US2808401A - Reaction products of primary fatty amines and aldose sugars - Google Patents

Reaction products of primary fatty amines and aldose sugars Download PDF

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US2808401A
US2808401A US320156A US32015652A US2808401A US 2808401 A US2808401 A US 2808401A US 320156 A US320156 A US 320156A US 32015652 A US32015652 A US 32015652A US 2808401 A US2808401 A US 2808401A
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fatty
amino groups
sugar
aldose
reaction products
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John G Erickson
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General Mills Inc
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General Mills Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/12—Acyclic radicals, not substituted by cyclic structures attached to a nitrogen atom of the saccharide radical

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  • the present invention relates to new compounds obtained by the reaction of fatty amines with aldose sugars and to the process of producing these compounds. These compounds contain a minimum of two fatty amino groups per molecule and may contain a number of fatty amino groups equivalent to the number of carbon atoms in the aldose sugar. The compounds vary in their properties withi the number of fatty amine groups.
  • the lower members of the group can be used directly as surface active agents or may be converted into other surface active agents by suitable reactions, such as sulfation, hydrogenation and the like.
  • the compounds containing larger numbers of fatty amino groups may be used to waterproof textiles, either by direct deposition on the fabric or by reaction with formaldehyde and subsequent insolubilization on the cloth.
  • the invention is applicable to aldopentoses, aldohexoses and aldoheptoses.
  • Suitable sugars which may be used in the present invention include galactose, glucose, gulose, idose, altrose, mannose, allose, ribose, xylose, lyxose, arabinose, and glucoheptose.
  • galactose glucose, gulose, idose
  • altrose mannose
  • allose ribose
  • xylose xylose
  • lyxose arabinose
  • glucoheptose glucoheptose
  • the fatty amines which may be used include the primary amines, either saturated or unsaturated, containing from 8-22 carbon atoms. These may be single, isolated amines, or may be mixed amines derived from the fatty acids of a fat or oil, or from any selected group of such fatty acids.
  • the temperature range suitable for reaction is approximately 40-100 C. Temperatures in excess of 100 C. tend toward excessive decomposition. A preferred range is 50-80 C. Lower temperatures within these ranges suflice for the introduction of two fatty amine groups into the sugar molecule. In order to obtain more highly substituted products it is necessary to employ temperatures within the upper portion of the ranges specified. The time required depends upon the temperature used and the product desired. To introduce 3 or 4 fatty amino groups requires about 4-6 hours at 60 C. To introduce 6 fatty amino groups into fructose, for example, may require from 6-8 hours at 75 C.
  • the reaction is preferably carried out in the presence of an aqueous solvent such as a mixture of water and a lower aliphatic alcohol.
  • an aqueous solvent such as a mixture of water and a lower aliphatic alcohol.
  • Alcohols such as methyl, ethyl, propyl, isopropyl and the like are suited for this purpose.
  • CH NR and all intermediate compounds are also formed. Cyclic products are also possible. Some of these are:
  • Example 2 Example 3 During the recrystallization of the reaction product described in Example 2, another product was isolated. Analysis showed that it had been formed by reaction of four mols of amine with one mol of sugar.
  • Example 4 A mixture of 18.5 parts of dodecylamine, 1.8 parts of glucose, and 100 parts of ethyl alcohol was stirred and heated at 60-65 for 11 hours and at 70-75 for 6 hours. It was then evaporated nearly to dryness under reduced pressure, chilled, filtered and washed with meth- Patented Oct. 1, 1957 anol. A recrystallization from methanol then gave a product which, as analysis showed, had been formed by a reaction between 6 mols of amine and 1 of sugar.
  • An aldose sugar-fatty amine reaction product the 5 aldose sugar containing from 5-7 carbon atoms, the fatty amine containing from 12-18 carbon atoms and the reaction product containing a number of fatty amino groups varying from 2 to the number of carbon atoms in the aldose sugar, one of said fatty amino groups being on the aldehyde carbon atom of said sugar.
  • Glucose-fatty amine reaction product the fatty amine containing from 12-18 carbon atoms and the reaction product containing from 2-6 fatty amino groups, one of said fatty amino groups being on the aldehyde carbon atom of said sugar.
  • Process of producing aldose sugar-fatty amine reaction products which comprises reacting an aldose sugar with a fatty amine containing from 12-18 carbon atoms in the range of to C. in the presence of at least 2 mols of amine per mol of aldose sugar.
  • Process of producing aldose sugar-fatty amine reaction products which comprises reacting an aldose sugar with a fatty amine containing from 12-18 carbon atoms, the fatty amine being employed in a molar ratio of at least 3 times that of the aldose sugar at a temperature within the approximate range of 50-80 C.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent REACTION PRODUCTS OF PRllVIARY FATTY AMINES AND ALDOSE SUGARS John G. Erickson, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of Delaware No Drawing. Application November 12, 1952, Serial No. 320,156
6 Claims. (Cl. 260-211) The present invention relates to new compounds obtained by the reaction of fatty amines with aldose sugars and to the process of producing these compounds. These compounds contain a minimum of two fatty amino groups per molecule and may contain a number of fatty amino groups equivalent to the number of carbon atoms in the aldose sugar. The compounds vary in their properties withi the number of fatty amine groups. The lower members of the group (those containing 2 or 3 fatty amino groups per molecule) can be used directly as surface active agents or may be converted into other surface active agents by suitable reactions, such as sulfation, hydrogenation and the like. The compounds containing larger numbers of fatty amino groups may be used to waterproof textiles, either by direct deposition on the fabric or by reaction with formaldehyde and subsequent insolubilization on the cloth.
It is, therefore, an object of the present invention to provide novel reaction products of fatty amines and aldose sugars in which the compounds contain at least two fatty amino groups per molecule.
It is another object of the present invention to pro vide a process of producing such compounds.
The invention is applicable to aldopentoses, aldohexoses and aldoheptoses. Suitable sugars which may be used in the present invention include galactose, glucose, gulose, idose, altrose, mannose, allose, ribose, xylose, lyxose, arabinose, and glucoheptose. By means of the present invention it is possible to introduce a fatty amino group onto each carbon atom of the aldose sugar.
The fatty amines which may be used include the primary amines, either saturated or unsaturated, containing from 8-22 carbon atoms. These may be single, isolated amines, or may be mixed amines derived from the fatty acids of a fat or oil, or from any selected group of such fatty acids.
In preparing these products it is desirable to use an excess of amine over the theoretical quantity of amine required to introduce the desired number of fatty amino groups into the sugar. Where it is desired to prepare more highly substituted products, it is preferred to use still a greater excess of amine than is required for the lower substitution products. For example, as high as 8 to 10 mols of amine per mol of sugar should be used where it is desired to introduce 5 or 6 fatty amino groups.
The temperature range suitable for reaction is approximately 40-100 C. Temperatures in excess of 100 C. tend toward excessive decomposition. A preferred range is 50-80 C. Lower temperatures within these ranges suflice for the introduction of two fatty amine groups into the sugar molecule. In order to obtain more highly substituted products it is necessary to employ temperatures within the upper portion of the ranges specified. The time required depends upon the temperature used and the product desired. To introduce 3 or 4 fatty amino groups requires about 4-6 hours at 60 C. To introduce 6 fatty amino groups into fructose, for example, may require from 6-8 hours at 75 C.
The reaction is preferably carried out in the presence of an aqueous solvent such as a mixture of water and a lower aliphatic alcohol. Alcohols such as methyl, ethyl, propyl, isopropyl and the like are suited for this purpose.
There are numerous possibilities for the structure of these compounds and for the course which the reaction takes. The following reactions indicate the courses which the reaction may take and the products which may be obtained.
CHO CH=NR CH2NHR HOH HOH =0 (IJHOH RNH. OHOH HOH *9 HOH 011011 GHOH HOH HOH HOH HzQH HaQH HzOH l RN H2 CHZNHR CHQNHR OHZNHR HNHR OHNHR O=NR C=NR 51E 3=0 (IJHOH HOH (BHOH ('JHOH CHOH CHOH JHOH (311.011 CHZOH H.011 A continuation of this process leads eventually to CHzNHR CHNHR OHNHR HNHR HNHR
CH=NR and all intermediate compounds are also formed. Cyclic products are also possible. Some of these are:
RNHC
bHOH RNHbH bu (2110B RNHbH bayou (an RNHbH Example 1 A mixture of 3.6 parts of galactose, 32.3 parts of octa decylamine, 120 parts of isopropyl alcohol and 35 parts of water was warmed to 60 C. and allowed to cool to room temperature once for each of 17 days. It was then filtered and the product was recrystallized from alcohol. Analysis showed that it had been formed from the reaction of three mols of amine with one of sugar.
Example 2 Example 3 During the recrystallization of the reaction product described in Example 2, another product was isolated. Analysis showed that it had been formed by reaction of four mols of amine with one mol of sugar.
Example 4 A mixture of 18.5 parts of dodecylamine, 1.8 parts of glucose, and 100 parts of ethyl alcohol was stirred and heated at 60-65 for 11 hours and at 70-75 for 6 hours. It was then evaporated nearly to dryness under reduced pressure, chilled, filtered and washed with meth- Patented Oct. 1, 1957 anol. A recrystallization from methanol then gave a product which, as analysis showed, had been formed by a reaction between 6 mols of amine and 1 of sugar.
I claim as my invention:
1. An aldose sugar-fatty amine reaction product, the 5 aldose sugar containing from 5-7 carbon atoms, the fatty amine containing from 12-18 carbon atoms and the reaction product containing a number of fatty amino groups varying from 2 to the number of carbon atoms in the aldose sugar, one of said fatty amino groups being on the aldehyde carbon atom of said sugar.
2. Glucose-fatty amine reaction product, the fatty amine containing from 12-18 carbon atoms and the reaction product containing from 2-6 fatty amino groups, one of said fatty amino groups being on the aldehyde carbon atom of said sugar.
3. Galactose-fatty amine reaction product, the fatty amine containing from 12-18 carbon atoms and the reaction product containing from 2-6 fatty amino groups, one
of said fatty amino groups being on the aldehyde carbon atom of said sugar.
4. Process of preparing aldose sugar-fatty amine reaction products containing at least 2 fatty amino groups which comprises reacting the aldose sugar with a fatty amine containing from 12-18 carbon atoms, the fatty amine being employed in excess of the theoretical quantity required for the introduction of the desired number of fatty amino groups, at a temperature within the range of 40 to 100 C.
5. Process of producing aldose sugar-fatty amine reaction products which comprises reacting an aldose sugar with a fatty amine containing from 12-18 carbon atoms in the range of to C. in the presence of at least 2 mols of amine per mol of aldose sugar.
6. Process of producing aldose sugar-fatty amine reaction products which comprises reacting an aldose sugar with a fatty amine containing from 12-18 carbon atoms, the fatty amine being employed in a molar ratio of at least 3 times that of the aldose sugar at a temperature within the approximate range of 50-80 C.
References Cited in the file of this patent UNITED STATES PATENTS 2,016,956 Calcott et al. Oct. 8, 1935 2,016,962 Flint et al. Oct. 8, 1935 2,181,929 Werntz Dec. 5, 1939 FOREIGN PATENTS 519,381 Great Britain Mar. 26, 1940 OTHER REFERENCES Votocek et al.: Collection of Trav. Chim. Tchecoslo- 5 vaquie, vol. 6, (1934), pages 77-96.

Claims (1)

  1. 4. PROCESS OF PREPARING ALDOSE SUGAR-FATTY AMINE REACTION PRODUCTS CONTAINING AT LEAST 2 FATTY AMINO GROUPS WHICH COMPRISES REACTING THE ALDOSE SUGAR WITH A FATTY AMINE CONTAINING FROM 12-18 CARBON ATOMS, THE FATTYAMINE BEING EMPLOYED IN EXCESS OF THE THEORETICAL QUANTITY REQUIRED FOR THE INTRODUCTION OF THE DESIRED NUMBER OF FATTY AMINO GROUPS, AT A TEMPERATURE WITHIN THE RANGE OF 40 TO 100*C.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918462A (en) * 1956-01-20 1959-12-22 Ciba Pharm Prod Inc Process for the preparation of amino-aldehydes
US3478015A (en) * 1966-11-14 1969-11-11 Yuki Gosei Yakuhin Kogyo Kk Process for reacting amino acid and an active carbonyl sugar in a polyhydric alcohol
US4021539A (en) * 1974-01-29 1977-05-03 Henkel & Cie G.M.B.H. Skin treating cosmetic compositions containing N-polyhydroxyalkyl-amines
FR2523150A1 (en) * 1982-03-11 1983-09-16 Cirta Ct Int Rech Tech Appliqu SURFACTANTS AND PROCESS FOR THE PREPARATION OF SUCH AGENTS

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016962A (en) * 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US2016956A (en) * 1932-11-04 1935-10-08 Du Pont Amino derivatives and process of preparing them
US2181929A (en) * 1937-09-21 1939-12-05 Du Pont Maltosamine and process for preparing it
GB519381A (en) * 1937-09-21 1940-03-26 Du Pont Manufacture of maltosamines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016962A (en) * 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US2016956A (en) * 1932-11-04 1935-10-08 Du Pont Amino derivatives and process of preparing them
US2181929A (en) * 1937-09-21 1939-12-05 Du Pont Maltosamine and process for preparing it
GB519381A (en) * 1937-09-21 1940-03-26 Du Pont Manufacture of maltosamines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918462A (en) * 1956-01-20 1959-12-22 Ciba Pharm Prod Inc Process for the preparation of amino-aldehydes
US3478015A (en) * 1966-11-14 1969-11-11 Yuki Gosei Yakuhin Kogyo Kk Process for reacting amino acid and an active carbonyl sugar in a polyhydric alcohol
US4021539A (en) * 1974-01-29 1977-05-03 Henkel & Cie G.M.B.H. Skin treating cosmetic compositions containing N-polyhydroxyalkyl-amines
FR2523150A1 (en) * 1982-03-11 1983-09-16 Cirta Ct Int Rech Tech Appliqu SURFACTANTS AND PROCESS FOR THE PREPARATION OF SUCH AGENTS
WO1983003252A1 (en) * 1982-03-11 1983-09-29 Michel, Jean-Pierre Surfactants and preparation method thereof

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