EP0470104A1

EP0470104A1 - A process for making 2-oxazolines

Info

Publication number: EP0470104A1
Application number: EP19900906187
Authority: EP
Inventors: William E. Fristad; Hans Theo Leinen; Horst Jürgen KRAUSE; Brigitte Hase; Peter Neumann
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1989-04-28
Filing date: 1990-04-19
Publication date: 1992-02-12
Also published as: CA2054708A1; EP0394849A1; DE3914133A1; WO1990013546A1; BR9007335A; JPH04504854A

Abstract

Selon un procédé de production de grandes quantités de 2-oxazolines, substituées en deuxième position avec des groupes C4-C6-alkyle de substitution d'aryle ou d'aralkyle, avec des groupes C1-C6-alkyle substitués par hydroxy ou alkoxy ou avec des groupes alkoxyalkoxyméthyle, on convertit des acides carboxyliques ayant la formule R1-COOH, dans laquelle R1 est un des substituants susmentionnés, ou des esters ou des glycérides de ceux-ci, avec du 2-aminoéthanol ou des éthanolamides de ces acides carboxyliques en présence de composés de titane ou de zirconium du type M(OR3)4, où M est Ti ou Zr.According to a process for the production of large quantities of 2-oxazolines, substituted in second position with C4-C6-alkyl groups of aryl or aralkyl substitution, with C1-C6-alkyl groups substituted by hydroxy or alkoxy or with alkoxyalkoxymethyl groups, carboxylic acids having the formula R1-COOH, in which R1 is one of the abovementioned substituents, or esters or glycerides thereof, are converted with 2-aminoethanol or ethanolamides of these carboxylic acids in the presence of titanium or zirconium compounds of type M (OR3) 4, where M is Ti or Zr.

Description

Process for the preparation of 2-oxazolines.

The invention relates to a process for the preparation of 2-oxazolines of the general formula I.

in the R-

an aryl or aralkyl radical optionally substituted in the aromatic nucleus, an alkyl group with 5 to 6 carbon atoms, a hydroxy-substituted alkyl group with 1 to 6 carbon atoms, an alkoxy-substituted alkyl group with 1 to 6 carbon atoms in the alkyl and 1 to 18 carbon atoms in the alkoxy group, or a radical of the general formula II

R2- (OC ₂ H ₅ ) p-0-CH2- (II)

in the

R2 is an alkyl or alkenyl group with 1 to 18

Carbon atoms, in particular a methyl group, and p is a number in the range from 1 to 10, in particular 1 to 2. means

by condensation of carboxylic acid ethanolamides or their precursors in the presence of catalysts in the liquid phase, precursors being carboxylic acids and esters of carboxylic acids with lower alkanols or glycerol and second component 2-aminoethanol.

2-0xazolines with a substituent in the 2-position are valuable products which are used, inter alia, as solvents or plasticizers and in particular as polymerization components.

Numerous processes have been described for producing this class of compound:

The simplest preparation is the cyclodehydration of N-2-hydroxyethyl-carboxamides (Che. Rev. 44, 447 ff (1949), Chem. Rev. 71, 485 ff (1971)). However, the cyclization of the unsubstituted N-2-hydroxyethyl-carboxamides requires very drastic conditions or the presence of special catalysts. While for the production of volatile, short-chain 2-alkyl-2-oxazoline reactions in the gas phase in the presence of dehydrating metal oxides such as Al2O3, SiO2 / Al2O3, Al2O3 iO2, iO2 or MgO have been found to be suitable, the more difficult are ¬ term, longer-chain 2-alkyl-2-oxazolines better in the liquid phase. Compounds of manganese, cobalt, molybdenum, tungsten, iron, cadmium, zinc and tin as well as rare earth metals have been described as catalysts for the liquid phase reaction (cf. US Pat. No. 3,562,263, BE-PS 666 829, CA 87) , 135353, CA. 87, 135352, U.S. Patent 3,681,329, U.S. Patent 3,681,333, EP-OS 00 33,752, U.S. Patent 4,543,414, U.S. Patent 4,354,029, U.S. Patent 4,443,611 , EP-OS 0 105 944 and EP-OS 0 164 219). Those described in the aforementioned publications However, catalysts do not lead to good yields when preparing longer-chain 2-fatty alkyl-2-oxazolines.

It has now been found that special titanium and zirconium compounds are outstandingly suitable as catalysts in a process of the type mentioned at the outset, it being possible to achieve yields of up to about 90% of theory, based on the starting compound.

Accordingly, the invention is directed to a method of the type mentioned, in which

a) carboxylic acids of the general formula III

Ri-COOH (III)

in which R ^{1 is} as defined above, esters of these carboxylic acids with monoalkanols having 1 to 4 carbon atoms or glycerides of these carboxylic acids with 2-aminoethanol or

b) ethanolamides of these carboxylic acids

in the presence of titanium or zirconium compounds of the general formula IV

M (OR ³ ) 4 (IV)

in the M tetravalent titanium or zirconium and R- an alkyl 90/13546 4

group with at least 2, in particular 2 to 4 carbon atoms, an acyl group with at least 2, in particular 2 to 10 carbon atoms or a 2-aminoethyleneoxy group or a radical of a beta-diketone of the general formula V.

R ^4l --CC == CCHH - CCOO - R ⁵ (V)

in which R ⁴ and R ^{5 are the} same or different radicals from the group formed by alkyl groups with 1 to 4 carbon atoms and optionally substituted in the p-position phenyl, where two of the groups R - together from the divalent radical of a dihydric alcohol with 2 to Can have 4 carbon atoms,

in the presence of titanyl acetylacetonate or

or in the presence of condensation products of titanium (IV) or zirconium (IV) tetraalkoxylates of the general formula IV, in which M and R-3 are as defined above, with polyfunctional alkanols, in particular with 3 to 12 carbon atoms and 2 to 6 hydroxyl groups ,

condensed and the 2-0xazolines thus obtained isolated with removal of the water and alcohol or glycerol formed.

The following carboxylic acids and their esters with lower alkanols or glycerol and their ethanol ide are used in particular as starting material in the process of the invention:

Benzoic acid, which may have 1 to 3 substituents; Typical substituents are C1-C4-alkyl groups, especially methyl, -CC4-alkoxy groups, especially methoxy, and halogen atoms such as chlorine and bromine; Phenylacetic acid or phenylpropionic acid, which may be substituted in the aromatic nucleus with 1 to 3 of the aforementioned substituents;

Capronic or enanthic acid;

Hydroxycarboxylic acids with 2 to 7 carbon atoms, in particular hydroxyacetic acid (glycolic acid), hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, in particular the omega-hydroxy-substituted isomers thereof and optionally their lactones;

alkoxy-substituted carboxylic acids which are formally alkylation products of the aforementioned hydroxycarboxylic acids and have 1 to 18 carbon atoms in the alkoxy group; methoxy-substituted carboxylic acids are preferred;

Ether carboxylic acids of the formula

R ² - (OC2H5) p-0-CH2-C00H

in which R ² and p are as defined above; typical examples of this are ether carboxylic acids which, by catalytic oxidation of adducts of ethylene oxide with primary, saturated or optionally also unsaturated alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol and hexanol, as well as saturated or unsaturated fatty alcohols including Technical mixtures of the same as Capron, Önanth, Capryl, Caprin, Undecenyl, Lauryl, Myristyl, Cetyl, Stearyl, Oleyl, Elaidyl, Linoleyl and Linoleyl alcohol can be obtained and for example in DE -A 26 36 123, EP-B 0 039 111, EP-B 0 018 681 and DE-A 31 35 946 are described.

Particularly preferred ether carboxylic acids are methoxy-ethoxy- and methoxy-ethoxyethoxyacetic acid. The carboxylic acid ethanolamides which can be used in the process of the invention can be obtained by customary processes, for example by reacting the acid chlorides or the C 1 -C 4 -alkyl esters of the carboxylic acids with ethanola in.

The titanium or zirconium compounds which can be used as catalysts in the process of the invention are known and for the most part are commercially available. Condensation products of titanium (IV) or zirconium (IV) tetraalkoxylates with multifunctional alkanols with 3 to 12 carbon atoms and 2 to 6 hydroxyl groups such as glycerol, trimethylolpropane and pentaerythritol are esterification and / or transesterification catalysts which e.g. in US-C 4,705,764, the contents of which are incorporated herein by reference. A suitable polyalkanol is also polyvinyl alcohol. The titanium or zirconium tetra- (2-aminoethoxylates), which are also suitable as catalysts, can be prepared from titanium or zirconium tetraalkoxylates and 2-aminoethanol.

According to a preferred embodiment of the invention, the catalysts used are esters of titanium acid (H4Tiθ) or zirconic acid (H4Zrθ) or mixed anhydrides of titanium or zirconic acid with organic acids of the general formula IV in which M = Ti or Zr and R ³ denotes an alkyl group with at least 2 or more than 2, in particular 2 to 4, carbon atoms or an acyl group derived from a monocarboxylic acid with 2 or more than 2, in particular 2 to 10, carbon atoms.

According to a further advantageous embodiment of the invention, catalysts from the group formed by titanium or zirconium tetraethylate, tetrapropylate, tetraisopropylate, tetrabutylate and tetraacetate are used. According to a further advantageous embodiment of the invention, titanium or zirconium acetylacetonates of the general formula (VI) are used as catalysts

(RδoJmMfACAJn _(V I)

in which R ^{6 is} an alkyl group having 1 to 4 carbon atoms, ACA is an acetylacetonate radical and the number 0 and n are 4 or m is 2 and n is 2.

According to a further advantageous embodiment of the invention, polycondensation products of esters of titanium acid with monoalkanols having 2 to 10 carbon atoms with pentaerythritol are used as catalysts.

According to a further advantageous embodiment of the invention, the catalysts to be used according to the invention are used in an amount of 0.1 to 10, preferably 0.5 to 5, in particular 0.5 to 3 mol%, based on carboxylic acid ethanolamide, or its forerunners.

According to a further advantageous embodiment of the invention, the condensation reaction is carried out at 150 to 270 ° C., the reaction preferably being carried out in vacuo and under a protective gas. The water of reaction formed can be distilled off together with the 2-oxazolines and separated from them during the distillation, it being possible to remove residual water entrained with customary drying agents such as anhydrous sodium sulfate or molecular sieve (4A). However, it is also possible to remove the water of reaction from the reaction mixture by azeotropic distillation using high-boiling entraining agents such as, for example, tetralin or Cu ol, before the actual distillation of the 2-oxazolines. According to a further preferred embodiment of the invention, the 2-oxazolines can be obtained directly from carboxylic acids or ^* . Carboxylic acid esters of the general formula VII

RI-COOR ⁷ (VII)

in which R ^{1 is} as defined above and R ^{7 is} hydrogen or an alkyl group having 1 to 4 carbon atoms, or from glycerides of the carboxylic acids of the formula R ^ -COOH, in particular triglycerides, by converting them to the carboxylic acid ethanolamides in the presence of ethanylamine and the reaction mixture is then allowed to react in a second reaction stage while further increasing the reaction temperature. Here, the technically easily accessible carboxylic acid methyl esters and glycerides are preferred as starting products. These are reacted in the presence of ethanolamine and the claimed catalysts in a first reaction stage at elevated temperature, preferably at atmospheric pressure, with removal of water and alcohol or glycerol to give carboxylic acid ethanolamides, and the reaction mixture is allowed to continue in a second reaction stage with a further increase in Reaction temperature, preferably in a vacuum. The ethanolamine is preferably used in a 50 to 400 mol% excess, based on the starting material, with unreacted or excess ethanolamine being removed from the reaction mixture before the second reaction stage. A reaction temperature of 100 to 170 ° C. is preferably used in the first reaction stage and a temperature of 175 to 250 ° C. is used in the second stage. The catalysts are preferably used in an amount of 0.1 to 10, preferably 0.5 to 5, in particular 0 , 5 to 3 mol%, based on the starting material used. Titanium tetraalcoholates, in particular selected from those of titanium tetraethylate, tetrapropylate, tetraisopropoxide and -tetrabutylate formed group used. Alternatively, mixed anhydrides of titanium acid with monocarboxylic acids, in particular those with 1 to 4 carbon atoms, preferably titanium tetraacetate, are used. Further preferred catalysts here are titanium or zirconium acetylacetonates of the general formula VI and the above-mentioned polycondensation products of esters of titanium acid with monoalkanols having 2 to 10 carbon atoms with pentaerythritol and titanium (IV) or Zr (IV) tetraaminoethanolates.

In this process variant, the reaction is preferably carried out in vacuo and the water of reaction formed is distilled together with the 2-0xazolines with further separation during the distillation, or the water of reaction is removed by azeotropic distillation before the 2-oxazolines are distilled.

It is particularly advantageous here to carry out the first and second reaction stages as a one-pot process in a reactor.

The invention is explained in more detail below on the basis of preferred exemplary embodiments.

Example 1.

2-phenyl-2-oxazoline.

In a stirring apparatus with a fractionating column, a descending cooler with distillation tanks, a vacuum device with a cold trap for the water of reaction, a thermometer and an inlet pipe for protective gas, a mixture was made

1042 g (7.5 mol) of methyl benzoate (98%), 921 g (15 mol) of ethanolamine (99.5%) and 25.5 g (0.075 mol, 1 mol%) of titanium tetrabutylate

submitted.

The reaction mixture was heated under nitrogen; the methanol formed at 128 to 160 ° C was distilled off at normal pressure.

The excess ethanolamine was then distilled off in vacuo at 87 ° C. and 20 hPa.

The benzoic acid ethanolamide thus obtained was heated in vacuo to 178-226 ° C., the 2-phenyl-2-oxazoline and water formed simultaneously distilling over at 122 ° C. and 20 hPa. Most of the water was condensed in the cold trap. In order to remove any entrained water from the distilled oxazoline, a molecular sieve (4 A) was added to the distillation vessel as a drying agent.

836.7 g (75% of theory, based on the methyl benzoate used) of 2-phenyl-2-oxazoline which still contained small amounts of benzoic acid ethanolamide were obtained. By distillation again on a thin-film evaporator (bp = 120 to 125 ° C. at 19 hPa), 775.3 g (70% of theory) of pure 2-phenyl-2-oxazoline were obtained with the following characteristics:

n _D ²⁰ = 1.5672

IR: 1650 (C = N); 1260, 1065 (C-0-C =); 975, 945, 900cm " ¹

(Oxazoline).

Example 2.

2-hydroxymethyl-2-oxazoline.

Analogously to the procedure described in Example 1, glycolic acid methyl ester was reacted with ethanolamine. The batches were:

135.1 g (1.5 mol) of glycolic acid methyl ester

184.2 g (3.0 mol) ethanolamine (99.5%)

5.1 g (0.015 mol, 1 mol%) of titanium tetrabutylate.

Yield = 31.6 g. Sublimation point = 98 ° C (21 hPa).

After recrystallization, 20.7 g of pure 2-hydroxymethyl-2-oxazoline were obtained.

Analysis:

C4H7NO2 (101.107)

Cber = 47.52 C _ge f = 47.5 H _ber = 6.98 H _gef = 7.00 Nfaer - 13.85 N _gef = 13.6

IR: 1680 (ON); 1209, 1099 (C-0-C =); 981, 956, 922cm- ¹ (oxazoline); ^{• Ϊ-H} NMR: delta (in ppm) = 4.76 (1H, s), 4.24 (2H, t, J = 7 Hz), 3.86 (2H, t, J = 7 Hz).

Example 3.

2- (5-hydroxypentyl) -2-oxazoline.

Analogously to the procedure of Example 1, caprolactone was reacted with ethanolamine. The batches were:

230.6 g (2.0 mol) caprolactone

245.5 g (4.0 mol) ethanolamine (99.5%)

6.8 g (0.02 mol, 1 mol%) of titanium tetrabutylate.

Yield: 249.8 g (approx. 80% purity).

Kp = 140 ° C (0.03 hPa).

After renewed vacuum distillation (bp = 114 ° C. at 1.2 hPa), 77.2% of the title compound were obtained in 95% purity.

Example 4.

Methoxymethyl-2-oxazoline.

Analogously to the procedure of Example 1, methoxyacetic acid was reacted with ethanolamine. The batches were:

180.2 g (2.0 mol) methoxyacetic acid (purity over 95%) 245.5 g (4.0 mol) ethanolamine

6.8 g (0.02 mol, 1 mol%) of titanium tetrabutylate:

Yield = 188.6 g (82% of theory).

Kp = 130 ° C to 163 ° C (167 hPa). After another vacuum distillation, 124.4 g (54% of theory) of pure 2-methoxymethyl-2-oxazoline were obtained; Bp 69 ° C / 20 hPa.

Analysis:

C5H9NO2 (115.134)

C er ^~ 52.16 C _ge f = 52.0

^H ber = 7.88 H _ge f = 7.94

Nber ^~ -> ■ - ^' N _gβ f = 12.3

IR: 1668 (C = N); 1191, 1122 (C-0-C =); 982, 948, 918 cm " ¹ (oxazoline);

^Ϊ -H-NMR: delta (in ppm) = 4.31 (2H, t, J = 7 Hz), 4.12 (2H, s), 3.90 (2H, t, J = 7 Hz), 3.46 (3H, s).

Example 5.

2- (2,5-dioxahexyl) -2-oxazoline.

Analogously to the procedure of Example 1, 3,6-dioxaheptanoic acid (methoxyethoxyacetic acid) was reacted with ethanolamine.

The batches were:

235 g (1.50 mol) 3,6-dioxaheptanoic acid (purity approx. 80 - 85%)

215 g (3 mol) ethanolamine (99.5%)

6.0 g (0.0175 mol, 1 mol%) of titanium tetrabutylate.

Yield = 209.1 g (88% of theory).

Kp = 140 to 180 ° C (0.5 hPa). After renewed vacuum distillation (bp = 57 to 66 ° C. at 0.01 hPa), 129.1 g (61% of theory) of the title compound were obtained.

Analysis:

C7H13NO3 (159.187)

_Cber = 52.82 C _ge f = 52.8

H _b er = 8.23 H = 8.51 _Found

NBER ^β 8 ^'80 _g ef = 8.77

n _D ² 0 = 1.4571

IR: 1669 (C = N); 1199, 1116 (C-0-C =); 982, 950, 907 cπr ¹ (oxazoline);

iH-NMR: delta (in ppm) = 4.30 (2H, t, J = 7 Hz), 4.24 (2H, s), 3.89 (2H, t, J = 7 Hz), 3.7446 (2H, dd, J = 3.4 Hz), 3.58 (2H, dd, J = 3.4 Hz), 3.38 (3H, s).

Example 6.

2- (2,5,8-trioxanonyl) -2-oxazoline.

Analogously to the procedure of Example 1, 3,6,9-trioxadecanoic acid (methoxyethoxyethoxyacetic acid) was reacted with ethanolamine. The batches were:

231.6 g (1.24 mol) 3,6,9-trioxadecanoic acid (purity approx. 95%) 159.6 g (2.6 mol) ethanolamine (99.5%) 44 g (0.013 mol, 1 mol%) titanium tetrabutylate.

Yield = 187.0 g (75% of theory).

Kp = 167 - 182 ° C (0.4 - 2.6 hPa). After renewed vacuum distillation (bp = 101-106 ° C. at 0.15 hPa), 149.1 g (59%) of the pure title compound were obtained.

Analysis:

CgH ₁₇ Nθ4 (203.24)

C _b er = 53.19 C _ge f = 53.8

^H calc = 8.43 H = 8.49 _Found

Nber = 6.89 N _ge f = 6.92

n _D 20 = 1.4602

IR: 1669 (C = N); 1198, 1109 (C-0-C =); 982, 950, 907 cm " ¹ (oxazoline);

^Ϊ -H-NMR: delta (in ρpm) = 4.30 (2H, t, J - 7 Hz), 4.23 (2H, s), 3.88 (2H, t, J = 7 Hz), 3.75 (2H, m), 3.70 (2H, m), 3.65 (2H, m), 3.55 (2H, m), 3.38 (3H, s).

Example 7.

Preparation of a 2-substituted-2-oxazoline from m-tolylic acid.

Analogously to the preparation for example 1, m-tolylic acid was reacted with ethanolamine to give 2- (3-methylphenyl) -2-oxazoline. The batches were:

347.3 g (2.5 mol) m-tolylic acid, 98% 307.0 g (5.0 mol) ethanolamine, 99.5% 25.5 g (0.075 mol, 3 mol%) titanium tetrabutylate

Yield = 241 g (60% of theory) of 2- (3-methylphenyl) -2-oxazoline.

KP = 128-142 ° C (16 hPa). IR: 1650 (C = N); 1268, 1067 (C-0-C =); 979, 951, 910 cm " ¹ (oxazoline).

iH-R: delta (in ppm) 7.78 (1H, s); 7.72 (1H, m); 7.29 (2H, m); 4.42 (2H, t, J = 7 Hz); 4.04 (2H, t, J = 7 Hz); 2.37 (3H, s).

Example 8.

Preparation of a 2-substituted-2-oxazoline from m-methoxybenzoic acid.

Analogously to the preparation for example 1, m-methoxybenzoic acid was reacted with ethanolamine to give 2- (3-methoxyphenyl) -2-oxazoline. The batches were:

232.9 g (1.5 mol) m-methoxybenzoic acid, 98% 184.2 g (3.0 mol) ethanolamine, 99.5% 15.3 g (0.045 mol, 3 mol%) titanium tetrabutylate

Yield = 116 g (44% of theory) of 2- (3-methoxyphenyl) -2-oxazoline.

Kp = 122 - 157 ° C (17-19 hPa)

IR: 1650 (C = N); 1270, 1043 (C-0-C =); 980, 951, 910 cm " ¹ (oxazoline).

- ^ - NMR: delta (in ppm) 7.54 (1H, dt, J = 6; 1 Hz); 7.50 (1H, t, J = 1 Hz); 7.32 (1H, t, J = 6 Hz); 7.03 (1H, dt, J = 6, 1 Hz); 4.43 (2H, t, J = 7 Hz); 4.06 (2H, t, J = 7 Hz); 3.86 (3H, s).

Example 9.

Preparation of 2-phenyl-2-oxazoline from methyl benzoate in the presence of tita (IV) -diisopropoxy-bis-acetylacetonate. Analogously to the preparation for example 1, methyl benzoate was reacted with ethanolamine to give 2-phenyl-2-oxazoline. The batches were:

272.3 g (2.0 mol) of methyl benzoate, 98%

244.3 g (4.0 mol) of ethanolamine, 99.5%

7.3 g (0.02 mol, 1 mol%) of titanium (IV) diisopropoxy-bis-acetylacetonate.

Yield = 236 g (82% of theory) of 2-phenyl-2-oxazoline.

Kp = 107 - 120 ° C (20 hPa)

Example 10.

Preparation of 2-phenyl-2-oxazoline from benzoic acid ethanol amide in the presence of titanium tetrabutylate.

Analogously to the preparation for example 1 (second stage), benzoic acid ethanolamide was converted to 2-phenyl-2-oxazoline. The batches were:

330.4 g (1.9 mol) benzoic acid ethanolamide, 95% 7.3 g (0.02 mol, 3 mol%) titanium tetrabutylate

Yield = 216 g (77% of theory) of 2-phenyl-2-oxazoline.

Kp = 112-114 ° C (19 hPa).

Claims

1. Process for the preparation of 2-oxazolines of the general formula I

in the Rl

an aryl or aralkyl radical optionally substituted in the aromatic nucleus, an alkyl group with 4 to 6 carbon atoms, a hydroxy-substituted alkyl group with 1 to 6 carbon atoms, an alkoxy-substituted alkyl group with 1 to 6 carbon atoms in the alkyl and 1 to 18 carbon atoms in the alkoxy group, or a radical of the general formula II

R ² - (OC ₂ H5) p-0-CH ₂ - (II)

in the

R ^{2 is} an alkyl or alkenyl group with 1 to 18

Carbon atoms, especially a methyl group, and p is a number in the range from 1 to 10, in particular 1 to 2,

means

by condensation of carboxylic acid ethanolamides or their precursors in the presence of catalysts in the liquid phase,

characterized in that one

a) carboxylic acids of the general formula III

R! -COOH (HI)

in the R! as defined above, esters of these carboxylic acids with monoalkanols having 1 to 4 carbon atoms or glycerides of these carboxylic acids with 2-aminoethanol or

b) ethanolamides of these carboxylic acids

in the presence of titanium or zirconium compounds of the general formula IV

M (OR ³ ) 4 (IV)

in which M is tetravalent titanium or zirconium and R ^{3 is} an alkyl group with at least 2, in particular 2 to 4, carbon atoms, an acyl group with at least 2, in particular 2 to 10, carbon atoms or a 2-aminoethyleneoxy group or a residue of a beta-diketone of the general formula V. R ⁴ -C = CH-CO-R ⁵ (V)

in which R ⁴ and R5 are identical or different radicals from the group formed by alkyl groups having 1 to 4 carbon atoms and optionally substituted in the p-position, phenyl, where in each case two of the groups R ³ together from the divalent radical of a dihydric alcohol with 2 can have up to 4 carbon atoms,

in the presence of titanyl acetylacetonate or

in the presence of condensation products of titanium (IV) or zirconium (IV) tetraalkoxylates of the general formula IV, in which M and R ^{3 are} as defined above, with multifunctional alkanols, in particular with 3 to 12 carbon atoms and 2 to 6 hydroxyl groups,

2. The method according to claim 1, characterized in that the catalysts are esters of titanium acid (H4Tiθ4) or zirconic acid (H4Zrθ4) or mixed anhydrides of Titan¬ acid or zirconic acid with organic acids of general formula IV, in which M = Ti or Zr and R ^{3 are} an alkyl group having 2 or more than 2, in particular 2 to 4, carbon atoms or an acyl group derived from a monocarboxylic acid having 2 or more, in particular 2 to 10, carbon atoms.

3. The method according to claim 1 or 2, characterized in that catalysts from the group formed by titanium or zirconium tetraethylate, tetrapropylate, tetraisopropoxide, tetrabutylate and tetraacetate are used.

4. The method according to claim 1 or 2, characterized in that tetra (aminoethyl) titanate or zirconate is used as a catalyst.

5. The method according to claim 1 or 2, characterized in that titanium or zirconium acetylacetonates of the general formula VI as catalysts

(RßojmMfACAJn (VI)

in which R ^ is an alkyl group with 1 to 4 carbon atoms,

ACA an acetylacetonate residue and

m the number 0 and n the number 4 or m the number 2 and n the number 2

mean used.

6. The method according to claim 1 or 2, characterized in that polycondensation products of esters of titanium acid with monoalkanols having 2 to 10 carbon atoms with pentaerythritol are used as catalysts.

7. The method according to at least one of claims 1 to 6, characterized in that the catalysts in amounts of 0.1 to 10, preferably 0.5 to 5, in particular 0.5 to 3 mol%, based on

Carboxylic acid monoethanolamide or precursor thereof used.

8. The method according to at least one of claims 1 to 7, characterized in that one carries out the condensation at 150 to 270 ° C.

9. The method according to at least one of claims 1 to 8, characterized in that one carries out the reaction in vacuo.

10. The method according to at least one of claims 1 to 9, characterized in that the reaction water or alkanol formed is distilled together with the 2-oxazolines and then or simultaneously or separately from these or before the distillation of the 2-oxazolines removed by azeotropic distillation.

11. The method according to at least one of claims 1 to 10, characterized in that in a first reaction stage carboxylic acids or carboxylic acid esters of the general formula VII

Rl-COOR ⁷ (VII)

in the Rl is as defined above and R ^{7 is} hydrogen or an alkyl group having 1 to 4 carbon atoms, or carboxylic acid glycerides in the presence of ethanolamine at elevated temperature and at atmospheric pressure to the fatty acid ethanolamides, water and alcohol or glycerol formed and removed Reaction mixture can react in a second reaction stage while further increasing the reaction temperature in vacuo.

12. The method according to claim 11, characterized in that the ethanolamine is used in a 50 to 400 mol% excess, based on the carboxylic acid, carboxylic acid ester or carboxylic acid glyceride used.

13. The method according to claim 11 or 12, characterized gekennzeich¬ net that before the second reaction stage unreacted or excess ethanolamine is removed from the reaction mixture.

14. The method according to at least one of claims 11 to 13, characterized in that one uses a reaction temperature of 100 to 170 ° C in the first reaction stage.

15. The method according to at least one of claims 11 to 14, characterized in that one uses a reaction temperature of 175 to 270 ° C in the second reaction stage.

16. The method according to at least one of claims 11 to 15, characterized in that titanium tetraalcoholates are used as the titanium acid ester.

17. The method according to at least one of claims 11 to 16, characterized in that titanium tetraalcoholates from the group formed by titanium tetraethylate, tetrapropylate, tetraisopropyl and tetrabutylate are used.

18. The method according to at least one of claims 11 to 15, characterized in that tetra (aminoethyl) titanate or zirconate is used as a catalyst.

19. The method according to at least one of claims 11 to 15, characterized in that mixed anhydrides of titanium acid with monocarboxylic acids are used.

20. The method according to at least one of claims 11 to 15, characterized in that one uses titanium tetraacetate.

21. The method according to at least one of claims 11 to 15, characterized in that titanium or zirconium acetylacetonates of the general formula VI are used as catalysts

(Rδθ) _m M (ACA) _n (VI)

used in which R **, ACA, m and n are as defined above.

22. The method according to at least one of claims 11 to 15, characterized in that poly¬ condensation products of esters of titanium acid with monoalkanols having 2 to 10 carbon atoms with pentaerythritol are used as catalysts.

23. The method according to any one of claims 11 to 22, characterized in that the catalysts in an amount of 0.1 to 10, preferably 0.5 to 5, in particular 0.5 to 3 mol%, based on carboxylic acids, carboxylic acid esters or carboxylic acid glycerides.

24. The method according to at least one of claims 11 to 23, characterized in that the water of reaction formed in the second reaction step is distilled off together with the 2-oxazolines and then or simultaneously removed or before azeotropic distillation of the 2-oxazolines Distillation removed.

25. The method according to at least one of claims 11 to 24, characterized in that one carries out the first and second reaction stage as a one-pot process.