US2993887A

US2993887A - Anhydro amides

Info

Publication number: US2993887A
Application number: US329921A
Authority: US
Inventors: John D Zech
Original assignee: Atlas Powder Co
Current assignee: Atlas Powder Co
Priority date: 1953-01-06
Filing date: 1953-01-06
Publication date: 1961-07-25
Anticipated expiration: 1978-07-25
Also published as: DE1005526B

Description

UnitediStates Patent 2,993,887 7 AN'HYDRO MIDES John D. Zech, Wilmington, Del., assignor to Atlas Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Jan. 6, 1953, Ser. No. 329,921 8 Claims. (Cl. 260-211) R is the residue of an anhydridized hexane pentol R is a monovalent hydrocarbon radical R is the hydrocarbon residue of a carboxylic acid having from 2 to 25 carbon atoms The compounds of the present invention are prepared by the reaction of a product from the reduction of a monosaccharide in the presence of a suitable primary amine with an organic carboxylic acid. Such products are identified as hexityl amines. Suitable hexityl amines include, but are not limited to, such amines as N-methyl glucamine, N-ethyl glucamine, N-butyl glucamine, N-phenyl glucamine, N-hydroxy' ethyl glucamine, N-cyclo hexyl glucamine, N-benzyl glucamine,. N-lauryl glucamine, N- cetyl glucamine, N-octadecyl glucamine, N-allyl glucamine, N-methyl fructamine, N-ethyl fructamine, etc. Suitable carboxylic acids include, but are not limited to, such carboxylic acids as acetic, caproic, capric, lauric, myristic, palmitic, oleic, stearic, linoleic, linolenic, eleostearic, behenic, benzoic, p-tertiary butyl benzoic, phenyl acetic, phenoxy acetic, 2,4-dichlorophenoxy acetic, 2,4,-

S-trichloro-phenoxy acetic, glycollic, lactic, ricinoleic, chloro-acetic, tall oil, cottonseed oil fatty acids, rosin, coconut oil fatty acids, etc.

When carboxylic acids are reacted with hexityl amines at temperatures in the range of about 180 to about 200 C., heterocyclic amides are formed through the elimination of two or more moles of water per mole of carboxylic .acid reacted with an equivalent amount of hexityl amine. The identity of the hexityl amine is lost, inasmuch as the heterocyclic ring structures that are formed as the result of anhydridization differ markedly from the structural configuration of the hexityl amine. While the exact structure of these heterocyclic amides has not been definitely established, there are several possibilities to be considered in theorizing as to the possible structure of these heterocyclic rings. It is to be understood that applicant neither intends nor desires to be bound by this explanation, but offers it only to explain the possible nature of the compounds covered by this invention. It seems from present investigation that the heterocyclic amides in question may be either monocyclic or dicyclic ring structures. Some possibilities are as follows:

CNg-HOH Patented July 25,1961

. O m-Nil-R,

to 220 0., preferably at temperatures of 180 C. to

200 C. until two or more moles of water have been eliminated. An inert gas may be used to facilitate the removal of water and also to protect the reactants from atmospheric oxidation. When a fatty carboxylic acid is 'mixed with a hexityl amine, a soap is formed which has a high viscosity at temperatures below C. To avoid this, it is often desirable to have both reactants preheated to about 150 to C. before mixing. Following the preheating of the reactants, they are then admixed and the temperatureraised to the desired reaction temperature as indicated above. In the early part of the reaction it is sometimes difiicult to raise the temperature above 160 C. due to severe foaming. This difficulty can be overcome .by holding the mixture at temperatures of 140 to 160 C.

for several hours or by the addition of some heterocyclic amide from a previous preparation. This same difficulty may be overcome by the addition of small amounts of lower alcohols, such as n-butyl alcohol, n-amyl alcohol, methyl isobutyl carbinol, etc., which later distill out as the reaction temperature is raised.

The following exampless are given by way of best illustrating the compounds covered by this invention-and are not to be taken as limiting the invention in any way.

Example 1 141 gms. ofoleic acid was added to 98 gms. of N- .methyl glucamine and heated for 2 hrs. at a reaction temperature of 168 to 184 C. During this reaction period 9.5 cc. of water was removed. The product had an acid number of 10, saponification number of 40 and a hydroxyl number of 436.

Example 2 166 gms. of erucic acid was added to 97 gms. of N-methyl glucamine and the mixture was heated for 50 minutes at a reaction temperature of 180 to 194 C. The reaction product had an acid number of 12.5, saponification number of 41.5 and a hydroxyl number of 426.

Example 3 100 gms. of lauric acid was added to 1101 gms. of N- methyl glucamine and the mixture was heated for 1 hr. at a reaction temperature of 192 to 197 C. The reaction product had an acid number of 7.0, a saponification number of 30 and a hydroxyl number of 485.

Example 4 142 gms. of stearic acid was added to 100 gms. of N- methyl glucamine and the mixture was heated for 2% hrs. at a reaction temperature of 182 to 196 C. yielding 10.5 cc. of water. The reaction product had an acid number of 5.8, a saponification number of 29.5 and a hydroxyl number of 348.

Example 5 250 gms. of lauric acid was added to 252 gms. of N-methyl glucamine and the mixture was heated for 3 hrs. at a reaction temperature of 150 to 185 C. during which time 29 cc. of water was given off and collected. The reaction product had an acid number of 19.5, a saponification number of 86 and a hydroxyl number of 685. It is to be observed that the high saponification number and hydroxyl number here is probably due to the fact that for the first 2% hrs. of the reaction the temperature range was 150 to 170 C., while the higher tem perature reaction, 170 to 185 0., was applied for but .6 hour. This accounts for the fact that less than 2 moles of water was removed.

Example 6 500 gms. of lauric acid was added to 495 gms. of N-methyl glucamine and the reaction mixture was heated for 1% hrs. at a temperature of 170 to 193 C. 25 cc. of butanol was added to the mixture, prior to heating, to reduce foaming. 83 cc. of water was eliminated from the reaction mass during the heating period. The product had an acid number of 7.4, a saponification number of 32.3 and a hydroxyl number of 505.

Example 7 705 gms. of oleic acid was added to 495 gms. of N- methyl glucamine and the reaction mixture was heated for 3 hrs. at a temperature of 1631 to 202 C. Prior to heating, 50 cc. of butanol was added to the reaction mixture to reduce foaming. During the heating, 77 cc. of water was eliminated from the reaction mass. The product had an acid number of 5.3, a saponification number of 25.8 and a hydroxyl number of 394.

Example 8 1001 gms. of lauric acid was added to 990 gms. of N-methyl glucamine. Prior to heating this mixture, 50 cc. of butanol and 35 cc. of methyl isobutyl carbinol were added to the reaction mixture to reduce foaming. The reaction mixture was heated for 3% hrs. at a reaction temperature of 160 to 192 C. During this time 166 cc. of water was given oil by the reaction mass. The product had an acid number of 6.4, a saponification number of 33.9 and a hydroxyl number of 479.

Example 9 1410 gms. of oleic acid was added to 990 gms. of N-methyl glucamine. To reduce foaming, 82.5 gms. of the product of Example 7 was added to the reaction mixture. The reaction mixture was heated for 1 /2 hrs. at a temperature of 160 to 195 'C., during which time 157 4 cc. of water was evolved and collected from the reaction mass. The resulting product had an acid number of 6.2, a saponification number of 29, and a hydroxyl number Example 10 172 gms. of tall oil (acid No. 163) and 98 gms. of N-methyl glucamine, were reacted at a temperature of 192 to 207 C. for 2% hrs. 15 cc. of water was evolved and collected during the reaction. The product was a soft, brown, resinous mass.

Example 12 52 gms. of N-ethyl glucamine and 7:1 gms. of cottonseed oil fatty acids were reacted at a temperature of 180 to 208 C. for 2 /2 hrs. 8.5 cc. of water was evolved and collected during the reaction. The product was a very viscous brown liquid.

Example 13 99.5 gms. of N-methyl glucamine and 98 gms. of coco nut fatty acids (average mol. wt. 192) were reacted by first melting the N-methyl glucamine and added rapidly to the fatty acids which were preheated to C. The mixture was heated at 184 to 202 C. for 2 hrs. 18 cc. of water was collected during the reaction. During the reaction, the reaction mixture was blanketed with nitrogen to assistthe removal of water.

Example 14 1501 gms. of N-methyl glucamine was melted and to it was added 1485 gms. of lauric acid which had been preheated to 160 C. The lauric acid was added gradually over a period of /2 hr. The reaction mixture was held at to 195 C. for 2% hrs. while blanketing with nitrogen. During this time 266 cc. of water was evolved. The reaction product was a viscous liquid which analyzed as follows: acid number 5.4, saponification number 27.8 and hydroxyl number 463.

It has been found that the products typified by the preceding examples are suitable for use as intermediates for the preparation of anhydro glucamines and N-sub' stituted anhydro glucamines. This can be accomplished by saponification, thus splitting off the amide to form either the anhydro glucamine or the N-substituted anhydro glucamine.

The compounds of the present invention exhibit valuable properties as non-corrosive anti-static agents. The method of application comprises the preparation of a solution of the desired compound at a concentration calculated to yield .3% to 1.0% solids pickup on the weight of the material being treated. These compounds can be applied from aqueous solutions or from suitable aliphatic or aromatic hydrocarbon solvents, etc., with the aid of a coupler if needed. It can be applied from an oil solution with the aid of a hydrophobic solubilizer or the oil mixture can be applied as a water emulsion, with the aid of a coupler and emulsifier. Suitable solutions of the compounds may be applied by spraying, pad roll, dye machine, dye bath or by roll applicator and the like. The following examples are supplied to show the effectiveness of the compounds of the present invention as textile anti-static agents.

Example 15 A 1% water solution of the lauric amide of anhydro N-methyl glucamine is heated to 60 C. A sample of Example 16 An oil soluble mixture is prepared by mixing equal parts of the lauric amide of anhydro N-methyl glucamine and sorbitan monopalmitate. 'I'he sorbitan monopal-mitate is here used as an emulsifier and coupling agent. The mixture is then added to a light textile grade oil to yield a solution of 1% solids concentration. This oil solution is then applied to nylon yarn as a lubricating anti-static finish. The treated yarn shows excellent resistance to static accumulation.

The compounds of the present invention may be applied as anti-static agents to fibers, staple fibers, felts, cords, threads, yarns, pellicles, filaments, fabrics, and the like. Textiles of either natural or synthetic origin may be so treated. Thus cellulosic fibers, regenerated protein fibers, polyacrylic fibers, polyester fibers, wool, silk, bast fibers, glass and the like are amenable to the use of the compounds of the present invention as anti-static agents.

It will be understood that the embodiments of the invention described in the specification and illustrated by the examples are only illustrative of the compounds and the manner in which they are produced. Various modifications can be made without departing from the principles of the invention.

What is claimed is:

1. Heterocyclic amides of the formula The empirical formula (C H (OH) represents the heterocyclic residue of a hexane pentol from which one mole of water has been removed which residue is joined with the N through a carbon linkage R is a monovalent hydrocarbon radical R is the hydrocarbon residue of a carboxylic acid having from 2 to 25 carbon atoms.

2. As a new composition of matter, an N-lower a1kyl- N-anhydrosorbitylamide of an aliphatic carboxylic acid that contains from eight to eighteen carbon atoms, said composition having the formula 0 RC ON-CH2CHOHCHCHOHCHOHlHg in which R is an alkyl group of one to four carbon atoms and R is a member of the class consisting of alkyl and alkenyl groups of seven to seventeen carbons.

3. As a new composition of matter, an N-lower alkyl- N-anhydrosorbitylamide of a fatty acid that contains from eight to eighteen carbon atoms, said comoposition having the formula in which R is an alkyl group of one to four carbon atoms and R is a residue of a fatty acid, said residue containing from seven to seventeen carbon atoms.

4. As a new composition of matter, an N-methyl- N- anhydrosorbitylamide of a 'fatty acid that contains from eight to eighteen carbon atoms, said composition having the formula O ROOIE-CHZCHOHiHGHOHCHOHlHB in which R is a residue of a fatty acid, said residue containing from seven to seventeen carbon atoms.

5. As a new composition of matter, N-methyl-N-anhydrosorbityllauramide having the formula 6. As a new-composition of matter, N-methyl-N-anhydrosorbitylamide of cocoanut oil fatty acids having the formula 0 RCON-CHzCHOHHCHOHCHOH H2 in which R is the residue of cocoanut oil fatty acids.

7. A method for the preparation of N-lower-alkyl-N- anhydrosorbitylamide of an aliphatic carboxylic acid having the formula 0 RC ON-OHnCHOH HCHOHOHOHAH 0 RCOIIT-CH OHOHOHCHOHCHOHlH1 in which R is an alkyl group of one to four carbon atoms and R is a residue of a fatty acid, said residue containing from seven to seventeen carbon atoms which comprises heating an N-lower alkylglucamine with a fatty acid containing from eight to eighteen carbon atoms until substantially exactly two molecular equivalents of water are evolved.

References Cited in the file of this patent UNITED STATES PATENTS 1,985,424 Piggott Dec. 25, 1934 2,653,932 Schwartz Sept. 29, 1953 2,703 798 Schwartz Mar. 8, 1955

Claims

1. HETEROCYCLIC AMIDES OF THE FORMULA