the process by entering into a transesterification reaction with the ester starting material. me methyl acetate produced is a more efficient acylating agent than the diol esteri under the process conditions, it readily combines with dimethylamine 10~3~6q to form N,N-dimethylacetamide with regeneration of the methanol. (This reaction course was observed experimentally using gas-liquid partition chromotography (glpc) analysis.) Both the transesterification and aminolysis reactions are accelerated by the catalyst.
An important feature of this method is the facility with which the complete conversion of the diol ester to the diol is accomplished. The purification of that product is accordingly made considerably easier. Any incompletely converted lower alkanol carboxylate intermediate (for example, methyl acetate as in equations 1 and 2) can be recycled with the excess ,~
amine and lower alkanol, and can in that way be ultimately used in the amide formation.
The process can be efficiently carried out by heating the combined ester, amine, alkanol and catalyst in an autoclave until a satisfactory conversion to the diol and amide is attained. me products can be isolated by distillation, with recycle of the alkanol (and unconverted lower alkanol carboxylate as mentioned supra) to the reaction vessel. The catalyst can be recycled in the distillation residue.
PREFERRED EMBODIMENT OF THE INVENTION
The following examples are set forth to illustrate more clearly the principle and practice of this invention to those skilled in the art. -Unless otherwise specified, where parts or percents are mentioned, they are parts or percents by weight.
EXAMPLE I -Dimethylamine gas was bubbled into a solution of 25.0 grams of 1,4-butanediol diacetate in 100 ml of methanol. When about 15 grams had been absorbed, 0.5 grams of sodium hydroxide was added. The mixture warmed spontaneously; analysis by glpc within three minutes showed that the diace-tate had already reacted with the solvent to produce an equilibrium mixture of methyl acetate, butanediol and the monoacetate, with but a small amount ,: . , ~ 8CH-1993 1073~67 of residual diacetate. A small amount of N,N-dimethylacetamide had also appeared.
The mixture was heated at reflux (50C) for one hour while more of the amine was bubbled in (total of about 50 grams). During this time, the acetates were consumed and the diol and amide were produced as the exclusive products. Direct quantitative glpc analysis of the mixture (chlorobenzene as added internal standard) at that point revealed the presence of 12.9 grams of 1,4-butanediol (100% yield) and 25.1 grams of N,N-dimethylacetamide (100% yield). -EXAMPLE II
A solution of 25.0 grams of 1,4-butanediol diacetate and 100 ml :
of methanol was saturated with dimethylamine gas, then treated with 0.5 grams of sodium methoxide. The mixture was examined by glpc within a minute of the catalyst addition and was found to be more than halfway converted r ` 15 to the equilibrated methyl acetate-diol monoacetate-diol diacetate mixture.
It was heated at reflux while dimethylamine was slowly added. After three - -hours at 60C, the solution was cooled and subjected to quantitative glpc - analysis, which revealed the presence of 12.2 grams of 1,4-butanediol (95%
yield) and 19.6 grams of N,N-dimethylacetamide (78% yield). Distillation -~ -afforded the isolated products for spectral comparison with authentic ~ -samples.
EXAMPLE III
A solution of 9.0 grams of dimethylamine in 43.0 grams of methanol -~
was combined in a "Vitro 400" pressure bot.le with 0.3 grams of potassium hydroxide and 10.0 grams of crude butanediol acetate obtained from allyl acetate via the oxo process (containing, as determined by glpc analysis of a completely acetylated sample, 60 m mols of 1,4-butanediol derivatives, c 3.9 m ls of 2-methyl-1,3-propanediol derivatives and 9.6 m mols of 1,2-~ 8CH -1993 10~346~
butanediol derivatives). The mixture was heated at 85C for 30 minutes, then cooled and subjected to glpc analysis. me essentially complete con-version to N,N-dimethylacetamide and the diols (1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol are indicated.
S EXAMPLE IV
A mixture of 7.3 grams of ethylene glycol diacetate, 9.0 grams of dimethylamine, 44.7 grams of methanol and 0.2 grams of sodium hydroxide was heated in a pressure bottle at 110-130C for one hour. me product mixture was cooled and subjected to quantitative glpc analysis, which indicated the presence of 2.8 grams of ethylene glycol (90% yield), 6.6 -~
grams of N,N-dimethylacetamide (76% yield) and 1.8 grams of methyl acetate (24% yield). On the basis of 76% conversion of the methyl acetate inter- - -mediate, the yield of N,N-dimethylacetamide was 100~.
EXAMPLE V
A mixture of 7.4 grams of 1,4-butenediol diacetate, 9.0 grams of dimethylamine, 44.7 grams of methanol and 0.2 grams of sodium hydroxide was heated in a pressure bottle at 150C for two hours. The product solution was cooled and subjected to quantitative glpc analysis, which indicated the presence of 7.1 grams of N,N-dimethylacetamide (96% yield) and 1.7 grams of 1,4-butenediol (45% yield).
EXAMPLE VI
A mixture of 8.7 grams of 1,4-butanediol diacetate, 9.0 grams of dimethylamine, 43.0 grams of methanol and 0.5 grams of lithium acetate dihydrate was heated at 140C for 20 minutes in a pressure bottle, then cooled `
and subjected to glpc analysis. The substantial conversion to 1,4-butanediol and N,N-dimethylacetamide was indicated.
~. .
EXAMPLE VII
A mixture of 11.8 grams of ethylene glycol diformate, 13.0 grams of dimethylamine, 23.4 grams of methanol and 5.0 grams of Rexyn~ 201 basic + --ion exchange resin (R4N OH form) was stirred at 25C for 30 minutes.
5 Analysis of the supernatant liquid showed that complete conversion to ethylene glycol and N,N-dimethylformamide had been effected in that time.
A quantitative analysis showed the presence of 5.7 grams of ethylene glycol (92% yield) and 13.9 grams of N,N-dimethylformamide (95% yield). A trace of methyl formate was also detected. -~ -EXAMPLE VIII
This example is included to show that the base catalyst promotes - :~
the aminolysis as well as the transesterification reaction in this process.
A mixture of 7.4 grams of methyl acetate, 9.0 grams of dimethylamine ;;
and 43.0 grams of methanol was stirred at 25C. After one hour, no N,N-dimethylacetamide could be detected. At that point, 0.3 grams of sodium hydroxide was added. Within minutes the presence of the amide was evident (glpc analysis). After two hours, the reaction was about 80% complete.
After 16 hours, no residual methyl acetate was detected; the conversion to N,N-dimethylacetamide was complete. -It will thus be seen that the objects set forth above among those ~- ~ made apparent from the preceding description are efficiently attained and since certain changes may be made in carrying out the above process and in the composition set forth without departing from the scope of this invention, it is intended that all matters contained in the above description shall be interpreted as illustrative and not in a limiting sense.
. . . . . . . . . . .
. . . ~ .
A quantitative analysis showed the presence of 5.7 grams of ethylene glycol (92% yield) and 13.9 grams of N,N-dimethylformamide (95% yield). A trace of methyl formate was also detected. -~ -EXAMPLE VIII
This example is included to show that the base catalyst promotes - :~
the aminolysis as well as the transesterification reaction in this process.
A mixture of 7.4 grams of methyl acetate, 9.0 grams of dimethylamine ;;
and 43.0 grams of methanol was stirred at 25C. After one hour, no N,N-dimethylacetamide could be detected. At that point, 0.3 grams of sodium hydroxide was added. Within minutes the presence of the amide was evident (glpc analysis). After two hours, the reaction was about 80% complete.
After 16 hours, no residual methyl acetate was detected; the conversion to N,N-dimethylacetamide was complete. -It will thus be seen that the objects set forth above among those ~- ~ made apparent from the preceding description are efficiently attained and since certain changes may be made in carrying out the above process and in the composition set forth without departing from the scope of this invention, it is intended that all matters contained in the above description shall be interpreted as illustrative and not in a limiting sense.
. . . . . . . . . . .
. . . ~ .
Claims (9)
1. A process for producing diols and N,N-dialkyl carboxylic acid amides which comprises reacting a diol carboxylic acid ester selected from the group consisting of acetate esters and formate esters of aliphatic diols with dialkyl amines wherein each alkyl group contains 1 to 4 carbon atoms in the presence of a lower alkanol and a transesterification-aminolysis catalyst selected from the group consisting of the alkali and alkaline earth metal hydroxides, and carboxylates and strongly basic ion exchange resins.
2. The process of claim 1 wherein the diol carboxylic acid esters are selected from the group consisting of the acetates and formates of 1,4-butanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol and ethylene glycol.
3. The process of claim 1 wherein the dialkyl amine is dimethyl-amine.
4. The process of claim 1 wherein the lower alkanol is methanol.
5. The process of claim 1 wherein the transesterifica-tion-aminolysis catalyst is selected from the group consisting of the alkali and alkaline earth metal hydroxides, and carboxylates.
6. The process of claim 1 wherein the transesterifica-tion-aminolysis catalyst is a strongly basic ion exchange resin.
7. The process of claim 1 wherein the diol is a mixture of 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol.
8. A process for producing 1,4-butanediol and N,N-dimethylacetamide which comprises reacting 4-acetoxybutanol with dimethylamine in the presence of methanol and a transesterification-aminolysis catalyst selected from the group consisting of the alkali and alkaline earth metal hydroxides, and carboxylates.
9. A process for producing 1,4-butanediol and N,N-dimethylacetamide which comprises reacting a diol carboxylic acid ester selected from the group consisting of 1,4-butanediol diacetate and 4-acetoxybutanol with dimethylamine in the presence of methanol and a transesterification-aminolysis catalyst selected from the group consisting of the alkali and alkaline earth metal hydroxides, and carboxylates or a strongly basic ion exchange resin.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54085575A | 1975-01-14 | 1975-01-14 |
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| Publication Number | Publication Date |
|---|---|
| CA1073467A true CA1073467A (en) | 1980-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA241,880A Expired CA1073467A (en) | 1975-01-14 | 1975-12-11 | Process for the production of diols and n,n-dialkyl carboxylic acid amides |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8193390B2 (en) | 2004-12-06 | 2012-06-05 | Basf Se | Method for the production of N,N-dimethylacetamide (DMAC) |
| US8338644B2 (en) | 2004-12-06 | 2012-12-25 | Basf Se | Method for the production of N,N-dimethylacetamide (DMAC) |
-
1975
- 1975-12-11 CA CA241,880A patent/CA1073467A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8193390B2 (en) | 2004-12-06 | 2012-06-05 | Basf Se | Method for the production of N,N-dimethylacetamide (DMAC) |
| US8338644B2 (en) | 2004-12-06 | 2012-12-25 | Basf Se | Method for the production of N,N-dimethylacetamide (DMAC) |
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