CA2141259A1 - Process for the preparation of betaines - Google Patents
Process for the preparation of betainesInfo
- Publication number
- CA2141259A1 CA2141259A1 CA 2141259 CA2141259A CA2141259A1 CA 2141259 A1 CA2141259 A1 CA 2141259A1 CA 2141259 CA2141259 CA 2141259 CA 2141259 A CA2141259 A CA 2141259A CA 2141259 A1 CA2141259 A1 CA 2141259A1
- Authority
- CA
- Canada
- Prior art keywords
- betaine
- acid
- temperature
- solution
- employed
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229960003237 betaine Drugs 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005956 quaternization reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims 1
- -1 tertiary amine compound Chemical class 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000002896 organic halogen compounds Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 22
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229960005215 dichloroacetic acid Drugs 0.000 description 11
- 239000000203 mixture Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229940080263 sodium dichloroacetate Drugs 0.000 description 2
- LUPNKHXLFSSUGS-UHFFFAOYSA-M sodium;2,2-dichloroacetate Chemical compound [Na+].[O-]C(=O)C(Cl)Cl LUPNKHXLFSSUGS-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940120124 dichloroacetate Drugs 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000003977 halocarboxylic acids Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- TWMFGCHRALXDAR-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCCN(C)C TWMFGCHRALXDAR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
Abstract
In the process described for the preparation of betaines the tertiary starting amine is first quaternized with an .omega.-haloalkanecarboxylic acid or a salt thereof, preferably in water as solvent, at a temperature of from 60 to 98°C
and at a pH of from 7 to 11, the tertiary amine compound and the haloalkanecarboxylic acid or salt thereof having been employed in a molar ratio of 1: from 1 to 1.5. The betaine solution obtained is then maintained at a pH of from 1 to 14 and at a temperature of from 95 to 170°C
until no further organically bonded halogen can be detected. The finished betaine solution has the required purity with regard to starting amine and to organic halogen compound.
and at a pH of from 7 to 11, the tertiary amine compound and the haloalkanecarboxylic acid or salt thereof having been employed in a molar ratio of 1: from 1 to 1.5. The betaine solution obtained is then maintained at a pH of from 1 to 14 and at a temperature of from 95 to 170°C
until no further organically bonded halogen can be detected. The finished betaine solution has the required purity with regard to starting amine and to organic halogen compound.
Description
21~259 -HOECHST AKTIENGESELLSCHAFT HOE 94/F 902J Dr.GL-nu Werk Gendorf Process for the preparation of betaines Description The invention relates to a process for the preparation of betaines of the formula 1 Rl-N+- ( CH2 ) y~COO~ ( 1 ) in which Rl is an alkyl radical having at least 8 carbon atoms or is the radical R4CoNH(CH2)X- in which R4Co is an acyl radical derived from a carboxylic acid having from 6 to 18 carbon atoms and x is 2, 3 or 4, R2 and R3 are identical or different and are an alkyl radical having from 1 to 4 carbon atoms or are the radical -(CH2)zOH where z = 1, 2 or 3 and y is 1, 2 or 3 by quaternization of a tertiary amine of the formula 2 Rl-N (2) in which Rl, R2 and R3 are as defined with an ~-haloalkanecarboxylic acid of the formula 3 X-(CH2)y~COOH (3) 21~1259 -in which X is a halogen and y is as defined or a salt thereof, in the liquid phase.
A procesæ of this kind is described in DE-A 42 05 880, where the quaternization is carried out in the aqueous phase at a temperature of from 115 to 180C. Using this relatively high reaction temperature, which leads to breakdown of the ~-haloalkanecarboxylic acid employed and of the ~-dihaloalkanecarboxylic acid present therein as an impurity, ensures that the betaine solutions obtained are virtually free from compounds contAin;ng organically bonded halogen (chlorine) such as sodium mono- and -dichloroacetate. However, the breakdown of haloalkane-carboxylic acid, i.e. one of the two reaction components, also meanæ that the betaine solution obtained contains a more or less substantial quantity of unreacted starting amine. In other words, the advantage of obtA;n;ng betaine solutions which are free from organically bonded halogen is countered by the disadvantage that these solutions are contAm;nAted with the amine compound employed.
In order to obtain betaine solutions which are free from starting amine and from organically bonded halogen, US-A 4 497 825 advocates carrying out the quaternization reaction at a pH of from 7.5 to 10.5. Although these betaine solutions contain virtually no residual amine compound, they are likely to contain an undesirably high residual quantity of organically bonded halogen in the form of the ~ono~A1ocarboxylic acid employed and/or of its impurity, namely dihalocarboxylic acid, as also referred to in the abovementioned DE-A 42 05 880.
The object of the invention, accordingly, is to provide a process for the preparation of betaine solutions which possess the desired purity with regard both to organi-cally bonded halogen and to amine compounds; in other words, the content of tertiary starting amine should be ~ 0.5% by weight and that of halocarboxylic acid compounds should be ~ 10 ppm each.
'~ 2 5 9 The process according to the invention comprises a) in a first reaction step, in which the tertiary amine and the ~-haloalkanecarboxylic acid or salt thereof are employed in a molar ratio of 1: from 1 to 1.5, preferably 1: from 1.03 to 1.3, carrying out quaternization at a temperature of from 60 to 98C, preferably from 70 to 95C, and at a pH of from 7 to 11, preferably from 8 to 10, to obtain a betaine solution having the desired purity with regard to starting amine, and b) in a second reaction step, adjusting the betaine solution obtained in the first step to a pH of from 1 to 14, preferably from 5 to 12, and maintaining it at a temperature of from 95 to 170C, preferably from 100 to 150C, until the betaine solution also has the desired purity with regard to organically bonded halogen.
In the process according to the invention the reaction between the tertiary amine and the haloalkanecarboxylic acid or the haloalkanecarboxylate salt, which is prefer-ably an alkali metal salt (for the sake of simplicity this description only uses the terms haloalkanecarboxylic acid or halocarboxylic acid) is carried out such that, first of all, a betaine solution is prepared which contains less than 0.5% by weight of starting amine, percentages by weight being based on the solution. This is achieved by a combination of selected values for the molar ratio of reaction components, the reaction tempera-ture and the pH of the reaction solution during the quaternization. Thus from 1 to 1.5 mol, preferably from 1.03 to 1.3 mol, of haloalkanecarboxylic acid are employed per mole of tertiary amine compound. The pH of the initial mixture is adjusted to from 7 to 11, prefer-ably from 8 to 10, and is maintained until the end of the quaternization. The temperature at which the quaterniza-tion reaction is carried out is from 60 to 98C, prefer-ably from 70 to 95C. The adjustment and maintenance of the specified pH of the mixture is effected (insofar as 2 ~ 9 this pH is not already present, as is the case, for example, when using haloalkanecarboxylate salts) by addition of a preferably aqueous alkali metal hydroxide solution, prior to and/or during the quaternization reaction. The resulting betaine solution (the reaction time for the quaternization is from about 6 to 20 hours) is pure with regard to starting amine, but not with regard to the monohalocarboxylic acid employed and the dihalocarboxylic acid.
This betaine solution is then, in a second step, brought to a temperature of from 95 to 170C, preferably from 100 to 150C, and maintained at this temperature until the halocarboxylic acid compounds under discussion have been broken down, in other words until virtually no further lS organically bonded halogen is present. Furthermore, in the betaine solution from the first step a pH of from 1 to 14, preferably from 5 to 12, is adjusted and main-tained, preferably with the aid of an aqueous mineral or carboxylic acid or of an aqueous alkali metal hydroxide solution. The addition of the acid solution or hydroxide solution to the betaine solution from the first step can be carried out before and/or while the latter solution is heated to the specified temperature of from 95 to 170C, preferably from 100 to 150C. The betaine solution is maintained at this temperature and at the specified pH
from 1 to 14, preferably from 5 to 12, until the content of organically bonded hydrogen is < 10 ppm (the reaction time for the breakdown of organically bonded halogen depends on temperature and pH which is in general from 3 to 50 hours). The resulting betaine solution now has the required purity with regard to amine and halocarboxylic acid compounds. Its betaine content (content of active substance) is in general from 20 to 55% by weight, preferably from 25 to 50% by weight; in other words, the solvent (the liquid phase) is employed in a quantity such that betaine solutions having this content of active substance are obtained. The solvent may be water, a lower alcohol such as methanol, ethanol, propanol, isopropanol '~14~25g and/or propylene glycol, or a mixture of water and alcohol, preference being given to water and to mixtures of water and alcohol. The water and also the other solvents may be employed as such or in the form of solutions of alkali metal hydroxide, amine compound and/or halocarboxylic acid compound. The process accord-ing to the invention may be carried out batchwise or continuously, for example in one or more stirred vessels which are arranged in series or in cascade formation. The betaine solutions as obtained already constitute valuable products. 8etaines, indeed, are surface-active compounds with a wide variety of possible applications. Because of their good skin compatibility they are employed princi-pally in bodycare.
With regard to the starting compounds - tertiary amine, ~-monohalocarboxylic acid or a salt thereof, preferably an alkali metal salt, and if desired alkali metal hydroxide - the following comments apply: the tertiary starting amines are of the formula 2 given at the beginning. The long alkyl radical R1 may also contain double bonds, preferably from 1 to 3. Preferred starting amines are those of the formula 2 in which Rl is an alkyl radical having from 8 to 18 carbon atoms or is a radical of the formula R4CoNH(cH2)x- in which R4Co is an acyl radical which is derived from a carboxylic acid having from 6 to 18 carbon atoms and x is 2, 3 or 4, and R2 and R3 are each methyl. Examples are dimethyloctylamine, dimethyllaurylamine, dimethylstearylamine, dimethylcoco-alkylamine, dimethyltallow-alkylamine and the like, and also lauroylaminopropyldimethylamine, stearoylamino-propyldimethylamine,cocoacylaminopropyldimethylamineand the like. The ~-halocarboxylic acid is preferably mono-chloroacetic acid or, respectively, sodium monochloro-acetate. The alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.
The invention is now illustrated in more detail with reference to examples according to the invention and 214~259 comparative examples.
Examples according to the invention Examples 1 to 3 relate to the first step of the process according to the invention:
Example 1 188 g (0.587 mol) of cocamidopropyl-N,N-dimethylamine (ami~o~;ne) and 345 g of water are introduced as initial charge into a 1 1 glass flask equipped with stirrer, thermometer, reflux co~n~er and dropping funnel. The mixture is heated to about 82C with ætirring. While maint~;n;ng this temperature of about 82C, 72.8 g (0.616 mol) of an 80% strength by weight aqueous solution of monochloroacetic acid are added dropwise to this suspension, slowly and continuously, over 5.5 hours, and also 53.7 g (0.671 mol) of a 50% strength by weight aqueous solution of NaOH, in order to establish a pH of from 8 to 9 (the molar ratio of amidoamine to monochloro-acetic acid is 1:1.05). After addition is complete the mixture is left to continue reacting at about 80C for 9 hours. The 30% strength by weight aqueous betaine solution obtained, with regard to cocamidoamine, mono-chloroacetic acid (MCA) and dichloroacetic acid (DCA), has the following contents in percent by weight or ppm, based on the solution:
Ami~o~m;ne: 0.14%
MCA: 0.1%
DCA: 110 ppm Example 2 Example 1 is repeated but with the following changes:
Molar ratio of amidoamine: MCA = 1:1.25 Temperature: 95C
21~259 pH: from 8 to 9 Time of continued reaction: 7 hours Results:
Amidoamine: 0.11%.
5 MCA: 0.13%
DCA: 100 ppm Example 3 Example 1 is repeated but with the following changes:
Molar ratio of amidoamine: MCA = 1:1.05 Temperature: 70C
pH: from 8 to 9 Time of continued reaction: 12 hours Results:
Amidoamine: 0.25%
MCA: 0.09%
DCA: 115 ppm Therefore the betaine solutions have the low value desired with regard to amidoamine but not with regard to MCA and DCA.
Examples 4 to 17 relate to the second step of the process according to the invention:
In the second step the MCA and DCA content of the betaine solution from the first step is reduced down to the ppm range while ret~; n; ng the low values for amidoamine. For convenience, only the betaine solution of Example 1 is employed.
Example 4 The betaine solution of Example 1 is adjusted to a pH of 12 using 50% strength by weight aqueous sodium hydroxide and is then stirred at a temperature of 105C for 48 hours in a stirred autoclave. The betaine solution obtained then has an MCA and DCA content of ~ 10 ppm each.
Examples 5 to 18 The betaine solution of Example 1 is adjusted to a defined pH with 50% strength by weight aqueous sodium hydroxide (Examples 5 to 15) or with from 30 to 36%
strength by weight aqueous hydrochloric acid (Examples 16 to 18), and is then stirred at a defined temperature for a greater or lesser period (reaction time) in a stirred autoclave. These reaction conditions and the result with regard to MCA and DCA content are compiled in the table below, together with the values for Example 4.
Using the process according to the invention, therefore, betaine solutions are obtained which have the low content required in each case with regard both to starting amine and to halogenated organic compounds (MCA and DCA).
Table Example No. 4 S 6 7 8 9 10 11 12 13 14 15 16 17 18 p~ 12 12 12 14 14 8 10 12 14 14 14 14 6 4.5 2 ~emperature (C~ 105 110 115 115 120 125 125 135 95 llo 105 115 135 135 135 Reaction time 48 20 20 16 3 24 16 3 50 16 20 6 5 4 5(h) MCA content ~ 10 ~ 10 c 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 (ppm) DCA content ~ 10 ~ 10 ~ 10 c 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~_ (ppm) ~_~
~' '~41259 Comparative Examples (Reworking of Examples 2.1 and 2.3 from DE-A 42 05 880) Comparative Example 1 59.3 g (0.51 mol) of sodium monochloroacetate, 154.3 g (0.5 mol) of cocamidopropyl-N,N-dimethylamine (cocamido-amine) and 355.7 g of water are introduced as initial charge into a 1 l autoclave and are heated to 120C, during which a pressure of 2.6 bar i8 established. After a reaction time of 8 hours the reaction solution is cooled. The product is characterized by the following data:
Sodium chloride content: 5.2%
Cocamidoamine content: 2.4%
Glycolic acid content: 0.37%
15 Sodium monochloroacetate content: ~ 20 ppm Sodium dichloroacetate content: ~ 10 ppm Comparative Example 2 Comparative Example 1 is repeated at a reaction tempera-ture of 140C. A pressure of 3.2 bar is established. The reaction time is again 8 hours. The product is character-ized by the following data:
Sodium chloride content: 5.2%
Cocamidoamine content: 2.5%
Glycolic acid content: 0.42%
25 Sodium monochloroacetate content: ~ 20 ppm Sodium dichloroacetate content: ~ 10 ppm
A procesæ of this kind is described in DE-A 42 05 880, where the quaternization is carried out in the aqueous phase at a temperature of from 115 to 180C. Using this relatively high reaction temperature, which leads to breakdown of the ~-haloalkanecarboxylic acid employed and of the ~-dihaloalkanecarboxylic acid present therein as an impurity, ensures that the betaine solutions obtained are virtually free from compounds contAin;ng organically bonded halogen (chlorine) such as sodium mono- and -dichloroacetate. However, the breakdown of haloalkane-carboxylic acid, i.e. one of the two reaction components, also meanæ that the betaine solution obtained contains a more or less substantial quantity of unreacted starting amine. In other words, the advantage of obtA;n;ng betaine solutions which are free from organically bonded halogen is countered by the disadvantage that these solutions are contAm;nAted with the amine compound employed.
In order to obtain betaine solutions which are free from starting amine and from organically bonded halogen, US-A 4 497 825 advocates carrying out the quaternization reaction at a pH of from 7.5 to 10.5. Although these betaine solutions contain virtually no residual amine compound, they are likely to contain an undesirably high residual quantity of organically bonded halogen in the form of the ~ono~A1ocarboxylic acid employed and/or of its impurity, namely dihalocarboxylic acid, as also referred to in the abovementioned DE-A 42 05 880.
The object of the invention, accordingly, is to provide a process for the preparation of betaine solutions which possess the desired purity with regard both to organi-cally bonded halogen and to amine compounds; in other words, the content of tertiary starting amine should be ~ 0.5% by weight and that of halocarboxylic acid compounds should be ~ 10 ppm each.
'~ 2 5 9 The process according to the invention comprises a) in a first reaction step, in which the tertiary amine and the ~-haloalkanecarboxylic acid or salt thereof are employed in a molar ratio of 1: from 1 to 1.5, preferably 1: from 1.03 to 1.3, carrying out quaternization at a temperature of from 60 to 98C, preferably from 70 to 95C, and at a pH of from 7 to 11, preferably from 8 to 10, to obtain a betaine solution having the desired purity with regard to starting amine, and b) in a second reaction step, adjusting the betaine solution obtained in the first step to a pH of from 1 to 14, preferably from 5 to 12, and maintaining it at a temperature of from 95 to 170C, preferably from 100 to 150C, until the betaine solution also has the desired purity with regard to organically bonded halogen.
In the process according to the invention the reaction between the tertiary amine and the haloalkanecarboxylic acid or the haloalkanecarboxylate salt, which is prefer-ably an alkali metal salt (for the sake of simplicity this description only uses the terms haloalkanecarboxylic acid or halocarboxylic acid) is carried out such that, first of all, a betaine solution is prepared which contains less than 0.5% by weight of starting amine, percentages by weight being based on the solution. This is achieved by a combination of selected values for the molar ratio of reaction components, the reaction tempera-ture and the pH of the reaction solution during the quaternization. Thus from 1 to 1.5 mol, preferably from 1.03 to 1.3 mol, of haloalkanecarboxylic acid are employed per mole of tertiary amine compound. The pH of the initial mixture is adjusted to from 7 to 11, prefer-ably from 8 to 10, and is maintained until the end of the quaternization. The temperature at which the quaterniza-tion reaction is carried out is from 60 to 98C, prefer-ably from 70 to 95C. The adjustment and maintenance of the specified pH of the mixture is effected (insofar as 2 ~ 9 this pH is not already present, as is the case, for example, when using haloalkanecarboxylate salts) by addition of a preferably aqueous alkali metal hydroxide solution, prior to and/or during the quaternization reaction. The resulting betaine solution (the reaction time for the quaternization is from about 6 to 20 hours) is pure with regard to starting amine, but not with regard to the monohalocarboxylic acid employed and the dihalocarboxylic acid.
This betaine solution is then, in a second step, brought to a temperature of from 95 to 170C, preferably from 100 to 150C, and maintained at this temperature until the halocarboxylic acid compounds under discussion have been broken down, in other words until virtually no further lS organically bonded halogen is present. Furthermore, in the betaine solution from the first step a pH of from 1 to 14, preferably from 5 to 12, is adjusted and main-tained, preferably with the aid of an aqueous mineral or carboxylic acid or of an aqueous alkali metal hydroxide solution. The addition of the acid solution or hydroxide solution to the betaine solution from the first step can be carried out before and/or while the latter solution is heated to the specified temperature of from 95 to 170C, preferably from 100 to 150C. The betaine solution is maintained at this temperature and at the specified pH
from 1 to 14, preferably from 5 to 12, until the content of organically bonded hydrogen is < 10 ppm (the reaction time for the breakdown of organically bonded halogen depends on temperature and pH which is in general from 3 to 50 hours). The resulting betaine solution now has the required purity with regard to amine and halocarboxylic acid compounds. Its betaine content (content of active substance) is in general from 20 to 55% by weight, preferably from 25 to 50% by weight; in other words, the solvent (the liquid phase) is employed in a quantity such that betaine solutions having this content of active substance are obtained. The solvent may be water, a lower alcohol such as methanol, ethanol, propanol, isopropanol '~14~25g and/or propylene glycol, or a mixture of water and alcohol, preference being given to water and to mixtures of water and alcohol. The water and also the other solvents may be employed as such or in the form of solutions of alkali metal hydroxide, amine compound and/or halocarboxylic acid compound. The process accord-ing to the invention may be carried out batchwise or continuously, for example in one or more stirred vessels which are arranged in series or in cascade formation. The betaine solutions as obtained already constitute valuable products. 8etaines, indeed, are surface-active compounds with a wide variety of possible applications. Because of their good skin compatibility they are employed princi-pally in bodycare.
With regard to the starting compounds - tertiary amine, ~-monohalocarboxylic acid or a salt thereof, preferably an alkali metal salt, and if desired alkali metal hydroxide - the following comments apply: the tertiary starting amines are of the formula 2 given at the beginning. The long alkyl radical R1 may also contain double bonds, preferably from 1 to 3. Preferred starting amines are those of the formula 2 in which Rl is an alkyl radical having from 8 to 18 carbon atoms or is a radical of the formula R4CoNH(cH2)x- in which R4Co is an acyl radical which is derived from a carboxylic acid having from 6 to 18 carbon atoms and x is 2, 3 or 4, and R2 and R3 are each methyl. Examples are dimethyloctylamine, dimethyllaurylamine, dimethylstearylamine, dimethylcoco-alkylamine, dimethyltallow-alkylamine and the like, and also lauroylaminopropyldimethylamine, stearoylamino-propyldimethylamine,cocoacylaminopropyldimethylamineand the like. The ~-halocarboxylic acid is preferably mono-chloroacetic acid or, respectively, sodium monochloro-acetate. The alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.
The invention is now illustrated in more detail with reference to examples according to the invention and 214~259 comparative examples.
Examples according to the invention Examples 1 to 3 relate to the first step of the process according to the invention:
Example 1 188 g (0.587 mol) of cocamidopropyl-N,N-dimethylamine (ami~o~;ne) and 345 g of water are introduced as initial charge into a 1 1 glass flask equipped with stirrer, thermometer, reflux co~n~er and dropping funnel. The mixture is heated to about 82C with ætirring. While maint~;n;ng this temperature of about 82C, 72.8 g (0.616 mol) of an 80% strength by weight aqueous solution of monochloroacetic acid are added dropwise to this suspension, slowly and continuously, over 5.5 hours, and also 53.7 g (0.671 mol) of a 50% strength by weight aqueous solution of NaOH, in order to establish a pH of from 8 to 9 (the molar ratio of amidoamine to monochloro-acetic acid is 1:1.05). After addition is complete the mixture is left to continue reacting at about 80C for 9 hours. The 30% strength by weight aqueous betaine solution obtained, with regard to cocamidoamine, mono-chloroacetic acid (MCA) and dichloroacetic acid (DCA), has the following contents in percent by weight or ppm, based on the solution:
Ami~o~m;ne: 0.14%
MCA: 0.1%
DCA: 110 ppm Example 2 Example 1 is repeated but with the following changes:
Molar ratio of amidoamine: MCA = 1:1.25 Temperature: 95C
21~259 pH: from 8 to 9 Time of continued reaction: 7 hours Results:
Amidoamine: 0.11%.
5 MCA: 0.13%
DCA: 100 ppm Example 3 Example 1 is repeated but with the following changes:
Molar ratio of amidoamine: MCA = 1:1.05 Temperature: 70C
pH: from 8 to 9 Time of continued reaction: 12 hours Results:
Amidoamine: 0.25%
MCA: 0.09%
DCA: 115 ppm Therefore the betaine solutions have the low value desired with regard to amidoamine but not with regard to MCA and DCA.
Examples 4 to 17 relate to the second step of the process according to the invention:
In the second step the MCA and DCA content of the betaine solution from the first step is reduced down to the ppm range while ret~; n; ng the low values for amidoamine. For convenience, only the betaine solution of Example 1 is employed.
Example 4 The betaine solution of Example 1 is adjusted to a pH of 12 using 50% strength by weight aqueous sodium hydroxide and is then stirred at a temperature of 105C for 48 hours in a stirred autoclave. The betaine solution obtained then has an MCA and DCA content of ~ 10 ppm each.
Examples 5 to 18 The betaine solution of Example 1 is adjusted to a defined pH with 50% strength by weight aqueous sodium hydroxide (Examples 5 to 15) or with from 30 to 36%
strength by weight aqueous hydrochloric acid (Examples 16 to 18), and is then stirred at a defined temperature for a greater or lesser period (reaction time) in a stirred autoclave. These reaction conditions and the result with regard to MCA and DCA content are compiled in the table below, together with the values for Example 4.
Using the process according to the invention, therefore, betaine solutions are obtained which have the low content required in each case with regard both to starting amine and to halogenated organic compounds (MCA and DCA).
Table Example No. 4 S 6 7 8 9 10 11 12 13 14 15 16 17 18 p~ 12 12 12 14 14 8 10 12 14 14 14 14 6 4.5 2 ~emperature (C~ 105 110 115 115 120 125 125 135 95 llo 105 115 135 135 135 Reaction time 48 20 20 16 3 24 16 3 50 16 20 6 5 4 5(h) MCA content ~ 10 ~ 10 c 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 (ppm) DCA content ~ 10 ~ 10 ~ 10 c 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~ 10 ~_ (ppm) ~_~
~' '~41259 Comparative Examples (Reworking of Examples 2.1 and 2.3 from DE-A 42 05 880) Comparative Example 1 59.3 g (0.51 mol) of sodium monochloroacetate, 154.3 g (0.5 mol) of cocamidopropyl-N,N-dimethylamine (cocamido-amine) and 355.7 g of water are introduced as initial charge into a 1 l autoclave and are heated to 120C, during which a pressure of 2.6 bar i8 established. After a reaction time of 8 hours the reaction solution is cooled. The product is characterized by the following data:
Sodium chloride content: 5.2%
Cocamidoamine content: 2.4%
Glycolic acid content: 0.37%
15 Sodium monochloroacetate content: ~ 20 ppm Sodium dichloroacetate content: ~ 10 ppm Comparative Example 2 Comparative Example 1 is repeated at a reaction tempera-ture of 140C. A pressure of 3.2 bar is established. The reaction time is again 8 hours. The product is character-ized by the following data:
Sodium chloride content: 5.2%
Cocamidoamine content: 2.5%
Glycolic acid content: 0.42%
25 Sodium monochloroacetate content: ~ 20 ppm Sodium dichloroacetate content: ~ 10 ppm
Claims (5)
1. A process for the preparation of a betaine of the formula 1 (1) in which R1 is an alkyl radical having at least 8 carbon atoms or is the radical R4CONH(CH2)X- in which R4CO is an acyl radical derived from a carboxylic acid having from 6 to 18 carbon atoms and x is 2, 3 or 4, R2 and R3 are identical or different and are an alkyl radical having from 1 to 4 carbon atoms or are the radical -(CH2)zOH
where z = 1, 2 or 3 and y is 1, 2 or 3 by quaternization of a tertiary amine of the formula (2) in which R1, R2 and R3 are as defined with an .omega.-haloalkanecarboxylic acid of the formula in which X is a halogen and y is as defined or a salt thereof, in the liquid phase, which com-prises a) in a first reaction step, in which the tertiary amine and the .omega.-haloalkanecarboxylic acid or salt thereof are employed in a molar ratio of 1: from 1 to 1.5, carrying out quaternization at a temperature of from 60 to 98°C and at a pH of from 7 to 11 to obtain a betaine solution having the desired purity with regard to starting amine, and b) in a second reaction step, adjusting the betaine solution obtained in the first step to a pH of from 1 to 14 and maintaining it at a temperature of from 95 to 170°C until the betaine solution also has the desired purity with regard to organically bonded halogen.
where z = 1, 2 or 3 and y is 1, 2 or 3 by quaternization of a tertiary amine of the formula (2) in which R1, R2 and R3 are as defined with an .omega.-haloalkanecarboxylic acid of the formula in which X is a halogen and y is as defined or a salt thereof, in the liquid phase, which com-prises a) in a first reaction step, in which the tertiary amine and the .omega.-haloalkanecarboxylic acid or salt thereof are employed in a molar ratio of 1: from 1 to 1.5, carrying out quaternization at a temperature of from 60 to 98°C and at a pH of from 7 to 11 to obtain a betaine solution having the desired purity with regard to starting amine, and b) in a second reaction step, adjusting the betaine solution obtained in the first step to a pH of from 1 to 14 and maintaining it at a temperature of from 95 to 170°C until the betaine solution also has the desired purity with regard to organically bonded halogen.
2. A process as claimed in claim 1, wherein the terti-ary amine and the .omega.-haloalkanecarboxylic acid or salt thereof are employed in a molar ratio of 1:
from 1.03 to 1.3 and are quaternized at a tempera-ture of from 70 to 95°C and at a pH of from 8 to 10.
from 1.03 to 1.3 and are quaternized at a tempera-ture of from 70 to 95°C and at a pH of from 8 to 10.
3. The process as claimed in claim 1 or 2, wherein the reaction step b) is carried out at a temperature of from 100 to 150°C and at a pH of from 5 to 12.
4. The process as claimed in one or more of claims 1 to 3, wherein the reaction steps a) and b) are carried out in water as the liquid phase.
5. The process as claimed in claim 4, wherein the water is employed in a quantity such that the finished betaine solution has a betaine content of from 20 to 55% by weight, percentages by weight being based on the solution.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4402693.5 | 1994-01-29 | ||
| DE4402693 | 1994-01-29 | ||
| DEP4407840.4 | 1994-03-09 | ||
| DE4407840A DE4407840A1 (en) | 1994-01-29 | 1994-03-09 | Process for the production of betaines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2141259A1 true CA2141259A1 (en) | 1995-07-30 |
Family
ID=25933385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2141259 Abandoned CA2141259A1 (en) | 1994-01-29 | 1995-01-27 | Process for the preparation of betaines |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0665213A1 (en) |
| JP (1) | JPH07278071A (en) |
| BR (1) | BR9500360A (en) |
| CA (1) | CA2141259A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114191841A (en) * | 2021-11-30 | 2022-03-18 | 宜兴市天石饲料有限公司 | Efficient betaine crystallization method and device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5696287A (en) * | 1996-07-22 | 1997-12-09 | Ducoa, L. P. | Process for making aqueous betaine solutions |
| DE19755558A1 (en) * | 1997-12-13 | 1999-06-17 | Henkel Kgaa | Odor-enhanced betaine solutions |
| CN100404117C (en) * | 2005-12-01 | 2008-07-23 | 江南大学 | Preparation method of alpha-alkyl betaine amphoteric surfactant |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2926479C2 (en) * | 1979-06-30 | 1981-10-08 | Th. Goldschmidt Ag, 4300 Essen | Process for the production of betaines |
| DE4205880A1 (en) * | 1992-02-26 | 1993-09-02 | Goldschmidt Ag Th | PROCESS FOR THE PRODUCTION OF BETAINES |
| DE4211190A1 (en) * | 1992-04-03 | 1993-10-07 | Hoechst Ag | Process for the preparation of aqueous betaine solutions |
-
1995
- 1995-01-21 EP EP95100812A patent/EP0665213A1/en not_active Withdrawn
- 1995-01-27 JP JP1169495A patent/JPH07278071A/en not_active Withdrawn
- 1995-01-27 CA CA 2141259 patent/CA2141259A1/en not_active Abandoned
- 1995-01-27 BR BR9500360A patent/BR9500360A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114191841A (en) * | 2021-11-30 | 2022-03-18 | 宜兴市天石饲料有限公司 | Efficient betaine crystallization method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0665213A1 (en) | 1995-08-02 |
| JPH07278071A (en) | 1995-10-24 |
| BR9500360A (en) | 1997-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5292942A (en) | Process for the preparation of aqueous betaine solutions | |
| US7183434B2 (en) | Process for the continuous quaternization of tertiary amines with an alkyl halide | |
| CA2141259A1 (en) | Process for the preparation of betaines | |
| US6444846B1 (en) | Process for preparing tetrafluoroborate salt and intermediates thereof | |
| CA1106411A (en) | Process for preparing bis (n,n-dialkylamino) alkyl ethers | |
| JPH0237341B2 (en) | ||
| CA2028047A1 (en) | Process for preparing quaternary ammonium compounds | |
| AU614464B2 (en) | Process for the preparation of antimicrobial formulations of 2-(alkylthio)ethanamine hydrohalides | |
| US5025038A (en) | Process for the preparation of antimicrobial formulations of 2-(alkylthio)ethanamine hydrohalides | |
| JP5843846B2 (en) | Mixtures of polyfluoroalkylsulfonamidoalkylamines | |
| US4845300A (en) | Synthesis of 2-(perfluoroalkyl) ethanethiols | |
| EP0009041B1 (en) | Process for preparing aromatic amide antioxidants | |
| EP0179443B1 (en) | Novel fluorine-containing amine amides and preparation thereof | |
| IE54312B1 (en) | Process for the preparation of beta-(2-methylpropoxy)-methyl-n-phenyl-n-(phenylmenthyl)-1-pyrrolidineethanamine | |
| JP3931737B2 (en) | Method for producing quaternary ammonium halide salt | |
| US4369145A (en) | Preparation of fluorobenzenesulfonyl fluorides by exchange fluorination | |
| CA1060037A (en) | Method of preparing mercaptans | |
| JP2837254B2 (en) | Method for producing N-alkyl- or N, N-dialkyl-1,2-diaminoethane | |
| WO1992002486A1 (en) | Processes for preparing secondary and tertiary amines | |
| JP3426785B2 (en) | Method for producing quaternary ammonium salt | |
| EP1140798A1 (en) | Process for the preparation of flowable concentrated betaine solution | |
| RU2149155C1 (en) | Method of preparing unsaturated chlorohydrocarbons | |
| JP3427518B2 (en) | Method for producing diallyldialkylammonium compound | |
| JPH082852B2 (en) | Method for producing surfactant | |
| KR910003635B1 (en) | Process for the preparation of 2-(2-naphthyloxy)propion anilide derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |