DE1005526B - Process for the preparation of heterocyclic, optionally esterified, carboxamides - Google Patents

Description

GERMAN

The invention relates to the production of heterocyclic, optionally esterified carboxamides, which are used as chemical intermediates, emulsifiers, wetting and dispersing agents, dyeing auxiliaries, antistatic agents, anti-corrosive agents, detergents, fabric softeners and lubricants as well can be used as additives to lubricants.

These compounds can be represented by the general formula

R ₁

RN-CO-R ₂

in which R is the radical of an anhydrated hexane pentol or a higher fatty acid ester of such a radical, R _{1 is} an alkyl radical and CO - R _{2 is} the acyl radical of a higher fatty acid with a maximum of 25 carbon atoms.

The compounds are made by heating N-alkylhexitylamines with higher fatty acids with a maximum of 25 carbon atoms in a molar ratio of 1: 1 to 1: 4 with elimination of water to 170 to 250 °, preferably to 180 to 200 °. Suitable N-alkylhexitylamines include, among others. N-methylglucamine, N-ethylglucamine, N-butylglucamine, N-phenylglucamine, N-Cyclohexylglucamine, N-Laurylglucamine, N-Cetylglucamine, N-octadecylglucamine, N-allylglucamine, N-methylfructamine and N-ethyl fructamine. Suitable fatty acids include, among others. Capron-, Caprin-, Laurin-, Myristic, palmitic, oil, stearic, linoleic, linolenic, Elaostearic, behenic and ricinoleic acids, tall oil acids, cottonseed oil and coconut oil fatty acids.

If the fatty acids are reacted in equimolar proportions with the hexitylamines at about 180 to 200 °, gp are obtained by splitting off two or more moles Water per mole of carboxylic acid formed heterocyclic amides. The hexitylamine changes his here Construction.

To facilitate the elimination of water as well as to protect the reactants from atmospheric agents For oxidation, an inert gas can be passed through the reaction vessel. Becomes a fatty acid with a hexitylamine mixed, the result is a soap that has a high viscosity below 155 °. To avoid this, it is often useful to preheat both reactants to about 150 to 160 ° before mixing, whereupon one mix them together and bring the temperature to 170 to 250 °. At the beginning of the implementation it is because of the strong foaming sometimes a little difficult to increase the temperature to over 160 °. This difficulty can be countered by first holding the mixture at 140 to 160 ° for several hours or add a small amount of a heterocyclic amide from a previous preparation batch, Method of manufacture

of heterocyclic, optionally

esterified carboxamides

Applicant:

Atlas Powder Company, Wilmington,
Del. (V. St. A.)

Representative: Dr. W. Beil, lawyer,
Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
V. St. v. America from January 6th and January 1st March 1953

John David Zech, Wilmington, Del. (V. St. A.),
has been named as the inventor

also by adding small amounts of lower alcohols, such as n-butyl alcohol, η-amyl alcohol, methyl isobutyl carbinol, which later evaporate at the elevated temperature of 170 to 250 °.

The following examples illustrate the production of non-esterified heterocyclic carboxamides according to the invention.

example 1

705 g of oleic acid were treated with 495 g of N-methylglucamine for 3 hours, initially at 161 ° and then at 170 to 202 ° warmed up. To reduce foaming, 50 ecm were added to the reaction mixture before heating Butanol added. 77 ecm of water was removed from the reaction mass during the heating. That Product had an acid number of 5.3, a saponification number of 25.8 and a hydroxyl number of 394.

Example 2

1001 g of lauric acid was added to 990 g of N-methylglucamine. Before heating, 50 ecm of butanol and 35 ecm of methyl isobutylcarbinol were added to this mixture to reduce foaming, whereupon the reaction mixture was kept at 160 ° and then at 170 to 192 ° for ^{3 ×} / _{4 hours.} During this time, 166 ecm of water were expelled from 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 3

1410 grams of oleic acid was added to 990 grams of N-methylglucamine. To reduce foaming were also 82.5 g of the reaction product of

609 867/429

Example 1 was added, whereupon the reaction mixture IV was kept _{at 170 ° to 195 ° for 2} hours, during which time 157 ecm of water were expelled and collected. The product obtained had an acid number of 6.2, a saponification number of 29 and a hydroxyl number of 400.

Nuts kept at 163 ° to 193 ° with stirring, whereupon 50 ecm of toluene were added and the mixture was refluxed for a further ₄ hours at 208 ° to 235 °. A total of 18 ecm of water was driven off. The toluene was then removed from the reaction mixture under 1 mm vacuum, leaving 234 g of a dark, viscous oil with an acid number of 11, a saponification number of 98 and a hydroxyl number of 144. This product is the monooleate of one

Example 4

52 g of N-ethylglucamine and 71 g of cottonseed oil fatty acid were held _{at 180 ° to 208 ° for 2V for 2} hours, io N-methyl-N-anhydrohexityl-oleylamide. during which time 8.5 ecm of water are split off and
were caught. The reaction product was a
very viscous brown liquid.

Example 8

A 3-liter, three-necked flask equipped with a stirrer, A thermometer and a reflux condenser were charged with 550 g of N-methylglucamine. That N-methylglucamine was melted and preheated with 1115 g on a steam bath within 5 minutes Lauric acid added. In the course of 55 minutes the temperature was increased to 180 °;

Example 5

99.5 g of N-methylglucamine and 98 g of coconut fatty acid (average molecular weight 192) were obtained
implemented by getting the N-methylglucamine first
melted and then added to the fatty acids previously heated to 160 °. The mixture was kept at 20 for 2 hours during this time, 77 ecm of an aqueous De-184 was maintained at 202 °, with 18 ecm of water being split off stülats. The reaction mixture was then

held at 190 to 207 ° for a further 5 ¹ Z ₂ hours, after which a total of 145 ecm of an aqueous distillate had passed. The reaction product was a dark, viscous liquid with an acid number of 9, a saponification number of 112, and a hydroxyl number of 197.

and were caught. To facilitate the elimination of water, nitrogen was added during the reaction passed the reaction mixture.

It is the monolaurate of an N-methyl-N-anhydrohexityl-laurylamide represent.

Example 9

A 2 liter three neck flask fitted with a stirrer and a thermometer was charged with 495 g of N-methylglucamine. That Methylglucamine was melted and 500 g

Example 6

74 grams (0.38 moles) of a mixture of N-methylglucamine
and N-methylfructamine (prepared by pressure hydrogenation of invert sugar in the presence of methylamine) were melted and added with 76 g (0.38 mol) 30
hot lauric acid is added quickly while stirring. That
Heating was carried out with stirring at 171 to 192 ° for 3 hours
continued for a long time and the resulting condensation
caught and measured. That way were
13.5 ecm (0.75 moles) of water is collected. 35 molten lauric acid was formed and a very viscous, water-soluble mixed amide was quickly added with stirring. The temperature was increased and IV _{2 with} an acid number of 10, a saponification number of 30.9 hours between 171 and 193 ° with simultaneous and a hydroxyl number of 465. Deposition of 83 ecm of water was maintained.

The 163.5 g of the product obtained in this way, which is also the subject of the invention, were

Production of heterocyclic esterified fatty acids- 40 together with 128 g of oleic acid in a 0.5-liter three-necked amide is carried out by heating the N-alkylhexitylamine flask with a stirrer, thermometer and condenser with the higher fatty acids in excess up to one added and then with stirring- 3 ^x / ₄ hours between a molar ratio of 1: 4. 195 and 204 ° held; during that time were

In general, the products have a better 9 ecm of water free. The result was a viscous brown Color if the reaction occurs at the lowest possible 45 liquid containing the monooleate of an N-methyl-N-an temperatures, but with acceptable esterification hydrohexityl-lauryl amides, and anhydration rates, carried out ". . . , "

will. It is also desirable to take measures for enticing

removal of the 70 g (0.36 mol) of the mixture mentioned in Example 6 from the condensation and esterification

to provide stirring water, e.g. B, a flush 50 of N-methylglucamine and N-methylfructamine and with an inert gas or the application of a 201 g (0.72 mol) oleic acid were 3 ^x / ₂ hours on ISf water tug. heated to 234 °. Here, 21 ecm of water was removed

The kind of fatty acid amide obtained can be distilled depending on. The ester amide obtained was oil-soluble and the reactants chosen could vary widely. had an acid number of 5.8, a saponification number of Higher saturated fatty acids usually give wax-55 96.1, a hydroxyl number of 143 and a nitrogen-like product, if the esterification was carried out so far, of 1.95%. is performed until all of the existing hydroxyl groups
heterocyclic amide are used up. The area
the partial ester amides of fatty acids range from
liquid to viscous or pulpy semisolid 60
Compounds and wax-like solids.

The following examples illustrate the preparation of heterocyclic esterified fatty acid amides according to the invention.

Claims (1)

Claim. Process for the preparation of heterocyclic, optionally esterified carboxamides, thereby characterized in that N-alkylhexitylamines with higher fatty acids with a maximum of 25 carbon atoms in a molar ratio of 1: 1 to 1: 4 with elimination of water be heated to 170 to 250 °. Example 7 _{Documents considered} : A 1 liter three-necked flask with a stirrer, Ther- · Beilstein's Handbook of Organic Chemistry, 4. Aufmometer and reflux condenser for azeotropic water situation, Vol. 31 (1938), pp. 170 to 172. abortion was with 65 g N-methylglucamine and 188 g Adrances in Carbohydrate Chemistry Vol. 3 (1948), Oleic acid: ':. The reaction mixture became 50 Mi- 70 p. 382.