US2816911A - Process for the preparation of n-alkyl beta-alanines - Google Patents
Process for the preparation of n-alkyl beta-alanines Download PDFInfo
- Publication number
- US2816911A US2816911A US412092A US41209254A US2816911A US 2816911 A US2816911 A US 2816911A US 412092 A US412092 A US 412092A US 41209254 A US41209254 A US 41209254A US 2816911 A US2816911 A US 2816911A
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- US
- United States
- Prior art keywords
- amine
- lower alkyl
- reaction
- excess
- carbon atoms
- 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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- 238000000034 method Methods 0.000 title claims description 9
- 150000001412 amines Chemical class 0.000 claims description 13
- -1 ACRYLATE ESTER Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010040914 Skin reaction Diseases 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000430 skin reaction Toxicity 0.000 description 1
- 230000035483 skin reaction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/38—Dispersants; Agents facilitating spreading
Definitions
- the present invention relates to the reaction between lower alkyl acrylates and long chain primary amines to form the adduct RNHC H COOR in which R is an aliphatic hydrocarbon chain containing from 8 to 22 carbon atoms and R is a lower alkyl group containing from 1 to 4 carbons atoms. These compounds may be hydrolyzed to form salts which are useful as surface active agents.
- Adducts of this type are disclosed in the Isbell Patent 2,468,014.
- the reaction mixture was maintained at temperatures of from 25-30 C. It has now been discovered that when operating at temperatures of 25-30 C. the reaction proceeds to form not only the monoadduct referred to above, but also to product substantial quantities of the diadduct RN(C H COOR It has also been discovered that by operating within the temperature range of 50 to 120 C. it is possible to control the reaction to form maximum percentages of the monoadducts. Since the hydrolized products derived from the monoadducts diifer in their properties from the hydrolyzed product of the monoadduct, it is frequently desirable to control the reaction so as to obtain the maximum quantity of each of these products.
- the present invention involves a process in which the maximum percentages of the monoadducts may be obtained.
- an object of the present invention to provide a novel process of reacting lower alkyl acrylate esters with primary fatty amines in order to obtain the monoadduct referred to above, while at the same time minimizing the formation of the diadduct and also minimizing the residual free primary amine in the reaction product.
- the fatty amines which may be employed in the pres- 2 16,911 Patented Dec. 17, 1957 2 en'tinve'ntion are the primary fatty a'minesin which the fatty group contains from 8m 22 carbon atoms. These maybe single isolated fatty amines or may be mixed fatty amines derived from the fatty acids of a fat or oil or from any selected fraction thereof. The amines may be either saturated or unsaturated.
- the acrylate esters which may be employed are the lower alkyl acrylates containing from 1 to 4 carbon atoms in the alcohol portion of the ester. These include methyl, ethyl, propyl, and butyl esters. Since methyl acrylate is readily available commercially, it is preferred.
- the amine and the acrylate ester are mixed, the acrylate ester being employed in an excess of from 10 to 30%. A preferred excess of the acrylate is from 15 to 30%.
- the reaction mixture is heated and agitated at temperatures within the approximate range of 50 to 120 C. The time period will vary depending upon the temperature and the particular ex cess of acrylate employed. At temperatures of 120 C. a time period of 1 hour is suitable whereas at temperatures of 80 to 100 C. up to 4 hours are required. At temperatures of around 60 C. time periods up to 6 hours are necessary. Extended reaction times at 120 C. over and above those required for the formation of the product are undesirable inasmuch as there is some tendency for the formation of the amino amide The following examples will serve to illustrate the invention:
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent PROCESS FOR THE PREPARATION OF N-ALKYL p-ALANINES David Aelony, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of Delaware No Drawing. Application February 23, 1954 Serial No. 412,092
2 Claims. (Cl. 260-482) The present invention relates to the reaction between lower alkyl acrylates and long chain primary amines to form the adduct RNHC H COOR in which R is an aliphatic hydrocarbon chain containing from 8 to 22 carbon atoms and R is a lower alkyl group containing from 1 to 4 carbons atoms. These compounds may be hydrolyzed to form salts which are useful as surface active agents.
Adducts of this type are disclosed in the Isbell Patent 2,468,014. In that patent the reaction mixture was maintained at temperatures of from 25-30 C. It has now been discovered that when operating at temperatures of 25-30 C. the reaction proceeds to form not only the monoadduct referred to above, but also to product substantial quantities of the diadduct RN(C H COOR It has also been discovered that by operating within the temperature range of 50 to 120 C. it is possible to control the reaction to form maximum percentages of the monoadducts. Since the hydrolized products derived from the monoadducts diifer in their properties from the hydrolyzed product of the monoadduct, it is frequently desirable to control the reaction so as to obtain the maximum quantity of each of these products. The present invention involves a process in which the maximum percentages of the monoadducts may be obtained.
In preparing surface active materials by this method, it is imperative that the quantity of unreacted primary amine in the product be maintained at a very low level. Many people experience undesirable skin reactions from contact with long chain primary amines. Accordingly, it is necessary either to insure that substantially all the primary amines are reacted or to employ some process which will remove unreacted amine from the reaction product. The removal of unreacted amine from the reaction product is diflicult and accordingly it is preferred to employ reaction conditions which will insure the complete reaction of the primary fatty amine employed as starting material. In order to insure more complete reaction, it is desirable to employ an excess of the acrylate ester in the addition reaction. However, the use of an excess of the acrylate ester has the tendency to increase the formation of the diadducts. It has been found that by employing an excess of the acrylate ester which is limited to from 10 to 30% of the theoretical quantity and by employing the temperature conditions referred to above it is possible to obtain high yields of the monoadduct with relatively low levels of the diadduct and at the same time substantially completely eliminating the residual primary amine.
It is, therefore, an object of the present invention to provide a novel process of reacting lower alkyl acrylate esters with primary fatty amines in order to obtain the monoadduct referred to above, while at the same time minimizing the formation of the diadduct and also minimizing the residual free primary amine in the reaction product.
The fatty amines which may be employed in the pres- 2 16,911 Patented Dec. 17, 1957 2 en'tinve'ntion are the primary fatty a'minesin which the fatty group contains from 8m 22 carbon atoms. These maybe single isolated fatty amines or may be mixed fatty amines derived from the fatty acids of a fat or oil or from any selected fraction thereof. The amines may be either saturated or unsaturated.
The acrylate esters which may be employed are the lower alkyl acrylates containing from 1 to 4 carbon atoms in the alcohol portion of the ester. These include methyl, ethyl, propyl, and butyl esters. Since methyl acrylate is readily available commercially, it is preferred.
In carrying on the reaction, the amine and the acrylate ester are mixed, the acrylate ester being employed in an excess of from 10 to 30%. A preferred excess of the acrylate is from 15 to 30%. The reaction mixture is heated and agitated at temperatures within the approximate range of 50 to 120 C. The time period will vary depending upon the temperature and the particular ex cess of acrylate employed. At temperatures of 120 C. a time period of 1 hour is suitable whereas at temperatures of 80 to 100 C. up to 4 hours are required. At temperatures of around 60 C. time periods up to 6 hours are necessary. Extended reaction times at 120 C. over and above those required for the formation of the product are undesirable inasmuch as there is some tendency for the formation of the amino amide The following examples will serve to illustrate the invention:
Dodecyl amine (187 g.) was heated to 60 C. Methyl acrylate (103 g., 20% excess) was added at once and Per- Percent Percent Percent See. No. Temp., Time, cent Amine primary sec. tert. amine] O. hours excess No. amine amine amine rt.
amine 1... -90 4 20 200. 1 2. 2 83. 8 l2. 6 6. 65 2- 80-90 4 30 197. l O 83. 9 14. 2 5. 9 3 120 4 10 192. 2 4. 9 77. 5 10. 9 7. l8 4.-.. 60 6 10 202. 0 7. 1 79. 8 9. 8 8. 1 5. 6 10 194.0 4.8 82.6 8.2 10.0 6.-.- 1 30 202. 7 3. 5 85. 5 9. 6 8.9
I hereby claim as my inventlonz 1. Process of preparing compounds having the formula RNHC H COOR in which R is an aliphatic hydrocarbon group containing from 8 to 22 carbon atoms and R is a lower alkyl group containing from 1 to 4 carbon atoms which comprises reacting the corresponding amine RNH with the corresponding lower alkyl acrylate ester, the ester being employed in an excess of from 10-30%, at temperatures within the approximate range of 50- 120 C.
2. Process of preparing compounds having the formula RNHC H COOR in which R is an aliphatic hydrocar- 3 w 4 bon group containing from 8-22 carbon atoms and R References Cited in the file of this patent is a lower alkyl group containing from 1 to 4 carbon UNITED STATES PATENTS atoms which comprises reacting the corresponding amino RNH with the corresponding lower alkyl acrylate ester, 2,017,537 Hoffman et 1935 the ester being employed in an excess of from 15-30%, at 5 2,438,091 Lynch 1948 2,468,012 Isbell Apr. 19, 1949 t t 'thi th t {so-120 c.
empem n e appmxma flange 2,720,536 Aelony et a1. Oct. 11, 1955
Claims (1)
1. PROCESS OF PREPARING COMPOUNDS HAVING THE FORMULA RNHC2H4COOR1 IN WHICH R IS AN ALIPHATIC HYDROCARBON GROUP CONTAINING FROM 8 TO 22 CARBON ATOMS AND R1 IS A LOWER ALKYL GROUP CONTAINING FROM 1 TO 4 CARBON ATOMS WHICH COMPRISES REACTING THE CORRESPONDING AMINE RNH2 WITH THE CORRESPONDING LOWER ALKYL ACRYLATE ESTER, THE ESTER BEING EMPLOYED IN AN EXCESS OF FROM 10-30%, AT TEMPERATURES WITHIN THE APPROXIMATE RANGE OF 50120*C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US412092A US2816911A (en) | 1954-02-23 | 1954-02-23 | Process for the preparation of n-alkyl beta-alanines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US412092A US2816911A (en) | 1954-02-23 | 1954-02-23 | Process for the preparation of n-alkyl beta-alanines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2816911A true US2816911A (en) | 1957-12-17 |
Family
ID=23631578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US412092A Expired - Lifetime US2816911A (en) | 1954-02-23 | 1954-02-23 | Process for the preparation of n-alkyl beta-alanines |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2816911A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223700A (en) * | 1960-06-11 | 1965-12-14 | Knoll Ag | Glycine amides |
| US3424771A (en) * | 1967-07-11 | 1969-01-28 | Lumin Chem Co | Novel amido derivatives useful as aids in detergent compositions |
| US5922909A (en) * | 1998-03-31 | 1999-07-13 | Akzo Nobel Nv | Process for the selective control of Zwitterionic amphoteric compositions |
| US10035757B2 (en) | 2010-06-03 | 2018-07-31 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2017537A (en) * | 1931-08-26 | 1935-10-15 | Ig Farbenindustrie Ag | Production of hydroxy-alkylamino carboxylic acid compounds |
| US2438091A (en) * | 1943-09-06 | 1948-03-16 | American Cyanamid Co | Aspartic acid esters and their preparation |
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
| US2720536A (en) * | 1953-11-18 | 1955-10-11 | Gen Mills Inc | Inactivation of primary amines in beta-alanine detergent mixture compositions |
-
1954
- 1954-02-23 US US412092A patent/US2816911A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2017537A (en) * | 1931-08-26 | 1935-10-15 | Ig Farbenindustrie Ag | Production of hydroxy-alkylamino carboxylic acid compounds |
| US2438091A (en) * | 1943-09-06 | 1948-03-16 | American Cyanamid Co | Aspartic acid esters and their preparation |
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
| US2720536A (en) * | 1953-11-18 | 1955-10-11 | Gen Mills Inc | Inactivation of primary amines in beta-alanine detergent mixture compositions |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223700A (en) * | 1960-06-11 | 1965-12-14 | Knoll Ag | Glycine amides |
| US3424771A (en) * | 1967-07-11 | 1969-01-28 | Lumin Chem Co | Novel amido derivatives useful as aids in detergent compositions |
| US5922909A (en) * | 1998-03-31 | 1999-07-13 | Akzo Nobel Nv | Process for the selective control of Zwitterionic amphoteric compositions |
| US10035757B2 (en) | 2010-06-03 | 2018-07-31 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
| US10167249B2 (en) | 2010-06-03 | 2019-01-01 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
| US10207983B2 (en) | 2010-06-03 | 2019-02-19 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
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