DE2625722A1 - PARABANIC ACID AMINALS - Google Patents

Description

Bayer Aktiengesellschaft 2625722

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk Str-kl

- L June 1976

Parabanic acid aminals

The invention relates to new parabanic acid aminals and a process for their production.

The structures of these new compounds are given by the general formula (I)

R ⁴ o _{/ R} 5

R * R5 °

reproduced,

wherein

R represents an optionally substituted aliphatic, aliphatic

table-aromatic or aromatic carbamoyl radical, R and R, identical or different, for hydrogen or

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an optionally substituted aliphatic, aliphatic-aromatic or aromatic radical,

R represents hydrogen or an optionally substituted one aliphatic, aliphatic-aromatic or aromatic carbamoyl radical and

R represents an optionally substituted aliphatic, aliphatic-aromatic or aromatic radical.

Optionally substituted aliphatic radicals are those with 1 to 20 carbon atoms, preferably with 1 to 16 carbon atoms to be understood, these radicals may optionally contain up to 2 double bonds or one triple bond. Of course, as aliphatic radicals also cycloaliphatic radicals with 5 to 12, preferably 5 and 6 carbon atoms in the ring system to understand.

Optionally substituted aromatic radicals are those with 6 to 14, preferably 6 to 10, in particular To understand 6 carbon atoms in the ring system, in the case of the phenyl radical this optionally also can then be linked to a further aryl radical via an oxygen or sulfur atom.

Carbamoyl radicals are radicals of the following structure:

H °
RNC

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R for an optionally substituted aliphatic radical, preferably with 1 to 16 carbon atoms, aliphatic-aromatic Radical or aromatic radical, preferably having 6 to 14 carbon atoms, as defined above.

Examples of possible substituents on the abovementioned aliphatic or aromatic radicals are:
Aryl with C _g - C ₁₆ (preferably phenyl), CN, NO ₂ , alkyl mercapto and alkoxy groups with preferably 1-4 C atoms, carbon ester groups, preferably those with lower aliphatic alcohols, preferably with 1 to 8, in particular 1 to 4 C Atoms, as well as the di-substituted amino group, preferably substituted by lower aliphatic radicals (preferably with 1-4 carbon atoms), halogens (preferably fluorine, chlorine, bromine), lower haloalkyl radicals (preferably with 1 to 4 carbon atoms and preferably with fluorine and / or chlorine) and, in the case of the aromatic and heterocyclic radicals, also lower alkyl groups, preferably with 1 to 4 carbon atoms.

The specified structure was determined by elemental analyzes,

1 13

Mass spectra, H-NMR spectra and 13 C-NMR spectra

ensured. In the IR spectra, the carbonyl bands typical of parabanic acids appear at 1710 - 1740 cm "
(strong) and at 1770 - 1800 cm (weak) next to urea carbon! bound up at 1630 - 1700 cm (strong).

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Another object of the invention is a process for the preparation of the parabanic acid aminals according to the invention, which is characterized in that one / \ -imidazolines of the formula (II)

(H)

R and R have the above meaning and

R is defined as R.

with monoisocyanate !! implements.

The process according to the invention for the preparation of the new parabanic acid aminals is generally as follows carried out:

The amounts of the starting substances can be chosen so that per mole / \ -imidazoline 0.5 to 10 moles - preferably 3-4 Moles - isocyanate groups are available.

In general, it is advantageous to carry out the reaction in a solvent or diluent, in which case the starting materials can be either dissolved or just suspended. Of course, it is also possible to carry out the reaction without the presence of a solvent or Le A 17 208 -A-

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Carry out thinner. Suitable for the procedure Solvents are compounds that are inert towards NCO groups, e.g. aromatic hydrocarbons, chlorinated ones aromatic hydrocarbons, benzonitrile, aliphatic hydrocarbons, esters and ketones. Are particularly suitable Toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, N-methylpyrrolidone, Dimethylformamide, dimethylacetamide, hexamethylphosphoric acid triamide, Tetramethylurea, nitromethane and nitrobenzene.

The reaction according to the invention is carried out in the temperature range from -20.degree. C. to 250.degree. Preferably between + 3O ⁰ C and 200 ° C, in particular between 80 ° C and
160 ° C worked.

It is generally advantageous to carry out the reaction with the exclusion of moisture.

It can be advantageous, especially when using highly volatile isocyanates, to work at a pressure higher than normal, for example at an excess pressure of 0.5 to
10, preferably 0.5 to 5 atmospheres.

To speed up the reaction and suppress side reactions it can be useful to use acidic or basic catalysts, especially those in isocyanate chemistry usual catalysts such. B. metal alcoholates, tert. Add amines.

The inventive reaction is exemplified by
the following reaction equation is described:

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CH. I ³ NH

"/ ~ Λ Γ

NH

CH ₃

Pur carrying out the process following / \ -imidazolines are preferred:

/ \ -Imidazoline

4-methyl-ZjT-imidazoline

4-ethyl-ZA-imidazoline

4-Cyclohexyl - / - A -imidazoline

4-phenyl-ZA -imidazoline

4- (p -chlorophenyl) - / \ -imidazoline 4,5-dimethyl-ZjP-imidazoline

^{5-ethyl-4-methyl-Z \ 2} -imidazoline 5-methyl-4-phenyl-Z \ 2 -imidazoline

Hexahydroben zimidazole

1- (MethylcarbamoyI) -ΖΛ -imidazoline 1- (n-Propylcarbamoyl) -ZA-imidazoline 1- (Cyclohexylcarbamoyl) -ZA -imidazoline 1- (Phenylcarbamoyl) -ZA-imidazoline 1- (3,4-Dichlorophenylcarbamoyl) -ZA-imidazoline

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1 - (p-Nitrophenylcarbamoyl) - / \ -imidazoline

1- (methylcarbamoyl) -4-methyl-ZA-imidazoline 1- (phenylcarbamoyl) hexahydrobenzimidazole

1- (p-Tolylcarbamoyl) -5- (naphthyl) -1- Z \ -imidazoline

For carrying out the method according to the invention preferred isocyanates are aliphatic monoisocyanates with 2-21 carbon atoms or aromatic monoisocyanates with Cy- -j_c carbon atoms.

Methyl, ethyl, allyl, n-propyl, η-butyl, iso-butyl, tert-butyl, n-amyl, Dodecyl, oleyl, stearyl, cyclohexyl, 1-chloro-ethyl-2-, Methoxy-methyl-, 1-cyano-propyl-3-, phenyl-, o-tolyl-, m-tolyl-, p-tolyl, benzyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-nitrophenyl-, 3-cyano-phenyl-, 4-methoxyphenyl-, 1-naphthyl isocyanate is used.

The compounds according to the invention can be used as auxiliaries for textiles and rubber, as well as Pharmaceuticals and plant protection products.

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example 1

7, O weight TeileZA -imidazoline and 50 parts by weight of cyclohexyl isocyanate are stirred for 25 hours at 110 ⁰ C in 25 parts by weight of toluene. On cooling, a precipitate separates out, which is filtered off with suction and washed with ether. 38.3 parts by weight of the parabanic acid derivative 1,3-dicyclohexyl-6,9-biscyclohexylcarbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro / 4.4 / -nonane with a melting point of 188 - are obtained. 19O ° C. CHN C ₃₁ H ₅₀ N ₆ O ₄ calc. 65.23 8.83 14.72

Found 65. 9.0 14.9

Example 2

2.8 parts by weight of ZA-imidazoline and 9 parts by weight of methyl isocyanate are heated to 150 ° C. in the containment tube for 50 hours. When it cools down, a resin-like product is formed that is rubbed in with cyclohexane. 2.5 parts by weight of the parabanoic acid derivative 1,3-dimethyl-6,9-bismethylcarbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro ^ j..47 nonane with melting point 272 are obtained ⁰ C. (decomposition)

IR (KBr): 1776 cm " ¹ , 1721 cm" ¹ , 1647 cm " ¹ (C = O) Example 3

3.5 parts by weight of Z \ ² -imidazo I in and 16.6 parts by weight of allyl isocyanate in 10 parts by weight of toluene are stirred at 110 ° C. for 26 hours. A colorless precipitate separates out on cooling and is filtered off with suction and washed with toluene. 3.8 parts by weight of the parabanoic acid derivative 1,3-diallyl-6,9-bis-allylcarbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro / 4,47nonane with a melting point of 171 ° C. are obtained .

MS: Molpeak 402

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Example 4

To 7 parts by weight / \ -imidazoline in 25 parts of chlorobenzene, 47.6 parts by weight of phenyl isocyanate are added dropwise at 100 ⁰ C in 1 hour. The mixture is subsequently stirred at 130 ° C. for 3 hours. A precipitate separates out on cooling and is filtered off with suction and washed with chlorobenzene. 23 parts by weight of the parabanic acid derivative 2,4-dioxo-1,3-diphenyl-6-phenylcarbamoyl-1,3,6,9-tetraaza-spiro / 4.47-nonane with a melting point of 248 C. are obtained. Found: 431, Ber .: 427.5

Example 5

9.45 parts by weight of 1-phenylcarbamoyl - / \ -imidazoline and 11.9 parts by weight of phenyl isocyanate are heated to 140 ° C. in 20 parts by weight of xylene for 1 hour. A precipitate separates out on cooling and is filtered off with suction and washed with a little toluene. 16.7 parts by weight of the parabanoic acid derivative 2,4-dioxo-1,3-diphenyl-6-phenylcarbamoyl-1,3,6,9-tetraaza-spiro £ 4.4_7nonane with a melting point of 246 ° C. are obtained.

Example 6

2.54 parts by weight of 1-methylcarbamoyl-Z_i-imidazoline and 7.98 parts by weight of p-tolyl isocyanate in 15 parts by weight of toluene, 63 hours at 11O ⁰ C is stirred. A colorless precipitate separates out on cooling and is filtered off with suction and washed with toluene. 3.8 parts by weight are obtained

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of the parabanic acid derivative 2,4-dioxo-6-methylcarbamoyl-1,3-di- (4-tolyl) -9- (4-tolylcarbamoyl) -1,3,6,9-tetraaza-spiro / T. 47nonane, mp 254 ° C.

Example 7

L-Δ ² -

1.68 parts by weight of 4-methyl-Z_A -imidazoline and 12.28 parts by weight of p-chlorophenyl isocyanate are stirred in 10 parts by weight of toluene at 110 ° C. for 73 hours. A colorless precipitate separates out on cooling and is filtered off with suction and washed with toluene. 12.7 parts by weight of the parabanic acid derivative 2,4-dioxo-1,3-bis (p-chloropheny1) -6,9-bis (p-chlorophenylcarbamoyl) -7-methyl-1,3,6 are obtained , 9-tetraaza-spiro / 4.4 / nonane with a melting point of 180 ° C. IR (KBr): 178 ^r 'cm " ¹ , 1725 cm" ¹ , 1683 cm' ¹ (C = 0)

Example 8

3.5 parts by weight of ΖΛ-imidazoline and 28.2 parts by weight of 3,4-dichlorophenyl isocyanate are stirred in 50 parts by weight of toluene at 110 ° C for 2 hours. Falls as it cools a colorless precipitate, which is filtered off and washed with cyclohexane. 24.0 parts by weight are obtained of the parabanic acid derivative 1,3-bis- (3,4-dichlorophenyl) -6,9-bis- (3,4-dichlorophenylcarbamoyl) -2,4-dioxo-1,3,6,9-tetraaza-spiro / 4.4 / nonan of m.p. 233-234 ° C

^C 31 ^H 18 ^C1 8 ^N 6 ° 4 ^C H Cl N

(822.2)

Ber. 45 .28 2. 21 34. 50 10 .22 found 45 .3 2. 3 34. 1 10 .1

Example 9

0.7 parts by weight / A -imidazoline and 5.3 parts by weight p-tolyl isocyanate are in 10 parts by weight of toluene 130 hours

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the stirred at 110 ⁰ C. A colorless precipitate separates out on cooling and is filtered off with suction and washed with toluene. 3.8 parts by weight of the parabanoic acid derivative 2,4-dioxo-i, 3-di-p-tolyl-6,9-di-p-tolylcarbamoyl-i, 3,6,9-tetraaza-spiro / f4 are obtained .47nonan of m.p. 248 C.

Example 10

1.24 parts by weight of hexahydrobenzimidazole and 7.52 parts by weight of 3,4-dichlorophenyl isocyanate are added to 10 parts by weight of chlorobenzene Stirred at 130 ° C. for 25 hours. On cooling, a colorless precipitate separates out, which is sucked off and mixed with ether is washed. 4.8 parts by weight of the parabanic acid derivative 1,3-bis- (3,4-dichlorophenyl) -6,9-bis- (3,4-dichlorophenylcarbamoyl) -2,4-dioxo-1,3,6 are obtained , 9-tetraaza-7,8-tetramethylene-spiro / 4.47nonane of m.p. 246 C.

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Claims (2)

Patent claims: , · -Ν
ι My Parabansäureaminale of the general formula (I), R «0 in the R is an optionally substituted aliphatic, aliphatic-aromatic or aromatic Uarbamoylre st, 3
R and R are identical or different, hydrogen or an optionally substituted aliphatic, aromatic or aliphatic-aromatic radical, or together form a ring, R is hydrogen or an optionally substituted aliphatic, aliphatic-aromatic or aromatic carbamoyl radical, R is an optionally substituted, aliphatic, mean aromatic or aliphatic-aromatic radical. 2. Process for the preparation of Parabansaureaminalen of the general formula (I), characterized in that one / \ -imidazoline of the general formula (II), Le A 17 208 - 12 - 709851/0169 INSPECTED R ² R ³ R ^e -NN (II) in the 3
R and R have the above meaning and R is hydrogen or an optionally substituted aliphatic, aliphatic-aromatic or aromatic carbamoyl radical, with monoisocyanates at temperatures from -2cP to 25O ° C converts. Le A 17 208 - 13 - 7 0 9 8 5 1/0169