DE954598C - Process for the production of an ethanolamine capsule or its esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED DECEMBER 20, 1956

GERMAN PATENT OFFICE PATENT LETTERING

CLASS 12 p GROUP 5 INTERNAT. CLASS C07d -

H 13984 IVb I is p

Dr. Wolfgang Gündel, Düsseldorf-Oberkassel, and Heinz Linden, Düsseldorf

have been named as inventors

Henkel & Cie. G. m. B. H., Düsseldorf-Holthausen

Process for the preparation of an ethanolamine derivative

or its esters

Patented in the territory of the Federal Republic of Germany from September 28, 1952.

Patent application suspended on June 21, 1956 Patent issued November 29, 1956

It has been found that N-oxethyl-hexahydrophthalimide or its ester can be obtained by N-oxethylphthalimide or its Esters in the presence of nickel catalysts and in the presence of alcohols as diluents hydrogenated.

The N-Oxäthylphthalimid serving as the starting material can be obtained in good yield by various known routes, e.g. B. by

Conversion of phthalimide with ethylene oxide (reports of the German Chemical Society, Vol. 50 [1917], p. 820) or starting directly from phthalic anhydride by reaction with monoethanolamine. The production of its esters by esterification with any carboxylic acids is also known and presents no fundamental difficulties.

The hydrogenation of Oxäthylphthalimids in the presence of a nickel catalyst proceeds preferentially on the aromatic ring, and the main product is obtained N-oxethyl-hexahydrophthalimide (I)

CO,

N—

OH

(I)

CO '

N - C ₂ H ₁ -OH

(II)

a colorless liquid, not yet described in literature, which does not solidify in a crystalline _{manner even when standing for a long time, with a bp x} 180 to 18i ^c . The amount of N-OxäthylphthaKmidin (II) which is also formed in this process and thus also that of the phthalide, which always appears as its companion, depends largely on the working temperature and the lower it is, the smaller it is. N-oxethyl-hexahydrophthalimide is significantly more resistant to saponifying agents than the easily cleavable N-oxethylphthalimide and, like this, can easily be converted into its esters with fatty acids of any kind. If it depends on the recovery of such esters, it is advantageous to start directly from the esters of N-Oxäthylphthalimids, since the latter, as has been found, can be hydrogenated in the presence of nickel catalysts at temperatures around 120 ° and at these temperatures the formation of Phthalimidines and phthalide are practically absent and as a result significantly better yields of esters of N-oxethyl-hexahydrophthalimide are achieved.

Since, according to information from Willstätter and Jaquet (reports of the German Chemical Society, Vol. 51 [1918], p. 774) the catalytic reduction of phthalimide to hexahydrophthalimide "only with the best platinum black " and, as the authors state, only in the absence of If alcohols succeed, the finding that the conversion of oxethylphthalimide or its esters into N-oxethylhexahydrophthalimide or its esters in the presence of normal technical nickel contacts and especially in the presence of alcohols as diluents was very surprising. The good yields were all the more surprising since it was not foreseeable that under the chosen reaction conditions the formation of the next reduction stage, N-oxethyl-hexahydrophthalimidine, would not occur.

The hydrogenation products obtained according to the process are valuable esterification components for the production of nitrogen-containing plasticizers for vinyl polymers that gel at low temperatures and other plastics.

example 1

191 parts by weight of N-Oxäthylphthalimid, dissolved or suspended in 300 parts by weight of butanol, are in the presence of 19 parts by weight of a nickel-diatomaceous earth catalyst at 165 ⁰ and an operating pressure of 200 atm. hydrogenated until there is no more uptake of hydrogen. The reaction material freed from the catalyst and butanol is broken down into its components by fractionation under reduced pressure. The at Kp. _X 110-179 ⁰ via continuous flow of 14.3 parts by weight provides 11.6 parts by weight of pure phthalide, melting at 72 ° corresponding to a yield of 8.7 ° / ₀ of theory. The main run, boiling at bp ₁₁ 179 to 182 °, was found, on the basis of its analysis and properties, to be N-oxethyl-hexahydrophthalimide, and the amount of 115 parts by weight corresponds to a yield of 59% of theory.

The residue, which solidifies in crystalline form in the cold, can be recrystallized from water or acetone 38.3 parts by weight of pure N-oxethylphthalimidine isolate from the F. 115 °, corresponding to a Yield of 21.6% of theory.

The here formed as the main product N-Oxäthylhexahydrophthalimid is a highly viscous, colorless, non-crystallizing even during prolonged standing liquid, bp. _X 180-181 °, which is very easy soluble both in water and in aromatic hydrocarbons and in the saponification mixture sterically different hexahydrophthalic acids.

Found: C 61.2%, H 7.6%, N 7.0%, OH number 286.

Calculated for C ₁₀ H ₁₅ O ₃ N: C 60.9%, H 7.6%, N 7.1%, OH number 284.

Example 2

261 parts by weight of the butyric acid ester of N-oxethylphthalimide (bp. _X 192 to 193 °, melting point 53 °) are dissolved in the same amount of butanol and, after the addition of 19 parts by weight of a nickel-diatomaceous earth catalyst, at 120 ° and an operating pressure of 200 atm . hydrogenated. After the catalyst and the solvent have been separated off, the material to be hydrogenated is expediently washed several times with water after being diluted with ether. The Buttersäureester obtained by distillation under reduced pressure, the N-Oxäthylhexahydrophthalimids is a colorless, mobile liquid, bp. _X 186 to 190 °. The amount of 221 parts by weight obtained corresponds to a yield of 83 "Y ₀ of theory.

Found: N 5.3%, saponification number 417.

Calculated: N 5.2%. Saponification Number 418.

Example 3

373 parts by weight of lauric acid ester of N-Oxäthylphthalimids (F. 39 to 40 ⁰ ) are dissolved in five times the amount of butanol and after the addition of 19 ^{parts by weight of a nickel-kieselguhr catalyst at no 0} and an operating pressure of 220 atm. hydrogenated. After removing the catalyst and distilling off the solvent, the lauric acid ester of N-oxethyl-hexahydrophthalimide remains as a yellow-colored oil which solidifies like an ointment after standing in the cold for a long time. 368 parts by weight are obtained. ■

Found: C 69.8%, -H 9.5%, N 3.9 ° / o ·

Calculated for C ₂₂ H ₃₇ O ₄ N: C 69.7%, H 9.7%, N 3.7% o

Example 4

Is hydrogenated according to the information in Example ^ 464 parts by weight of the neutral succinic acid ester of N-Oxäthylphthaümids (mp 134 ° at 130 ° is obtained after the same work-up

468 parts by weight of the neutral succinic acid ester of N-oxethyl-hexahydrophthalimide. The ester Accrues as a highly yiscous, yellow oil that resembles an ointment when standing for a long time.

Found: C 61.7%, H 6.9 ° / ₀ , N 5.7%.

Calculated: for C ₂₄ H ₃₂ O ₈ N ₂ : C 60.6 ° / ₀ , H 6.8 ° / ₀ , N 5.9%

Claims (1)

PATENT CLAIM: Process for the production of an ethanolamine derivative or its esters, characterized in that that one N-Oxäthylphthalimid or its ester in the presence of nickel catalysts and in the presence of alcohols as' diluent to N-oxethyl-hexahydrophthalimide or its esters hydrogenated. SJ 609 546/471 6.56 (609 716 12. 56)