US2720536A - Inactivation of primary amines in beta-alanine detergent mixture compositions - Google Patents
Inactivation of primary amines in beta-alanine detergent mixture compositions Download PDFInfo
- Publication number
- US2720536A US2720536A US393015A US39301553A US2720536A US 2720536 A US2720536 A US 2720536A US 393015 A US393015 A US 393015A US 39301553 A US39301553 A US 39301553A US 2720536 A US2720536 A US 2720536A
- Authority
- US
- United States
- Prior art keywords
- alanine
- primary amines
- aldehyde
- primary
- inactivation
- 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 - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 23
- 150000003141 primary amines Chemical class 0.000 title claims description 23
- 239000003599 detergent Substances 0.000 title claims description 22
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 title claims 5
- 230000002779 inactivation Effects 0.000 title description 3
- 229940000635 beta-alanine Drugs 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 8
- 230000000415 inactivating effect Effects 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 description 20
- 239000000047 product Substances 0.000 description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- -1 alkali metal salts Chemical class 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 208000017520 skin disease Diseases 0.000 description 2
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 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
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
Definitions
- the present invention relates to the inactivation of primary amines in [ii-alanine detergent mixture compositions.
- the fi-alanine detergents contemplated by the present invention are those having the following formula: RNHCHzCHzCOOH in which R is the long-chain aliphatic hydrocarbon group containing from 8 to 22 carbon atoms. In place of the acid the salts and esters may be used.
- detergents may be made as disclosed in Isbell Patent 2,468,012. According to that patent primary fatty amines are condensed with methyl acrylate to obtain the ester addition compound. This compound may then be hydrolized to the acid or converted to a salt such as the alkali metal salts, ammonium salts, and other organic base salts.
- any free primary amine remains in the reaction mixture. It has now been found however, that under some reaction conditions a small quantity of free primary amine may remain in the reaction mixture and is difficult to remove. These free primary amines may cause skin disorders and accordingly it is desirable to obtain a detergent composition which is free from the primary fatty amines. It has now been discovered that by reacting the detergent composition with an aldehyde that the fatty primary amine may be modified in such a way that the detergent composition does not cause skin disorders in case of persons sensitive to primary amines.
- a wide variety of primary fatty amines may be employed for the preparation of these detergents.
- These amines may contain from 8 to 22 carbon atoms and may be the mixed amines obtained from the mixed fatty acids of an oil or from any selected individual acid or any selected group of acids.
- the amines may be the saturated or unsaturated.
- These amines may be reacted with an acrylate ester especially the lower aliphatic acrylate esters in which the alcohol group of the ester contains from 1 to 4 carbon atoms.
- ester addition compound thus obtained rather than any of the hydrolysis products such as the acid or salts.
- aldehyde The process of inactivating the primary amines involves the simple addition of an aldehyde to the detergent product.
- aldehydes A wide variety of aldehydes may be employed including both aromatic and aliphatic aldehydes. Benzaldehyde and salicylaldehyde has been found to be particularly effective. Likewise the aliphatic aldehydes such as butyraldehyde has been found to be very effective. Other aldehydes such as formaldehyde and. glyoxal may also be used but are generally not as desirable as some of the preferredaldehydes referred to above.
- the aldehyde is merely added to the reaction mixture and no special reaction conditions arerequired.
- the reaction proceedsat room temperature in a reasonable period of time.
- these detergents are not ordinarily used immediately the aldehyde may simply be added to the reaction mixture and reaction will have been completed by the time that the detergent is used after having distributed through the normal channels of commerce. If desired the reaction may be speeded up by employing higher temperatures. Likewise it is not necessary to employ solvents, catalysts or other reaction aids, although, of course these may be used if desired.
- Example 1 To prepare the p-alanine methyl ester, distilled amine derived from coconut fatty acids was used. This product had an amine number of 274.6. Amine number is defined as the mg. of KOH equivalent to the free amine in 1 g. of product. It is determined by titrating a solution of the amine in ethyl alcohol toluene to a bromcresol green end point with aqueous hydrochloric acid. Also, it may be determined by titrating with perchloric acid in anhydrous acetic acid solution, as described by Terry, Eilar, and Moe in Analytical Chemistry (volume 24 for 1952).
- the coco amine (306 g.) was heated to C. under a vacuum of 10 mm. Thereafter, it was cooled to 40 C. and methyl acrylate (142 g.) was added over a period of 8 minutes. The mixture was agitated at 40 C. for 6 hours. Vacuum was applied and the mixture was heated to 100 C. at 40p to remove volatile material.
- the product weighed 438 g. It had an amine number of 188.6, a primary amine content of 8.2 and a secondary amine content of 83.9.
- To this ester (20 g.) was added salicylaldehyde (1.1 g.) and the solution was allowed to stand for 24 hours. The primary amine content at the end of this time had decreased to 0.5%.
- Example 2 The above experiment was repeated save that 0.96 g. of benzaldehyde was used instead of salicylaldehyde. In this instance the final product had a primary amine content of 0.
- Example 3 Amine number 170.9 Primary amine content 1.4 Secondary amine content 81.2 Tertiary amine content 13.7
- a process of inactivating free primary amines in a fl-alanine detergent composition in which the 'fl-alanine contains an aliphatic hydrocarbon substituent of from '8 to 22 carbon atoms on the amino nitrogen which comprises reacting said 'fl-alanine detergent composition with an aldehyde which is reactive with primary amines to produce products inert to human skin.
- a process of inactivating free primary amines in a B-alanine detergent composition in which the fl-alanine contains an aliphatic hydrocarbon substituent of from 8 'to 22 carbon'atorns on the amino nitrogen which comprises reacting said p-alanine detergent composition 15 with a quantity of an aldehyde substantially equivalent to the freeuprimary amine content of the detergent composition, said aldehyde being reactive with primary amines to produce products inert to human skin.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United SW68 fi O INACTIVATION F PRIMARYAMINES IN p-ALANINE DETERGENT 'MIXTURE COMPOSITIONS 1 1 David Aelony and Harold Wittcolf, Minneapolis, Minn.,
assignors to GeneralMills, Inc., a corporation of Delaware No Drawing. Application November 18, "1953,. Serial No. 393,015
5 Claims. (Cl. 260-482) The present invention relates to the inactivation of primary amines in [ii-alanine detergent mixture compositions. The fi-alanine detergents contemplated by the present invention are those having the following formula: RNHCHzCHzCOOH in which R is the long-chain aliphatic hydrocarbon group containing from 8 to 22 carbon atoms. In place of the acid the salts and esters may be used.
These detergents may be made as disclosed in Isbell Patent 2,468,012. According to that patent primary fatty amines are condensed with methyl acrylate to obtain the ester addition compound. This compound may then be hydrolized to the acid or converted to a salt such as the alkali metal salts, ammonium salts, and other organic base salts.
Heretofore it has not been considered that any free primary amine remains in the reaction mixture. It has now been found however, that under some reaction conditions a small quantity of free primary amine may remain in the reaction mixture and is difficult to remove. These free primary amines may cause skin disorders and accordingly it is desirable to obtain a detergent composition which is free from the primary fatty amines. It has now been discovered that by reacting the detergent composition with an aldehyde that the fatty primary amine may be modified in such a way that the detergent composition does not cause skin disorders in case of persons sensitive to primary amines.
It is therefore an object of the present invention to provide a process of inactivating primary amine in alanine detergent mixture compositions by means of an aldehyde. It is also an object of the present invention to provide a novel fl-alanine detergent mixture composition in which free primary fatty amine has been inactivated by means of an aldehyde.
As disclosed in the Isbell patent a wide variety of primary fatty amines may be employed for the preparation of these detergents. These amines may contain from 8 to 22 carbon atoms and may be the mixed amines obtained from the mixed fatty acids of an oil or from any selected individual acid or any selected group of acids. The amines may be the saturated or unsaturated. These amines may be reacted with an acrylate ester especially the lower aliphatic acrylate esters in which the alcohol group of the ester contains from 1 to 4 carbon atoms.
For the purpose of inactivating free primary amines it is preferred to treat the ester addition compound thus obtained rather than any of the hydrolysis products such as the acid or salts. However, it is also possible to inactivate the primary amine by treatment either of the acid obtained by hydrolysis of the ester or by treating the alkali metal salts such as sodium and potassium salts of the acid.
The process of inactivating the primary amines involves the simple addition of an aldehyde to the detergent product. A wide variety of aldehydes may be employed including both aromatic and aliphatic aldehydes. Benzaldehyde and salicylaldehyde has been found to be particularly effective. Likewise the aliphatic aldehydes such as butyraldehyde has been found to be very effective. Other aldehydes such as formaldehyde and. glyoxal may also be used but are generally not as desirable as some of the preferredaldehydes referred to above.
The aldehyde is merely added to the reaction mixture and no special reaction conditions arerequired. The reaction proceedsat room temperature in a reasonable period of time. Thus since these detergents are not ordinarily used immediately the aldehyde may simply be added to the reaction mixture and reaction will have been completed by the time that the detergent is used after having distributed through the normal channels of commerce. If desired the reaction may be speeded up by employing higher temperatures. Likewise it is not necessary to employ solvents, catalysts or other reaction aids, although, of course these may be used if desired. It is preferred to employ approximately an amount of the aldehyde equivalent to the free primary fatty amine. Generally this will result in a reduction of the free amine content to considerably less than 1% even when starting with a detergent composition containing as high as 10% of the free primary fatty amines. Naturally, if desired, excess aldehyde may be used.
Example 1 To prepare the p-alanine methyl ester, distilled amine derived from coconut fatty acids was used. This product had an amine number of 274.6. Amine number is defined as the mg. of KOH equivalent to the free amine in 1 g. of product. It is determined by titrating a solution of the amine in ethyl alcohol toluene to a bromcresol green end point with aqueous hydrochloric acid. Also, it may be determined by titrating with perchloric acid in anhydrous acetic acid solution, as described by Terry, Eilar, and Moe in Analytical Chemistry (volume 24 for 1952).
The coco amine (306 g.) was heated to C. under a vacuum of 10 mm. Thereafter, it was cooled to 40 C. and methyl acrylate (142 g.) was added over a period of 8 minutes. The mixture was agitated at 40 C. for 6 hours. Vacuum was applied and the mixture was heated to 100 C. at 40p to remove volatile material. The product weighed 438 g. It had an amine number of 188.6, a primary amine content of 8.2 and a secondary amine content of 83.9. To this ester (20 g.) was added salicylaldehyde (1.1 g.) and the solution was allowed to stand for 24 hours. The primary amine content at the end of this time had decreased to 0.5%.
Example 2 The above experiment was repeated save that 0.96 g. of benzaldehyde was used instead of salicylaldehyde. In this instance the final product had a primary amine content of 0.
Example 3 Amine number 170.9 Primary amine content 1.4 Secondary amine content 81.2 Tertiary amine content 13.7
This product (357 g.) was mixed with butyraldehyde (12 g.) and allowed to stand overnight at room temperature. 'The primary amine content of the treated material decreased from 1 .4 to- 0.09
We claim as our invention:
I. A process of inactivating free primary amines in a fl-alanine detergent composition in which the 'fl-alanine contains an aliphatic hydrocarbon substituent of from '8 to 22 carbon atoms on the amino nitrogen, which comprises reacting said 'fl-alanine detergent composition with an aldehyde which is reactive with primary amines to produce products inert to human skin.
2. A process of inactivating free primary amines in a B-alanine detergent composition in which the fl-alanine contains an aliphatic hydrocarbon substituent of from 8 'to 22 carbon'atorns on the amino nitrogen which comprises reacting said p-alanine detergent composition 15 with a quantity of an aldehyde substantially equivalent to the freeuprimary amine content of the detergent composition, said aldehyde being reactive with primary amines to produce products inert to human skin.
3. Process according to claim 1 in which the aldehyde is benzaldehyde.
4. Process according to claim 1 in which the aldehyde is salicylaldehyde.
5. Process according to claim 1 in which the aldehyde 10 is butyraldehyde.
References Cited in thefile of this patent UNITED STATES PATENTS 2,468,012 Isbell Apr. 19; 1949
Claims (1)
1. A PROCESS OF INACTIVATING FREE PRIMARY AMINES IN A B-ALANINE DETERGENT COMPOSITION IN WHICH THE B-ALANINE CONTAINS AN ALIPHATIC HYDROCARBON SUBSTITUENT OF FROM 8 TO 22 CARBON ATOMS ON THE AMINO NITROGEN, WHICH COMPRISES REACTING SAID B-ALANINE DETERGENT COMPOSITION WITH AN ALDEHYDE WHICH IS REACTIVE WITH PRIMARY AMINES TO PRODUCE PRODUCTS INERT TO HUMAN SKIN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US393015A US2720536A (en) | 1953-11-18 | 1953-11-18 | Inactivation of primary amines in beta-alanine detergent mixture compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US393015A US2720536A (en) | 1953-11-18 | 1953-11-18 | Inactivation of primary amines in beta-alanine detergent mixture compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2720536A true US2720536A (en) | 1955-10-11 |
Family
ID=23552942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US393015A Expired - Lifetime US2720536A (en) | 1953-11-18 | 1953-11-18 | Inactivation of primary amines in beta-alanine detergent mixture compositions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2720536A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2816911A (en) * | 1954-02-23 | 1957-12-17 | Gen Mills Inc | Process for the preparation of n-alkyl beta-alanines |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
-
1953
- 1953-11-18 US US393015A patent/US2720536A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2816911A (en) * | 1954-02-23 | 1957-12-17 | Gen Mills Inc | Process for the preparation of n-alkyl beta-alanines |
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