CA2084335A1 - Method of producing storage stable 1-di-(c1- to c3-) alkylamino-2,3-propanediols - Google Patents

Method of producing storage stable 1-di-(c1- to c3-) alkylamino-2,3-propanediols

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Publication number
CA2084335A1
CA2084335A1 CA 2084335 CA2084335A CA2084335A1 CA 2084335 A1 CA2084335 A1 CA 2084335A1 CA 2084335 CA2084335 CA 2084335 CA 2084335 A CA2084335 A CA 2084335A CA 2084335 A1 CA2084335 A1 CA 2084335A1
Authority
CA
Canada
Prior art keywords
glycidol
amine
propanediols
alkylamino
reaction
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.)
Abandoned
Application number
CA 2084335
Other languages
French (fr)
Inventor
Peter Goetz
Alois Moehlenkamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of CA2084335A1 publication Critical patent/CA2084335A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

1-Di-(C1- to C3-) alkylamino-2,3-propanediols can be produced in known manner from glycidol and di(C1- to C3-) alkyl amines. The resulting compounds, which are colourless in themselves, become discoloured during storage. According to the invention this disadvantage can be eliminated by heat treatment at 150 to 200°C for 0.5 to 5 hours before the dialkyl aminopropanediol is purified by distillation. The method is particularly applicable to manufacture of storage stable 1-dimethylamino-2, 3-propanediol.

Description

20843~5 The invention relates to a method of producing storage stable l-Di-(Cl- to C3-) alkylamino-2, 3-propanediols, more particularly dimethyl aminopropanediol, from glycidol and the corresponding Di(Cl,- to C3)-alkyl amines. Products manufactured according to the invention show practically no discoloration after storage.

1-Dialkylamino-2, 3-propanediols can be manufactured in known manner from glycerol monochlorohydrin and a dialkyl amine.
1-Di-(Cl- to C3-) alkylamino-2, 3-propanediols manufactured by this method are storage stable, i. e. do not become appreciably discoloured after storage, but the method is environmentally harmful since a salt is produced from the liberated hydrochloric acid. In an alternative method, in which the reactant is glycidol (2, 3-epoxypropanol) instead of glycerol monochlorohydrin, the corresponding dialkyl aminopropanediols can be produced with a high yield and without any salt being formed. The manufacture of dialkyl aminopropanediols from glycidol and secondary amines has been exhaustively described, see "Glycidol, Properties reactions and applications" by A. Kleemann and R. Wagner, A. HUthig Verlag (1981), pages 90-94. The reactants can be added in equimolar proportions. As in the case of primary amines or ammonia, however, an excess of amine is advantageous. The reaction can be performed in the presence of inert solvents or in the absence thereof, if there is an excess of amine (compare EP-B O 038 409, DE 30 14 098 C2).

One hitherto unexplained disadvantage of the method via 20843~5 glycidol is that the resulting lower dialkyl aminopropanediols, more particularly dimethyl aminopropanediols, become yellow during storage. This discoloration is observed a short time after distillation.
The discoloration is initially pale yellow and becomes more intense after a few days until it reaches a maximum, and cannot be suppressed either by increased distillation or by measures such as exclusion of air and light.

The invention improves the known method of producing l-Di-(Cl- to C3-) alkylamino-2, 3-propanediols from glycidol and corresponding Di-(C1- to C3-) alkylamine by reacting glycidol with Di-(C1- to C3)-alkyl amine in the molar ratio of 1 to more than 1 in the presence or absence of a solvent and distillative processing of the distillation mixture, so as to obtain l-Di-(Cl- to C3-) alkylamino-2, 3-propanediols which are storage stable, i.e. do not become appreciably discoloured. It has been found that this problem can be solved if the reaction mixture, substantially freed from unreacted amine and any solvents, is heat-treated at 50 to 200C for O.S to 5 hours and subsequently distilled.

Thermal treatment is of, particular importance in manufacturing l-dimethylamino-2, 3-propanediol, which has 208~33~

become important as a starting product in the manufacture of textile aids. Heat-treatment in the case of l-dimethylamino-2, 3-propanediol is preferably carried out at 160 to 190C
and within 1 to 3 hours.

The reaction between glycidol and the dialkyl amine is brought about at a molar ratio of 1 to more than 1, preferably 1 to more than 2, more particularly 1 to 2 - 3.
The dialkyl amines used contain 2 to 6 carbon atoms.
Dimethyl amine and diethyl amine are preferred, but other dialkyl amines with different alkyl groups can be used. The excess amine also serves as a solvent. However, other solvents can be used in the reaction, e.g. organic solvents from the series of low-boiling alcohols and ethers or water.
Preferably no organic solvents are used apart from the excess amine and optionally water. A substantially water-free reaction medium is preferred for simplicity of operation.
The reaction can be performed in a continuous apparatus or batchwise.

To avoid polymerising the glycidol, glycidol is always added to the amine and not vice versa. The reaction temperature is advantageously below 100C, more particularly in the range from 30 to 60C. When dialkyl amines with a boiling point 2~8~335 below 60C are used, the reaction is advantageously carried out at the pressure which occurs at the chosen reaction temperature. At the end of,the reaction, the reaction mixture is substantially freed from unreacted amine and any S solvents present. This is done by known methods of distillation and/or by desorption, using inert gases. The reaction mixture, after being substantially freed from low-boiling constituents, is heat-treated at normal or elevated pressure.

l-Di-(Cl- to C3-) alkylamino-2, 3-propanediol heat-treated according to the invention is practically colourless after distillation and does not change colour even after prolonged storage. It could not be foreseen that discoloration during storage, which was recognised as a serious disadvantage of the known process, could be avoided by simple heat-treatment of the crude dialkyl aminopropanediol or the reaction mixture for preparing it via glycidol.

Surprisingly, heat-treatment does not result in any measurable loss of output.

Example 1 2S Production of l-dimethylamino-2, 3-propanediol using water as a solvent.

2o8433s Substances used:

683 g = 5 mol of dimethyl amine in the form of a 33% solution in water and 296 g = 4 mol glycidol.

Method of reaction:

The aqueous amine was placed in a flask and heated to 50C.

The glycidol was then added with agitation in 3 hours at a rate such that the temperature did not rise above 75C. The mixture was then agitated at 50C for a further 2 hours.
First the water and excess amine were removed from the reaction mixture by distillation. The crude product was then heated to 175C at normal pressure for 2 hours and then cooled to 50C. The l-dimethyl aminopropanediol was then distilled at 10 mbar and a head temperature of 90C. The yield was 343 g dimethyl aminopropanediol, corresponding to 72% of the theoretical relative to the amount of glycidol used.

Colour measurements:

Immediately after distillation: 50 Hazen After 6 months storage (without special precautions): 80 Hazen Example 2 Manufacture of l-dimethylamino-2, 3-propanediol without solvent.

Substances used:

77.6 kg = 114 1 = 1.72 kmol of dimethyl amine (anhydrous) and Sl.0 kg = 45.8 1 = 0.69 kmol glycidol.

Method of reaction:

The dimethyl amine was placed in a pressure reactor (useful volume: 160 1) equipped with an agitator and metering pump and heated to 40C, the resulting pressure being 3 to 4 bar.
Within 4.5 hours, the glycidol was added at a rate such that the temperature did not exceed 40C. In the process the pressure dropped. After the metered addition, the mixture was agitated at 40C for 1 hour in order to react the glycidol completely. The temperature was then raised to 60C
and most of the excess amine (about 42 kg) was removed. In order to remove the remaining dimethyl amine, the reaction mixture was processed in a distillation vessel at a bottom temperature of 60C and a pressure of 10 mbar. The crude product was heated to 175C at normal pressure for 2 hours 2 ~ (~ 1 3 .~ !5 and then cooled to 60C. The dimethyl aminopropanediol was then distilled at 10 mbar and at a head temperature of 90C.
The product was 75.2 kg dimethyl aminopropanediol, corresponding to 92% of the theoretical yield relative to the-glycidol used.

Colour measurements:

Immediately after distillation: 30 Hazen After 6 months storage (without special precautions): 80 Hazen After six months storage with exclusion of air and light: 45 Hazen Comparative example l-dimethylamino-2, 3-propanediol was prepared as per Example 2 but without heat-treatment at 175C. The yield was 92% of the theoretical.
Colour measurements:

Immediately after distillation: 150 Hazen After 6 months storage (without special precautions): >1000 Hazen After 6 months storage with exclusion of air and light: 400 Hazen

Claims (10)

1. A method of producing l-Di-(C1- to C3-) alkylamino-2, 3-propanediols by reacting glycidol with symmetrical or asymmetrical Di(C1- to C3-) alkylamines in the molar ratio of 1 to more than 1 in the presence or absence of a solvent and by distillative processing of the reaction mixture, wherein the reaction mixture, substantially freed from unreacted amine and any solvents, is heat-treated at 150 to 200C for 0.5 to 5 hours and subsequently distilled.
2. A method according to claim 1, wherein 1-dimethylamino-2,
3-propanediol is produced from glycidol and dimethylamine.

3. A method according to claim 2, wherein the heat-treatment is carried out at 160 to 190C for 1 to 3 hours.
4. A method according to claim 1, 2 or 3, wherein the molar ratio is 1 to more than 2.
5. A method according to claim 4, wherein the molar ratio is 1, to 2 or 3.
6. A method according to claim 1, 2, 3 or 5, effected in the absence of a solvent other than an excess of the amine.
7. A method according to claim 6, wherein water is used as a solvent in addition to the amine.
8. A method according to claim 1, 2, 3, 5 or 7, effected in a continuous or batchwise manner.
9. A method according to claim 1, 2, 3, 5 or 7, wherein the reaction temperature is below 100C.
10. A method according to claim 9, wherein the reaction temperature is 30 to 60C.
CA 2084335 1991-12-14 1992-12-02 Method of producing storage stable 1-di-(c1- to c3-) alkylamino-2,3-propanediols Abandoned CA2084335A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4141349.0 1991-12-14
DE19914141349 DE4141349C1 (en) 1991-12-14 1991-12-14

Publications (1)

Publication Number Publication Date
CA2084335A1 true CA2084335A1 (en) 1993-06-15

Family

ID=6447109

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2084335 Abandoned CA2084335A1 (en) 1991-12-14 1992-12-02 Method of producing storage stable 1-di-(c1- to c3-) alkylamino-2,3-propanediols

Country Status (4)

Country Link
EP (1) EP0547402A3 (en)
JP (1) JPH05255208A (en)
CA (1) CA2084335A1 (en)
DE (1) DE4141349C1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284930B1 (en) 1999-07-30 2001-09-04 E.I. Du Pont De Nemours And Company Process for the preparation of 3-hydroxypropanal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3014098C2 (en) * 1980-04-12 1984-08-30 Degussa Ag, 6000 Frankfurt Process for the preparation of 1-amino-propanediol- (2,3)

Also Published As

Publication number Publication date
JPH05255208A (en) 1993-10-05
EP0547402A3 (en) 1993-09-08
DE4141349C1 (en) 1993-06-03
EP0547402A2 (en) 1993-06-23

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