US2787633A - Acceleration of fatty amine addition reactions - Google Patents
Acceleration of fatty amine addition reactions Download PDFInfo
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- US2787633A US2787633A US413460A US41346054A US2787633A US 2787633 A US2787633 A US 2787633A US 413460 A US413460 A US 413460A US 41346054 A US41346054 A US 41346054A US 2787633 A US2787633 A US 2787633A
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- fatty
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- 150000001412 amines Chemical class 0.000 title description 16
- 238000007259 addition reaction Methods 0.000 title description 4
- 230000001133 acceleration Effects 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 150000002825 nitriles Chemical class 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-YZRHJBSPSA-N (214C)propan-2-ol Chemical compound [14CH](C)(C)O KFZMGEQAYNKOFK-YZRHJBSPSA-N 0.000 claims 1
- LRHPLDYGYMQRHN-DOMIDYPGSA-N 61990-73-6 Chemical compound CCC[14CH2]O LRHPLDYGYMQRHN-DOMIDYPGSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-HQMMCQRPSA-N Ethanol-14C Chemical compound C[14CH2]O LFQSCWFLJHTTHZ-HQMMCQRPSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 16
- 150000003141 primary amines Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 241000605112 Scapanulus oweni Species 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 2
- 101100346764 Mus musculus Mtln gene Proteins 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- -1 aliphatic alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 241000288748 Chrysochloridae Species 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 206010040914 Skin reaction Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 231100000430 skin reaction Toxicity 0.000 description 1
- 230000035483 skin reaction Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Definitions
- the present invention relates to the acceleration of the addition reaction between primary fatty amines and alpha beta unsaturated acid derivatives of the acrylate type.
- primary fatty amines and alpha beta unsaturated acid derivatives of the acrylate type such as the lower aliphatic esters and nitriles of acrylic acid, methacrylic acid, crotonic acid.
- an object of the present invention to provide a process of condensing fatty amines with acrylate type compounds in the presence of lower aliphatic alcohols or dioxane in order to accelerate the addition rate.
- the reaction is applicable to the long chain primary fatty amines of the type RNHz in which R is an aliphatic hydrocarbon group containing from 8 to 22 carbon atoms.
- R is an aliphatic hydrocarbon group containing from 8 to 22 carbon atoms.
- These primary amines are conventionally produced from fatty acids by way of the nitrile.
- the amines which may be used in the present invention are those which may be derived from the whole fatty acids of a fat or oil, from any selected fraction thereof, or from any individual fatty acid. Since the starting fatty acids may be either saturated or unsaturated, the resulting amines may likewise be either saturated or unsaturated.
- the acrylate derivatives to which the present invention is applicable are the nitriles and lower aliphatic esters of acrylic acid, crotonic acid and .methacrylic acid.
- the alcohol portion of the ester may bean alkyl group cohtaining from 1 to 4 carbon atoms. Since these compounds are readily available in form of their methyl esters these are preferred.
- the alcohols which may be employed are the lower aliphatic alcohols, methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanolsand tertiary butanols.
- 1,4 dioxane likewise serves to accelerate this reaction.
- the quantity of the additive need be relatively small. Thus even when such a lowproportion as 2% 'based on the total weight of the reactants is employed, the reaction speeds up materially. Generally quantities of from 5 to are preferred although it ispossible to use up to 25%. No particular advantage is obtained using quantities of additive over 25% and actually the use of larger quantities usually requires some recovery technique.
- the amine and the additive material are mixed and heated to the desired reaction temperature and maintained at this temperature during and after the addition of the acrylate.
- the reaction requires a United States Patent 0 2,787,633 Patented Apr. 2, 1957 somewhat extended period of time. Accordingly, it is preferred to carry out the reaction'at' temperatures of from 60 to 120 C. At these temperatures with the additive present the reactionmay be essentially complete in from 1 to 35 minutes.
- addition compounds are frequently hydrolized to the salts to form surfactants. Accordingly, the small quantity of alcohol or-dioxane which may be present may be allowed to remain in the reaction mixture during the saponification. If desired, of course, the additive may be vaporized from the reactionmixture prior to saponification but usually this is not necessary.
- the invention In addition to speedingup the rate of reaction, the invention also has other advantages. Inasmuch as these adducts are frequently used as intermediates for the preparation of surfactants, it is desirable that the quantity of free primary amine in the product be reduced to a minimum inasmuch as the free primary amines may produce undesirable skin reactions. Heretofore, in order to attain this end it has been customary to use a large excess of methyl acrylate. The recovery of the excess methyl acrylate has involved an additional processing step. a
- the use of the excess .methyl acrylate has also presented an additional problem.
- the reaction of primary fatty amines with methyl acrylate may involve the addition of a single acrylate unit to the primary amine or it may involve the addition of two acrylate units inasmuch as there are two availablehydrogens on the primary amine.
- the reaction of primary fatty amines with methyl acrylate may involve the addition of a single acrylate unit to the primary amine or it may involve the addition of two acrylate units inasmuch as there are two availablehydrogens on the primary amine.
- the use of the excess acrylate which serves to reduce the free primary amine content also serves to increase the quantity of diadduct.
- the saponification of sizeable quantities of the adduct may be carried out in an autoclave using concentrated alkali such as a 50% aqueous solution of sodium hydroxide. Some alcohol is, of course, liberated due to the saponification of the ester. If this is the only alcohol present, however, the saponified product is a heavy paste which is diflicult to handle. If suflicient alcohol is present so that the total solids content of the saponified product is to a slurry is obtained which can readily be pumped. If water is present in the saponified mixture so that the saponified product contains 70 to 75 solids, the product is a stiff paste which cannot be pumped.
- concentrated alkali such as a 50% aqueous solution of sodium hydroxide.
- EXAMPLE 1 211 g. (1 g. mole) of a special coco amine (stripped of Ca and C10 amines) were placed in a one liter three necked flask equipped with mechanical stirrer, thermometer, reflux condenser and Mantle heater. Methanol .(23 g.) was added and the, solution heated to reflux at 90 C. To the refluxing solution 94.6 g. (1.1 g. moles) of methyl acrylate was added over a period of 2 to 3 minutes. Three samples of the reaction mixture were taken and chilled to stop reaction. One was taken immediately after methyl acrylate was added, another four minutes later and a third fifteen minutes after the completion of addition of the acrylate. They were called the one, five and fifteen minute samples. The results of the analyses of these samples are given in Table 1, Examples 7, 8 and 9.
- Process which comprises reacting a primary fatty amine in which the fatty group contains from 8 to 22 carbon atoms with a compound selected from the group consisting of the nitriles and lower alkyl esters of acrylic acid, methacrylic acid, and crotonic acid in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, tertiary butanols and dioxane, said additive being present in the quantity of from 2 to 25% based on the total weight of reactants.
- Process which comprises reacting a primary fatty amine in which the fatty group contains from 8 to 22 carbon atoms with a lower alkyl acrylate in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, tertiary butanols and dioxane, said additive being present in a quantity of from 225% based on the total weight of reactants.
- an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, tertiary butanols and dioxane
- Process which comprises reacting a fatty primary amine in which the fatty group contains from 8 to 22 carbon atoms with a substantially equimolar amount of a lower alkyl acrylate at a temperature of approximately 60 to approximately C. in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols,nicemas tiaiy butanols and dioxane, said additive being present in a quantity of from 2-25% based on the total weight of reactants.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ACCELERATIDNOF FATTY AMINE ADDITHON REACTIONS Stuart A. Harrison and David Aelony, Minneapoiis, Minn, assignors to General Mills, Inc., a corporation of Delaware No Drawing. Application March 1, 1954, Serial No. 413,460
6 Claims. (Cl. 260--465.5)
The present invention relates to the acceleration of the addition reaction between primary fatty amines and alpha beta unsaturated acid derivatives of the acrylate type. such as the lower aliphatic esters and nitriles of acrylic acid, methacrylic acid, crotonic acid.
Condensations of this type have previously been disclosed as shown in Isbell Patent 2,468,012. It has now been discovered that it is possible to materially accelerate the reaction rate in this type of addition by carrying out the reaction in the presence of a lower aliphatic alcohol or 1,4 dioxane. The quantity of the alcohol or dioxane employed may be relatively small, much less than is customarily considered as a solvent quantity.
It is, therefore, an object of the present invention to provide a process of condensing fatty amines with acrylate type compounds in the presence of lower aliphatic alcohols or dioxane in order to accelerate the addition rate.
The reaction is applicable to the long chain primary fatty amines of the type RNHz in which R is an aliphatic hydrocarbon group containing from 8 to 22 carbon atoms. These primary amines are conventionally produced from fatty acids by way of the nitrile. Accordingly, the amines which may be used in the present invention are those which may be derived from the whole fatty acids of a fat or oil, from any selected fraction thereof, or from any individual fatty acid. Since the starting fatty acids may be either saturated or unsaturated, the resulting amines may likewise be either saturated or unsaturated.
The acrylate derivatives to which the present invention is applicable are the nitriles and lower aliphatic esters of acrylic acid, crotonic acid and .methacrylic acid. The alcohol portion of the ester may bean alkyl group cohtaining from 1 to 4 carbon atoms. Since these compounds are readily available in form of their methyl esters these are preferred.
The alcohols which may be employed are the lower aliphatic alcohols, methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanolsand tertiary butanols. In addition it has been observed that 1,4 dioxane likewise serves to accelerate this reaction.
The quantity of the additive need be relatively small. Thus even when such a lowproportion as 2% 'based on the total weight of the reactants is employed, the reaction speeds up materially. Generally quantities of from 5 to are preferred although it ispossible to use up to 25%. No particular advantage is obtained using quantities of additive over 25% and actually the use of larger quantities usually requires some recovery technique.
The amine and the additive material are mixed and heated to the desired reaction temperature and maintained at this temperature during and after the addition of the acrylate. At room temperature the reaction requires a United States Patent 0 2,787,633 Patented Apr. 2, 1957 somewhat extended period of time. Accordingly, it is preferred to carry out the reaction'at' temperatures of from 60 to 120 C. At these temperatures with the additive present the reactionmay be essentially complete in from 1 to 35 minutes.
These addition compounds are frequently hydrolized to the salts to form surfactants. Accordingly, the small quantity of alcohol or-dioxane which may be present may be allowed to remain in the reaction mixture during the saponification. If desired, of course, the additive may be vaporized from the reactionmixture prior to saponification but usually this is not necessary.
In addition to speedingup the rate of reaction, the invention also has other advantages. Inasmuch as these adducts are frequently used as intermediates for the preparation of surfactants, it is desirable that the quantity of free primary amine in the product be reduced to a minimum inasmuch as the free primary amines may produce undesirable skin reactions. Heretofore, in order to attain this end it has been customary to use a large excess of methyl acrylate. The recovery of the excess methyl acrylate has involved an additional processing step. a
The use of the excess .methyl acrylate has also presented an additional problem. The reaction of primary fatty amines with methyl acrylate may involve the addition of a single acrylate unit to the primary amine or it may involve the addition of two acrylate units inasmuch as there are two availablehydrogens on the primary amine. For many purposes it is preferred to obtain the monoadduct. This has been difficult to accomplish when it is also desired to obtain a product with low primary amine content. The use of the excess acrylate which serves to reduce the free primary amine content also serves to increase the quantity of diadduct. By means of the present invention it is possible to carry on this reaction using only a very slight excess of the acrylate and to obtain a product which is very low in free primary amine and also very low in the diadduct. At the same time the reaction is completed in a period of a few minutes as compared with several hours as previously require Theuse of an alcohol or dioxane also is advantageous during the step of saponifying the adduct. As was pointed out above, these ester adducts are usually saponified with alkali to obtain the salt. In order to obtain a saponified product which is easy to dry, it is necessary to have a high solids content. The saponification of sizeable quantities of the adduct may be carried out in an autoclave using concentrated alkali such as a 50% aqueous solution of sodium hydroxide. Some alcohol is, of course, liberated due to the saponification of the ester. If this is the only alcohol present, however, the saponified product is a heavy paste which is diflicult to handle. If suflicient alcohol is present so that the total solids content of the saponified product is to a slurry is obtained which can readily be pumped. If water is present in the saponified mixture so that the saponified product contains 70 to 75 solids, the product is a stiff paste which cannot be pumped. By having sufiicient .alcohol present during the addition reaction, to obtain the advantages'previously presented for this addition reaction, it-is possible to saponify the adduct with 50% aqueous sodium hydroxide and obtain asaponified product having70 to 75% solids which is convenient to handle. There is no need to have more alcohol present during thesaponification than that necessary to give a solids content of 70 to 75% and actually excess alcohol may be undesirable in this stage because of undesirable side reactions.
The following examples will serve to illustrate the invention.
The results of the various examples are indicated in the following tables. The products not specifically referred to in the examples were prepared under similar conditions with the variations indicated in the table.
Table I Percent Product Analyses, Percentage Product Moles of Moles of Additive Reaction Reaction of Amines Number Amine Amine Methyl Additive Based on 'lemp., Time Acrylete Reactants degrees Primary Secondary Tertiary 1 1. 1 23. 1 G0. 1 2. 0 1 1. 1 60 18. G 70. 1 7. G 1 1. 1 60 10. 73. 8 11.8 1 1. 1 90 18. 9 74. 9 2. 3 1 1. l 00 13. 6 78. 4 4. 1 1 1. 1 90 7. 4 S0. 5 8. 2 1 1. 1 7. 00 4. 8 91. 1 4. 0 1 1.1 7. 90 5.0 91. 2 3. 8 1 1. 1 7. 90 3. 0 91. 7 5.3 1 1. 3 95 5.3 87. 2 7. 3 1 1. 15 15 75 0 Q2. 0 7. l 1 1.15 7. 5 80-100 MEL.-- 1.0 83. 4 8. 8 1 1. 1 7. 5 9O 15 :Min.-.. 4 89. 0 4. 0 Dodecyl..- 1 1. 15 l4 Dioxane.-. 5. 5 90 15 Min.... 5. 4 81. 8 7. 9 Coco 1 1.15 Benzene-.- 6. 75 90 15 M 19.1 76.0 S. 8
Table II Percent Product Analyses, Percentage Product Amine and No. Methanol Reaction Reaction of Amines Number of Moles Second Reactant Moles Based on 'lemp., "Iime,
Reactants degrees Minutes Primary Secondary Tertiary Dodecyl, 1 Mole Acrylonitrile 1.15 0 90 15 33. 8 64. 7 0 do do 1. 15 5 90 15 3. 8 94. 3 0 d0 Ethyl Crotonate 1. 15 0 9O 15 60. 2 38. 0
do (in 1.15 5 90 15 48. 4 50. 2
EXAMPLE 1 EXAMPLE 5 211 g. (1 g. mole) of a special coco amine (stripped of Ca and C10 amines) were placed in a one liter three necked flask equipped with mechanical stirrer, thermometer, reflux condenser and Mantle heater. Methanol .(23 g.) was added and the, solution heated to reflux at 90 C. To the refluxing solution 94.6 g. (1.1 g. moles) of methyl acrylate was added over a period of 2 to 3 minutes. Three samples of the reaction mixture were taken and chilled to stop reaction. One was taken immediately after methyl acrylate was added, another four minutes later and a third fifteen minutes after the completion of addition of the acrylate. They were called the one, five and fifteen minute samples. The results of the analyses of these samples are given in Table 1, Examples 7, 8 and 9.
EXAMPLE 2 Using a set-up similar to that described in Example 1, .5 g. mole of dodecyl amine containing 22.2 g. of methanol was heated to reflux (79-80 C.) and .575 g. mole of methyl acrylate was rapidly added. The temperature dropped to 75 C. and remained at this temperature. After fifteen minutes the mixture was stripped and analyzed. The results are shown in Table 1, Example 11.
EXAMPLE 3 100 g. of dodecyl amine (0.538 mole) containing 7.6 g. of methanol was heated to 90". C. and 32.8 g. (.619 mole) acrylonitrile added. After 15 minutes at this temperature the product was stripped and analyzed. For results see Table II, Example 2.
EXAMPLE 4 100 g. of dodecyl amine (0.538 mole) containing 10.6 g. of methanol was heated to 90C. and 70.5 g. (0.619 mole) of ethyl crotonate added. After 15 minutes the product was stripped and analyzed. Results are given in Table 11, Example 4. i
Thirty-two lbs. of methanol was added to 125 lbs. of distilled hydrogenated tallow amine (100% primary amine). The mixture was stirred and heated to C. in a closed kettle. Fifty-three lbs. of methyl acrylate was pumped in over a period of 18 minutes keeping the temperature below 100 C. The temperature was then brought to 100 C. and held there for one hour. Caustic soda (50% solution) was pumped into the stirred ester during a period of 17 minutes. The temperature was maintained at 95105 C. by cooling. A free flowing slurry of the soap was obtained which was dried on hot rolls to give a flaked product containing 98% solids.
We hereby claim as our invention:
1. Process which comprises reacting a primary fatty amine in which the fatty group contains from 8 to 22 carbon atoms with a compound selected from the group consisting of the nitriles and lower alkyl esters of acrylic acid, methacrylic acid, and crotonic acid in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, tertiary butanols and dioxane, said additive being present in the quantity of from 2 to 25% based on the total weight of reactants.
2. Process which comprises reacting a primary fatty amine in which the fatty group contains from 8 to 22 carbon atoms with a lower alkyl acrylate in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, tertiary butanols and dioxane, said additive being present in a quantity of from 225% based on the total weight of reactants.
3. Process which comprises reacting a fatty primary amine in which the fatty group contains from 8 to 22 carbon atoms with a substantially equimolar amount of a lower alkyl acrylate at a temperature of approximately 60 to approximately C. in the presence of an additive selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanols, terenemas tiaiy butanols and dioxane, said additive being present in a quantity of from 2-25% based on the total weight of reactants.
4. The process of claim 1 in which said additive is methanol.
5. The process of claim 2 in which said additive is methanol.
6. The process of claim 3 in which said additive is methanol.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. PROCESS WHICH COMPRISES REACTING A PRIMARY FATTY AMINE IN WHICH THE FATTY GROUP CONTAINS FROM 8 TO 22 CARBON ATOMS WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE NITRILES AND LOWER ALKYL ESTERS OF CRYLIC ACID, METHACRYLIC ACID, AND CROTONIC ACID IN THE PRESENCE OF AN ADDITIVE SELECTED FROM THE GROUP CONSISTING OF METHANOL, ETHANOL, PROPANOL, ISOPROPANOL, N-BUTANOL, SECONDARY BUTANOLS, TERTIARY BUTANOLS AND DIOXANE, SAID ADDITIVE BEING PRESENT IN THE QUANTITY OF FROM2 TO 2K% BASED ON THE TOTAL WEIGHT OF RACTANTS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US413460A US2787633A (en) | 1954-03-01 | 1954-03-01 | Acceleration of fatty amine addition reactions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US413460A US2787633A (en) | 1954-03-01 | 1954-03-01 | Acceleration of fatty amine addition reactions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2787633A true US2787633A (en) | 1957-04-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US413460A Expired - Lifetime US2787633A (en) | 1954-03-01 | 1954-03-01 | Acceleration of fatty amine addition reactions |
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| US (1) | US2787633A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3028415A (en) * | 1959-05-01 | 1962-04-03 | Gen Mills Inc | Preparation of acrylonitrile di-adducts of primary aliphatic amines |
| US3157689A (en) * | 1964-11-17 | Certificate of correction | ||
| US3264341A (en) * | 1961-07-03 | 1966-08-02 | Armour & Co | Preparation of dicyanoethylated fatty amines |
| US3522620A (en) * | 1964-02-13 | 1970-08-04 | Lion Fat Oil Co Ltd | Windshield wiper blade |
| US4035409A (en) * | 1974-12-18 | 1977-07-12 | Texaco Inc. | Hydrocarbyl amine substituted propionic ester |
| US5359123A (en) * | 1991-02-12 | 1994-10-25 | Nippon Paint Co., Ltd. | Polyoxyalkylene polyamines having secondary amino groups |
| JP2007314489A (en) * | 2006-05-29 | 2007-12-06 | Koei Chem Co Ltd | Method for manufacturing beta-alanine compound, piperidone compound and aminopiperidine compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1992615A (en) * | 1931-09-10 | 1935-02-26 | Ig Farbenindustrie Ag | Amino nitrile and process of producing same |
| US2195974A (en) * | 1936-05-19 | 1940-04-02 | Ig Farbenindustrie Ag | Process of producing new amino-carboxylic acids |
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
-
1954
- 1954-03-01 US US413460A patent/US2787633A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1992615A (en) * | 1931-09-10 | 1935-02-26 | Ig Farbenindustrie Ag | Amino nitrile and process of producing same |
| US2195974A (en) * | 1936-05-19 | 1940-04-02 | Ig Farbenindustrie Ag | Process of producing new amino-carboxylic acids |
| US2468012A (en) * | 1945-08-06 | 1949-04-19 | Gen Mills Inc | Beta amino propionates |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3157689A (en) * | 1964-11-17 | Certificate of correction | ||
| US3028415A (en) * | 1959-05-01 | 1962-04-03 | Gen Mills Inc | Preparation of acrylonitrile di-adducts of primary aliphatic amines |
| US3264341A (en) * | 1961-07-03 | 1966-08-02 | Armour & Co | Preparation of dicyanoethylated fatty amines |
| US3522620A (en) * | 1964-02-13 | 1970-08-04 | Lion Fat Oil Co Ltd | Windshield wiper blade |
| US4035409A (en) * | 1974-12-18 | 1977-07-12 | Texaco Inc. | Hydrocarbyl amine substituted propionic ester |
| US5359123A (en) * | 1991-02-12 | 1994-10-25 | Nippon Paint Co., Ltd. | Polyoxyalkylene polyamines having secondary amino groups |
| JP2007314489A (en) * | 2006-05-29 | 2007-12-06 | Koei Chem Co Ltd | Method for manufacturing beta-alanine compound, piperidone compound and aminopiperidine compound |
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