CA1105486A - Process for the manufacture of glycolic acid esters - Google Patents
Process for the manufacture of glycolic acid estersInfo
- Publication number
- CA1105486A CA1105486A CA290,707A CA290707A CA1105486A CA 1105486 A CA1105486 A CA 1105486A CA 290707 A CA290707 A CA 290707A CA 1105486 A CA1105486 A CA 1105486A
- Authority
- CA
- Canada
- Prior art keywords
- glycolic acid
- acid esters
- manufacture
- acid ester
- formic acid
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE MANUFACTURE OF GLYCOLIC ACID ESTERS
Abstract of the disclosure:
Glycolic acid esters are prepared by reacting paraformal-dehyde or trioxane or a mixture thereof with a formic acid ester in the liquid phase at a temperature of from 70 to 200°C in the presence of a strongly acidic organic sulfonic acid catalyst.
Abstract of the disclosure:
Glycolic acid esters are prepared by reacting paraformal-dehyde or trioxane or a mixture thereof with a formic acid ester in the liquid phase at a temperature of from 70 to 200°C in the presence of a strongly acidic organic sulfonic acid catalyst.
Description
HOE 76/~ 264 ~ S9~36 This invention relates to a process for the manu~acture of glycolic acid esters from paraformaldehyde or trioxane and formic acid esters in the liquid phase.
It is known to react solutions of formaldehyde or its li-near and cyclic polymers (particularly paraformaldehyde and tri-oxane) with carbon mono~ide in the presence of alcohols to obtain glycolic acid esters. Because of the low reactivity of carbon monoxide, the reaction is generally carried out at a temperature of approximately 200C under a pressure of about 400 bars.
The high reaction pressure and the use of a gaseous reac-tion component which, especially with carbon mono~ide, requires considerable expenditure pèrtaining to apparatus, is an impor-tant technological and thus economic disadvantage of the known processes as compared to processes carried out in liquid phase which do not cause such problems.
The present invention provides a process for the manu~acture of glycolic acid esters which comprises reactin~ paraformalde-hyde or trioxane or a mixture thereof with formic acid esters in the liquid phase at a temperature of from 70 to 200C in the presence of an organic sulfonic acid catalyst.
Surprisingly, the process of the invention has decisive ad-vantages over the methods hitherto proposed. The use of ~ormic acid esters according to the invention allows of carr~ing out the process at atmospheric pressure or, iE the reaction i5 carri-ed out at a temperature above the boiliny point of the respec-tive formic acid ester, at a relatively low excess pressure or 20 to 30 bars. A still higher pressure OL 200 bars, for example, is also possible, but in general ir does not o~fer an~ advanta~e~
29 Hence, expensive investments necessary for a high pressure pro~
~S~136 cess are superfluous when, according to the invention, a formic acid ester,instead of carbon monoxide and an alcohol,is react-ed with paraformaldehyde or trioxane. Extensive safety measur-es as required in a process using carbon monoxide can also be dispensed with.
As catalysts there can be used, on principle, all strongly acidic or~c sulfonic acid ccmpounds as the velocity of the reaction (CH2O)n + n HCOOR n HO-CH2-COOR
distinctly depends on the acid strength of the catalyst.
Especially suitable organic sulfonic acids are p-toluene-sulfonic acid, benzene-sulfonic acid, ~- or B-naphthalene-sulfonic acid, methane-sulfonic acid, ethane-sulfonic acid, he~ane-sulfonic acicl, or trifluoromethane sulro-nic acid.
The amount of catalyst to be used can vary within wide li-mits, in general it ranges from 0.1 to 100 mol %t preferably 5 to 50 mol ~, calculated on the formic acid ester used.
The molar ratio of paraformaldehyde and/or trioxane (cal-culated on their formaldehyde content) to the respective forrn,ic acid ester is not critical~ Preferably, a ratio in the range of from 0.5 to 2 is chosen.
The reaction is carried out at a temperature of frorn 70 to 200C, preferably 90 to 1~0C.
In the process of the invention on principle `all formic zc esters HCOOR are suitable. Especially suitable radicals R are alkyl, cycloalkyl and alkaryl having up to 8 carbon atoms, for example methyl, ethyl, propyl, i-propyl, n-butyl, isobutyl, tert.butyl, cyclohe~yl, benzyl, n-octyl and 2-ethyl-hexyl.
29 To carry out the process of the invention the mlxture of .~ HOE 76/F 264 paraformaldehyde and/or trioxane, formic acid ester and catalyst is heated at atmospheric pressure or slight excess pressure.
At a reaction temperature a~ove the boiling point of the res-pective formic acid ester an excess pressure up to 50 bars prov-ed to be advantageous to prevent the ester from evaporating from the liquid phase. The presence of an inert gas, for exarnple nitrogen, is possible.
The process of the invention can be carried out in any ap-paratus suitable for reactions in the liquid phase with or with-out the appllcation of excess pressure, for example in an enamel-ed autoclave.
The reaction mixture can be worked up according to known methods, for example the glycolic acid ester formed is directly ~ distilled off from the reaction mixture.
Glycolic acid esters are used for many technologica1 appli-cations. By hydrolysis of the esters glycolic acid can be ol)-tained in very pure form.
~he hydrogenolysis of glycolic acid methyl ester is ~sed in industry to produce glycol. Glyco~ic acid n-butyl ester is a commercial varnish improving agent. Quite genera.l.l.y, glycs-lic acid e~sters are characterized by an excellent dissolving power for polymers, copolymers, nitrocellulose, cellulose ethers, cel.luloid, chlorinated rubber and resins.
The following examples illustrate the invention.
It is known to react solutions of formaldehyde or its li-near and cyclic polymers (particularly paraformaldehyde and tri-oxane) with carbon mono~ide in the presence of alcohols to obtain glycolic acid esters. Because of the low reactivity of carbon monoxide, the reaction is generally carried out at a temperature of approximately 200C under a pressure of about 400 bars.
The high reaction pressure and the use of a gaseous reac-tion component which, especially with carbon mono~ide, requires considerable expenditure pèrtaining to apparatus, is an impor-tant technological and thus economic disadvantage of the known processes as compared to processes carried out in liquid phase which do not cause such problems.
The present invention provides a process for the manu~acture of glycolic acid esters which comprises reactin~ paraformalde-hyde or trioxane or a mixture thereof with formic acid esters in the liquid phase at a temperature of from 70 to 200C in the presence of an organic sulfonic acid catalyst.
Surprisingly, the process of the invention has decisive ad-vantages over the methods hitherto proposed. The use of ~ormic acid esters according to the invention allows of carr~ing out the process at atmospheric pressure or, iE the reaction i5 carri-ed out at a temperature above the boiliny point of the respec-tive formic acid ester, at a relatively low excess pressure or 20 to 30 bars. A still higher pressure OL 200 bars, for example, is also possible, but in general ir does not o~fer an~ advanta~e~
29 Hence, expensive investments necessary for a high pressure pro~
~S~136 cess are superfluous when, according to the invention, a formic acid ester,instead of carbon monoxide and an alcohol,is react-ed with paraformaldehyde or trioxane. Extensive safety measur-es as required in a process using carbon monoxide can also be dispensed with.
As catalysts there can be used, on principle, all strongly acidic or~c sulfonic acid ccmpounds as the velocity of the reaction (CH2O)n + n HCOOR n HO-CH2-COOR
distinctly depends on the acid strength of the catalyst.
Especially suitable organic sulfonic acids are p-toluene-sulfonic acid, benzene-sulfonic acid, ~- or B-naphthalene-sulfonic acid, methane-sulfonic acid, ethane-sulfonic acid, he~ane-sulfonic acicl, or trifluoromethane sulro-nic acid.
The amount of catalyst to be used can vary within wide li-mits, in general it ranges from 0.1 to 100 mol %t preferably 5 to 50 mol ~, calculated on the formic acid ester used.
The molar ratio of paraformaldehyde and/or trioxane (cal-culated on their formaldehyde content) to the respective forrn,ic acid ester is not critical~ Preferably, a ratio in the range of from 0.5 to 2 is chosen.
The reaction is carried out at a temperature of frorn 70 to 200C, preferably 90 to 1~0C.
In the process of the invention on principle `all formic zc esters HCOOR are suitable. Especially suitable radicals R are alkyl, cycloalkyl and alkaryl having up to 8 carbon atoms, for example methyl, ethyl, propyl, i-propyl, n-butyl, isobutyl, tert.butyl, cyclohe~yl, benzyl, n-octyl and 2-ethyl-hexyl.
29 To carry out the process of the invention the mlxture of .~ HOE 76/F 264 paraformaldehyde and/or trioxane, formic acid ester and catalyst is heated at atmospheric pressure or slight excess pressure.
At a reaction temperature a~ove the boiling point of the res-pective formic acid ester an excess pressure up to 50 bars prov-ed to be advantageous to prevent the ester from evaporating from the liquid phase. The presence of an inert gas, for exarnple nitrogen, is possible.
The process of the invention can be carried out in any ap-paratus suitable for reactions in the liquid phase with or with-out the appllcation of excess pressure, for example in an enamel-ed autoclave.
The reaction mixture can be worked up according to known methods, for example the glycolic acid ester formed is directly ~ distilled off from the reaction mixture.
Glycolic acid esters are used for many technologica1 appli-cations. By hydrolysis of the esters glycolic acid can be ol)-tained in very pure form.
~he hydrogenolysis of glycolic acid methyl ester is ~sed in industry to produce glycol. Glyco~ic acid n-butyl ester is a commercial varnish improving agent. Quite genera.l.l.y, glycs-lic acid e~sters are characterized by an excellent dissolving power for polymers, copolymers, nitrocellulose, cellulose ethers, cel.luloid, chlorinated rubber and resins.
The following examples illustrate the invention.
2~ E X A M P L E 1:
In a glass tube sealed by melting 0.6 g of paraformal-dehyde, l.2 g of formic acid methyl ester and 0.9 ml of tri~
fluoromethane-sulfonic acid were heated for l hour to 120C.
29 The reaction mixture contained l.l g o~ glycolic acid methyl ester, corresponding to a yield of 61 mol ~, calculated on the starting compounds used.
E X A M P L E 2:
. .
In an enameled autoclave 12 g of trioxane (= 0.4 mol of CH20), 41 g ~0.4 mo].) of formic acid n-butyl ester and 1.2 ml of methane-sulfonic acid were heated for 1 hour to 157C. The reaction mixture contained 17.5 g of glycolic acid n-butyl ester, corresponding to a yield of 33 mol %.
, 5 -
In a glass tube sealed by melting 0.6 g of paraformal-dehyde, l.2 g of formic acid methyl ester and 0.9 ml of tri~
fluoromethane-sulfonic acid were heated for l hour to 120C.
29 The reaction mixture contained l.l g o~ glycolic acid methyl ester, corresponding to a yield of 61 mol ~, calculated on the starting compounds used.
E X A M P L E 2:
. .
In an enameled autoclave 12 g of trioxane (= 0.4 mol of CH20), 41 g ~0.4 mo].) of formic acid n-butyl ester and 1.2 ml of methane-sulfonic acid were heated for 1 hour to 157C. The reaction mixture contained 17.5 g of glycolic acid n-butyl ester, corresponding to a yield of 33 mol %.
, 5 -
Claims (3)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a glycolic acid ester in which paraformaldehyde, trioxane or a mixture thereof is reacted with a formic acid ester in the liquid phase at a temper-ature of from 70 to 200°C in the presence of an organic sulfonic acid catalyst.
2. A process as claimed in claim 1 in which the reaction is carried out at a temperature of from 90 to 180°C.
3. A process as claimed in claim 1 or claim 2 in which the catalyst is present in an amount of from 0.1 to 100 mol %, calculated on the amount of formic acid ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2652072.9 | 1976-11-15 | ||
| DE19762652072 DE2652072A1 (en) | 1976-11-15 | 1976-11-15 | PROCESS FOR THE PRODUCTION OF GLYCOLIC ACID ESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105486A true CA1105486A (en) | 1981-07-21 |
Family
ID=5993221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,707A Expired CA1105486A (en) | 1976-11-15 | 1977-11-14 | Process for the manufacture of glycolic acid esters |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5398924A (en) |
| BE (1) | BE860878A (en) |
| CA (1) | CA1105486A (en) |
| DE (1) | DE2652072A1 (en) |
| FR (1) | FR2370716A1 (en) |
| GB (1) | GB1595231A (en) |
| IT (1) | IT1088881B (en) |
| NL (1) | NL7712392A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201615762D0 (en) | 2016-09-16 | 2016-11-02 | Johnson Matthey Davy Technologies Ltd | Process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5128615B2 (en) * | 1972-10-03 | 1976-08-20 |
-
1976
- 1976-11-15 DE DE19762652072 patent/DE2652072A1/en not_active Withdrawn
-
1977
- 1977-11-10 NL NL7712392A patent/NL7712392A/en not_active Application Discontinuation
- 1977-11-11 IT IT2961077A patent/IT1088881B/en active
- 1977-11-14 GB GB4728577A patent/GB1595231A/en not_active Expired
- 1977-11-14 JP JP13580177A patent/JPS5398924A/en active Pending
- 1977-11-14 CA CA290,707A patent/CA1105486A/en not_active Expired
- 1977-11-15 FR FR7734232A patent/FR2370716A1/en active Pending
- 1977-11-16 BE BE182662A patent/BE860878A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1595231A (en) | 1981-08-12 |
| BE860878A (en) | 1978-05-16 |
| JPS5398924A (en) | 1978-08-29 |
| DE2652072A1 (en) | 1978-05-24 |
| NL7712392A (en) | 1978-05-17 |
| IT1088881B (en) | 1985-06-10 |
| FR2370716A1 (en) | 1978-06-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |