DE2718103A1 - Amide gp.-substd. (thio)hydantoin prepn. - by reacting maleimide with amine and then (thio)cyanate and cyclising - Google Patents

Abstract

Amide gp-substd (thio)hydantoins are prepd. by (a) reacting maleimides having formula (I): (where R1 and R2 are H or an aliphatic gp. R5 is H or an opt. substd aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or heterocyclic gp. and k is 1-3, esp. 1-2) with a prim. mono- or polyamine (b) reacting the prod. with an organic mono- or polyiso (thio)cyanate and (c) cyclising by heating opt. in the presence of catalysts. Monohydantoins can be used as plant-protective agents or as pharmaceuticals. Poly(thio)hydantoins are heat-stable and used as lacquers(claimed), e.g. for metal sheets and wires, as adhesives, foils and mouldings. (A) can be built into polymers to increase heat-stability. (I) are prepd. smoothly and in high yields. In an example 1,3-diphenyl-5-(phenylaminocarbonyl-methylene)-hydantoin was prepd. by (i) reacting aniline and N-Ph maleimide, (ii) reacting prod. with PhNCO and (iii) cyclising.

Description

Process for the preparation of with amide groups

modified (thio) hydantoins The manufacture of containing amide groups modified hydrantions is already known. In doing so, these connections are made through Reaction of aspartic acid esters with isocyanates or isothiocyanates, then Cyclization to hydantoin-5-acetic acid esters and by reaction with amines under Elimination of alcohols formed.

It has now been found that modification with amide groups - preferably in the 5-position - hydantoins are obtained smoothly and with very good yields if amines are used with optionally substituted and optionally prepared in situ maleimides reacts, the asparaginimides formed react with isocyanate or isothiocyanate leaves and cyclized under thermal and catalytic influence.

The invention therefore relates to a process for the preparation of (thio) hydantoins substituted with amide groups, which is characterized in that maleic acid imides of the general formula (I) in which R1 and R2, identical or different, are hydrogen or an aliphatic radical, R5 is hydrogen or an optionally substituted aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or heterocyclic radical and k is an integer from 1-3, preferably 1-2 , means, reacts with a primary mono- or polyamine, the reaction product reacts with an organic mono- or polyiso- (thio) cyanate and cyclized by subsequent heating, optionally in the presence of catalysts.

Maleimides are suitable for the process according to the invention Imides of the general formula (I), in which preferably R1 and R2 for hydrogen or a C1-C18 alkyl radical, which may optionally be substituted with halogen (chlorine, Bromine) can be substituted, and R5 for hydrogen, an alkyl radical with C1-C20, a cycloalkyl radical with C5-C12, optionally with halogen (preferably chlorine, Bromine), with a hydroxy, alkoxy with C1-C18 alkoxycarbonyl - with C2-C18 C18 or an alkoxycarbonyl group, an aryl radical with C6-C16, which optionally with halogen (preferably chlorine, bromine), nitro, alkyl with C1-C18, Haloalkyl with C1-C18, hydroxy-, hydroxyalkoxy- with C1-C18 alkoxycarbonyl- with C2-C18 or hydroxycarbonyl groups can be substituted with an aralkyl radical C7-C18 or a heterocyclic radical with C5-C12 and N, 0 and / or S atoms in the Ring.

Heterocyclic radicals are preferably aromatic or cycloaliphatic 5- and 6-rings containing one or more oxygen, nitrogen and / or sulfur atoms contain, e.g. furan, pyridine, thiophene, imidazole, pyrimidine and piperazine derived residues. R5 particularly preferably represents hydrogen, an alkyl radical with C1-C8, an aryl radical with C6-C16 such as phenyl, naphthyl, bisphenyl or above O, S, S02, CH2, CH3-C-CH3 or CO linked diphenyl radicals.

Imides of maleic acid such as maleic acid imide, N-methyl-malein, acid imide, N-butyl maleic acid imide, N-phenyl maleic acid imide, bismaleimide based on hexamethylenediamine, Diaminodiphenylmethane, phenylenediamine, tolylenediamine and naphthylenediamine are used very particularly preferably. The production of maleimides takes place from the maleamic acids by elimination of water and is from the literature well known.

The mono- or polyamines used in the reaction according to the invention are preferably those of the general formula (II) in which R3 has the meaning of R5 with the exception of hydrogen, and 1 is an integer from 1-3, preferably 1-2.

R3 is particularly preferably derived from an alkyl radical with C1-C181 one Cycloalkyl radical with C5-C6 or optionally with halogen, C1-C3 alkyl or C1-C3-alkoxy groups substituted aryl radical with C6-C16 such as phenyl, naphthyl, Bisphenyl, benzyl or diphenyl radicals linked via 0, S, S02, CH2, CH3-C-CH3 or CO away. Primary amines such as plethylamine, ethylamine, butylamine, Cyclohexylamine, ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, technical mixtures of trimethylhexamethylenediamine, 1,4-diamino-cyclohexane, (isophoronediamine), 1-aminomethyl-5-amino-1 3, 3-trimethyl-cyclohexane, 4,4'-diaminodicyclohexylmethane, Ethanolamine, propanolamine, isopropanolamine, aniline, aminophenol, 3- and 4-aminobenzoic acid or their esters benzylamine, m- and p-phenylenediamine, 2,4- and 2,6-diaminotoluene or their technical mixtures, m- and p-xylylenediamine or their technical mixtures, 1,5-naphthylenediamine, benzidine, 4,4'-diaminodiphenylmethane and their technical isomer mixtures, 2,2-bis- (4-aminophenyl) -propane, 4,4-diaminodiphenyl ether used for the inventive method.

As mono (thio) isocyanates in the context of the invention are aliphatic and aromatic compounds optionally substituted by heteroatoms with an NC0 group in the molecule, e.g. alkyl isocyanates such as ethyl, methyl, Butyl, dodecyl and stearyl isocyanate, aromatic, optionally substituted Monoisocyanates such as phenyl, tolyl, isopropyl, nonylchlor, tetrachloro, pentachloro, Benzyl, bromophenyl isocyanate or isocyanatobenzoic acid ester, -phthalic acid ester, isophthalic acid ester, isocyanatobenzonitrile, cycloaliphatic isocyanates such as cyclohexyl isocyanate and unsaturated isocyanates such as allyl, oleyl, cyclohexenyl isocyanate.

Starting components to be used according to the invention are also used aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic Polyisocyanates / preferably diisocyanates' under consideration (cf. Annalen, 562, p 75 to 136), for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1 3- and / or -1,4-phenylene diisocyanate, perhydro-2, 4 'and / or -4,4' -diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these Isomers, diphenylmethane-2,4'- and / or 4,4'-diisocyanate, naphthylene-1,5-diisocyanate, Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, such as they are obtained by aniline-formaldehyde condensation and subsequent phosgenation and are described, for example, in British patents 874 430 and 848 671, perchlorinated aryl polyisocyanates, such as those described in German Auslegeschrift 1 157 601 are described, polyisocyanates containing carbodiimide groups, such as are described in German patent specification 1 092 007, diisocyanates as they in U.S. Patent 3,492,330 containing allophanate groups Polyisocyanates, such as are e.g.

in British Patent 99 890, Belgian 761 626 and published Dutch patent application 7 102 524, Polyisocyanates containing isocyanurate groups, such as those in German patents 1 022 789, 1 222 067 and 1 027 394 as well as in the German Offenlegungsschriften 1 929 034 and 2004 048, polyisocyanates containing urethane groups, as for example in the Belgian patent 752 261 or in the US patent 3,394,164, polyisocyanates containing acylated urea groups according to German Patent 1,230,778, polyisocyanates containing biuret groups, such as, for example, in German Patent 1 101 394 in British Patent 889 050 and in French patent 7 017 514 Telomerization reactions produced polyisocyanates, such as those in the Belgian Patent specification 723 640 are described, polyisocyanates containing ester groups, as described, for example, in British Patents 956,474 and 1,072,956, in U.S. Patent 3,567,763 and in the German patent specification 1 231 688 named are, reaction products of the above isocyanates with acetylene according to the German Patent Specification 1,072,358.

It is also possible to use the technical isocyanate production distillation residues containing isocyanate groups, if appropriate dissolved in one or more of the aforementioned polyisocyanates to be used. Further it is possible to use any mixtures of the aforementioned polyisocyanates.

Mono- or polyiso (thio) cyanates of the general types are preferably suitable Formula (III) 4 R4 (-NC0) z or R (-NCS) z (III) in which R4 the meaning of R5 with the exception of hydrogen, and z is an integer from 1-3, preferably 1-2.

Preferably steep R4 for an aliphatic radical with 1-20 carbon atoms, which is optionally substituted by halogen, C1-C6-alkyl and / or C6-C16-aryl groups can be an aromatic radical with 6-12 carbon atoms, a cycloaliphatic radical with 5-12 carbon atoms' an aliphatic-aromatic radical with 7-20 carbon atoms and one Aromatic or cyclcaliphatic radical containing heteroatoms such as N, O or S with 5-12 carbon atoms.

Particularly preferred are aliphatic radicals with 2-12 carbon atoms, or an aryl radical such as phenyl, tolyl, naphthyl, diphenylmethane, diphenyl ether, diphenyl or Diphenyl radicals linked via S, S02, CO or CH3-C-CH3.

The technically easily accessible mixtures are preferably used from toluene diisocyanates, m-phenylene diisocyanate, phenyl isocyanate and its substitution products, as well as phosgenated condensates of aniline and formaldehyde with a polyphenylene-methylene structure and the symmetrical compounds 4,4'-diisocyanato-diphenylmethane, 4,4'-diisocyanato-diphenyl ether, p-phenylene diisocyanate, 4,4'-diisocyanato-diphenyldimethyl methane, analogous hydroaromatic Diisocyanates and aliphatic diisocyanates with 2 - 12 carbon atoms such as hexamethylene diisocyanate and isophorone derived diisocyanates.

The isocyanates can be in free form, furthermore partially or completely also in the form of their compounds containing reactive hydrogen when they react, accessible derivatives which react as releasers under the reaction conditions can be used.

Preferred releasers are those derived from lactams, e.g.

Caprolactam, accessible acyl ureas and the carbamic acid esters obtained from aromatic and aliphatic mono- and polyhydroxy compounds, which, for example, have the general formulas are used, where R and z have the meaning given above and A is the organic radical of a monohydroxy compound and B is the organic radical of a bis- or trisfunctional hydroxy compound, preferably an aliphatic radical with 1-10 carbon atoms, a cycloaliphatic radical with 5 - 10 carbon atoms, an aliphatic-aromatic radical with 7-12 carbon atoms and an aromatic radical with 6-12 carbon atoms, each of which can also be substituted with alkyl and / or aryl groups, and n for a whole Number from 1 to 1000, preferably 1 to 100.

Examples are the carbamic acid esters from phenol, isomeric cresols, their technical mixtures and similar aromatic hydroxyl compounds, aliphatic Mono alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Diethylene glycol monomethyl ether, cyclohexanol, benzyl alcohol and aliphatic di- or polyols such as ethylene glycol and trimethylolpropane are listed.

The urethanes can be used as such or only through in situ Implementation can be generated with alcohols.

Instead of the mono and (poly) isocyanates mentioned, the analogous (Poly) isothiocyanates can be used.

The method according to the invention can be represented by the following equation: where the radicals R1 R have the meaning given above and for k, 1 and z = 1 a monomolecular compound and for k and / or 1 and / or z> 1 a higher molecular weight compound is formed, the hydantoin rings via the radicals R5 and / or R3 and / or R4 are linked, and n is an integer from 1-1,000, preferably 1--100.

The reaction between the maleimides and the amines takes place generally at temperatures from -200 ° C. to 2000 ° C., preferably optionally in inert solvents and optionally in the presence of an effective amount an acidic catalyst. The acidic catalyst can also be used as a solvent will. Carboxylic acids such as acetic acid, butyric acid, Pivalic acid, benzoic acid or trichloroacetic acid, phenol, and cresols by electrophiles Substitution of acidified phenols.

The reaction between the aminimides and the iso (thio) cyanates takes place generally between -200C and 1200C, preferably at 200C to 800C, if appropriate in inert solvents, the customary, known catalysts of amine-iso (thio) cyanate addition can be used.

Preferred inert solvents are aliphatic or aromatic Hydrocarbons and their halogenation products in question, such as diisopropylbenzene, Methylnaphthalene, di- or trichlorobenzene or polar solvents such as N-methylpyrrolidone, Dimethylformamide, dimethylacetamide, phenol, cresols or xylenols.

The cyclization to the hydantoins containing amide groups can in the presence of the catalysts known in hydantoin production, preferably Triethylamine, dimethylaniline, Dabco, acetic acid, pivalic acid, benzoic acid or Metal catalysts such as BF3, titanium tetrabutylate or iron acetylacetonate at temperatures from 1200.degree. C. to 250.degree. C., preferably 150.degree. C. to 2000.degree. In general reaction times of 1-10 hours are necessary.

The reaction is generally carried out using stoichiometric Quantities carried out. However, one of the components can also be used in excess to obtain polymers with additional reactive groups. The work-up the reaction products take place in the usual way, e.g. by distillation or Crystallization process. Polymer products can be applied directly to sheet metal or wires be burned in in a known manner. However, they can also be caused by failures, e.g. with acetone or methanol, obtained in pure form and thus further processed into foils, for example will.

The hydantoins modified with amide groups obtained according to the invention can have an amide group and optionally in the presence of other reactive ones Groups on the radicals R3, R4 and R5 in polymers of various types to increase built into the temperature resistance of these polymers will, e.g. by reaction with mono- or polycarboxylic acids and their derivatives or with Mono- or polyalcohols to polyester with increased thermal resistance. the Monohydantoins can be used as pesticides or as pharmaceutical products Find use.

The polyhydantoins according to the invention are distinguished by special features Temperature resistance and are suitable for use as adhesives, varnishes, Films and moldings. Their properties can vary for different areas of application by adding fillers, pigments and low and high molecular weight components, e.g. for the production of lacquers and foils by mixing with polyesters or polyamides, can be varied within wide limits.

Example 1: 1,3-Diphenyl-5- (phenylaminocarbonyl-methylene) hydantoin 26.6 parts of the compound (from aniline and N-phenylmaleimide) are dissolved in 100 ml of 0-dichlorobenzene, mixed with 11.9 parts of phenyl isocyanate and left to stand overnight. After adding 0.1 g of 1,4-diaza-bicyclo L2,2,2octane, the solution is stirred for 6 hours at 1750 ° C., the solvent is distilled off in vacuo and toluene is added to the residue. The resulting krist. Precipitate is filtered off with suction and recrystallized from ethyl acetate.

NMR and IR spectra (for hydantoin 1715 and 1770 cm 1; for amide 1690 cm 1) prove the calculated structure.

Analysis: calc. 71.6% C, 4.93% H and 10.9% N found. 71.7% C 5.1% H and 10.9% N Example 2: 1-Cyclohexyl-3-phenyl-5- (phenylaminocarbonylmethylene) hydantoin 17.3 parts of N-phenyl-maleimide are dissolved in 50 parts of cresol and 9.9 parts of cyclohexylamine added dropwise at 30-350C.

After 2 hours of stirring at room temperature, the solution is with 11.9 g of phenyl isocyanate are added and the mixture is left to stand overnight. After 2 hours Reaction at 2000C, the solvent is distilled off in vacuo and the oily one Residue dissolved in ethanol. After cooling, 19.1 g of krist. Precipitation obtained by NMR and IR analysis (for hydantoin 1705 and 1765 cm; for amid 1690 cm) the structure belonged to.

Analysis: calc .: 70.6% C 6.38% H and 10.7% N found: 70.9% C 6.5% H and 10.6% N Example 3 35.8 parts of the bisimide from maleic anhydride and 4,4'-diaminodiphenylmethane are dissolved in 185 parts of cresol, mixed with 1.5 ml of acetic acid and reacted with 18.6 parts of aniline at 120 ° C. for 15 hours.

The resulting solution is at 35-40 ° C with 25 parts of 4,4'-Diisocynato-diphenylmethane added, left to stand overnight, with 0.1 part 1,4-diaza-bicyclot2,2,2ioctane added and allowed to react for 6 h at 2000C.

There are 263 g of a 30% polyhydantoin amide varnish with a viscosity of 4900 cP at 25 ° C. The IR spectrum shows the characteristic of hydantoin Bands at 1715 and 1770 cm 1 and the band at 1695 that is characteristic of amide cm 1. A paint film baked onto a metal sheet shows, in addition to very good thermal Properties good elasticity.

Example 4 a) 173 parts of N-phenylmaleimide, 1 liter of acetic acid and 99 parts of 4,4'-diaminodiphenylmethane are stirred for 1 hour at 1000 ° C. and, after cooling, the precipitate formed (175 parts) is filtered off with suction, washed and dried.

b) 54.4 parts of the adduct prepared according to a) are in 238 parts Dissolved cresol and reacted at 35-400C with 25 g of 4,4'-diisocyanatodiphenylmethane. The resulting solution is left to stand overnight with 0.1 g of diazo-bicycloC2,2,2joctane added and condensed for 6 h at 2000C. There are 316 g of a 25% amide-modified Polyhydantoin varnish obtained with a viscosity of 700 cP at 250C, its IR spectrum the bands characteristic of hydantoin at 1780 and 1775 cm -1 as well as those for Amid characteristic band at 1695 cm An elastic band burned onto a sheet metal Lacquer film shows very good thermal properties.

Claims (1)

Claims: 1. A process for the preparation of (thio) hydantoins substituted with amide groups, characterized in that maleic acid imides of the general formula (I) in which R1 and R2S are identical or different, represent hydrogen or an aliphatic radical, R is hydrogen or an optionally substituted aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or heterocyclic radical and k is an integer from 1-3, preferably t-2, means, reacts with a primary mono- or polyamine, reacts the U-setzugsprodukt with an organic bno- or polyiso- (thiolcyanate and is cyclized by subsequent heating, optionally in the presence of catalysts, 2. Use of the (thio ) hydantoine as varnishes.