DE1959705A1 - 1-subst uracil derivs - Google Patents

Abstract

1-Subst. uracil derivs. Title cpds. of formula (I):(where R1 is an opt. subst. aliphatic, araliphatic, aryl or heterocyclic residue and R2 and R3 are H or opt. subst. aliphatic, araliphatic, aryl or heterocyclic residues or are linked so as to form an opt. subst. ring system) useful as plant protection agents or intermediates therefore are prepd. by reacting an imine R1-CH2-CR2=N-R1 with Cl-CO-N=C=O, opt. in the presence of an insert solvent.

Description

Process for the preparation of uracil derivatives The invention relates to a new process for the preparation of uracil derivatives which are obtained by using compounds of the general formula where R1, R2 and R3 are an optionally substituted, aliphatic, araliphatic, aryl or heterocyclic radical and where R2 and R3 together with the carbon atoms they carry can be part of an optionally substituted ring system and where R2 and R3 can also be hydrogen with N-chlorocarbonyl isocyanate, optionally in the presence of an inert solvent, in a temperature range from about 0 to + 200 ° C.

In general, it has proven to be useful to carry out of the process the reaction components in the lower temperature range (approx. 0 - 600C), preferably to be combined at room temperature and after the slightly exothermic has subsided To heat the reaction until the elimination of hydrogen chloride has ended. this will generally carried out in the range from about 60 to about 2000C, preferably 90-1300C.

The reaction components are used in approximately stoichiometric proportions. The compounds obtainable by the present process correspond to the general formula in which the radicals R1, R2 and R3 have the meaning given above.

As optionally substituted aliphatic radicals (R1, R2, R3) are straight-chain and optionally branched alkyl radicals with 1-20, preferably 1 - 8 carbon atoms to be understood, which optionally also have a double or May contain triple bond.

Of course, the term aliphatic radicals also fall under the term cycloalphatic radicals with 3 - 12, preferably 5, 6 or 8 carbon atoms in the Ring system. Lower 0-alkyl and S-alkyl radicals may be used as substituents on the aliphatic radical (preferably 1 - 4 carbon atoms) and halogens (preferably fluorine, chlorine, Bromine), CN and also lower alkyl groups on the cycloalkyl radical (preferably 1-4 Called carbon atoms. Particularly preferred aliphatic radicals (R2, R3) are straight-chain and optionally branched alkyl radicals with 1 to 6 carbon atoms.

Araliphatic radicals (R1, R2, R3) contain 1 in the aliphatic part - 4, preferably 1 or 2 carbon atoms and in the aromatic part the naphthyl, but preferably the phenyl radical.

Aromatic radicals (max. 3 radicals R1, R2, R3) are those with up to to understand 14 carbon atoms in the ring system, deraphthyl, in particular however, the phenyl radical should be mentioned as preferred.

Heterocyclic radicals (max. 2 of the radicals R1, R2, R3, pre-suctioned R1) contain 5, 6 or 7 ring members, preferably as heteroatoms or groups Oxygen, sulfur or a lower alkyl radical (preferably 1-4 carbon atoms) substituted nitrogen atom may be mentioned and where the hetero ring system is optionally can also be fused with a benzene ring, which optionally also partially can be hydrogenated.

In the event that R2 and R3 together are components of a possibly Form substituted ring, including 3, 4, 5, 6 and 12-membered, at least to understand partially hydrogenated carbocyclic ring systems, optionally with can be fused to a 6-membered carboexclic ring system or in which a CH2 group through an N-lower alkyl radical, but preferably through an oxygen or sulfur atom is replaced.

Preferred substituents on such ring systems are lower ones Alkyl radicals (especially 1-4 carbon atoms) called.

As a substituent on the araliphatic- ,. aromatic or

heterocyclic ring systems come in addition to those already for the aliphatic Remains mentioned nor the nitro group and lower (preferably 1 or 2 carbon atoms) Haloalkyl groups (preferably fluorine, chlorine) into consideration, where the halogen atoms can be the same or different; a preferred haloalkyl radical is exemplary called the trifluoromethyl radical.

Azomethines and ketimines used as amino components are for example: p-trifluoromethyl-phenylamine, p-nitrophenylamine, Methylamine, isopropylamine, t-butylamine, cyclohexylamine, allylamine, ß-chloroethylamine, ß-naphthylamine, benzylamine, stearylamine, ß-cyanoethylamine, aetylamine, n-propylamine, n-butylamine, isobutylamine, 2-ethylhexylamine, dodecylamine, tetradecylamine, hexadecylamine.

2-aminopyridine, 2-amino-thiazole, 2-amino-benzothiazole, 2-amino-1-methyl-cyclohexane, Hexahydro-benzylamine, 2-chloro-aniline, 3-nitroaniline, 2-chloro-4-nitro-aniline, 5-chloro-2-aminotoluene 4-chloro-3-amino-benzotrifluoride, 1-amino-2-phenylaethane, 2-amino-1-isopropylbenzene, 5-amino-1,2,4-trimethylbenzene, 5,6,7,8-tetrahydronaphthylamine- (1), 1-amino-naphthalene, 3,5-dichloroaniline, 2,4,5-trichloroaniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 2,5-dichloroaniline, 3-chloroaniline, 4-chloroaniline, 4-chloro-2-nitroaniline, aniline, 2-nitroaniline, 4-nitroaniline, 5-chloro-2-nitroaniline, 4-chloro-3-nitroaniline, 3-chloro-4-nitroaniline, 4,6-dichloro-2-nitroaniline, 2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-amino-toluene, 3-chloro-2-aminotoluene, 4-chloro-2-aminotoluene, 5-nitro-4-amino-1,3-dimethyl-benzene, 6-nitro-4-amino-1,3-dimethyl-benzene, 5-amino-1,3-dimethyl-benzene, 5-amino-1,3-bistrifluoromethyl-benzene, 2-amino-1,4-dimethylbenzene,, 2-amino-1-methyl-3-ethylbenzene, 6-amino-1,2,4-trimethylbenzene, 2-amino-1,3,5-trimethyl-benzene, 2-amino-1,3-diethyl-benzene, 4-amino-1,3-dimethyl-5-ethyl-benzene, 4-amino-1-methyl-3,5-diethylbenzene, 2-amino-1,3-diisopropylbenzene, 5,6,7,8-tetrahydro-naphthylamine- (2), ß-bromo-ethylamine, 1-cyano-1-phenylethylamine, 1-cyano-1-methyl-ethylamine, 5-chloro-2-amino-benzotrifluoride, 6-chloro-2-aminotoluene, 4,5-dichloro-2-aminotoluene, 3-nitro-2-aminotoluene, 4-nitro-2-aminotoluene, 5-nitro-2-aminotoluene, 6-nitro-2-aminotoluene, 4-chloro-5-nitro-2-aminotoluene, 3-aminotoluene, 4-chloro-3-aminotoluene, 6-chloro-5-aminotoluene, 4,6-dichloro-3-aminotoluene, 4-amino-toluene, 2-chloro-4-aminotoluene, 2-nitro-4-aminotoluene, 3-nitro-4-aminotoluene, 2-amino-1-ethylbenzene, 1-amino-1-phenyl-ethane, 2,3-dimethylaniline, 3,4-dimethylaniline, 2,6-dimethylaniline, 2,4-dimethylaniline.

As carbonyl components, for example: Cyclopentanone, Cyclohexanone, cyclododecanone, isophorone, methylcyclohexane dihydroisophorone, aceto'phenon ' 4-chloro-acetophenone, propiophenone, acetone, methyl-ethyl-ketone, methyl-propyl-ketone, Diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, Dipropyl ketone, 3-methyl-heptanone- (5), acetaldehyde, propionaldehyde, butyraldehyde, 2-methyl-pentanal- (5), heptanal, 3-phenylpropionaldehyde, p-tolylacetaldehyde, methyl vinyl ketone, Methyl isopropenyl ketone, mesityl oxide, 1-phenyl-buten- (1) -one- (3), 5-methyl-1-phenyl-hex-1 -en-3-one, 4-acetyl-biphenyl, phenyl-acetophenone.

The method according to the invention is explained using the following example: The new compounds obtainable by the process are valuable starting compounds for crop protection agents and can also be used directly as such.

EXAMPLE 1 To a solution of 53 g (0.5 mol) of N-chlorocarbonyl isocyanate in 400 g of chlorobenzene, 73.5 g (0.5 mol) of the ketimine from acetone and benzylamine are added at 30 to 35 ° C. over the course of one hour. The mixture is stirred for 15 minutes and heated to 1300 G over the course of 3 hours. At approx. 850 C a very lively evolution of HCl begins. After cooling, the precipitated product is filtered off with suction, washed with a little chlorobenzene and cyclohexane and dried. 85 g (78% of theory) of 3-benzyl-4-methyluracil with a melting point of 2360 C (Lit .: 2340 C) are obtained Analysis: Calc .: C: 66.6% H: 5.55% O: 14.81% N: 12.95% Found: C: 66.7% H: 5.6% O: 14.8% N: 13.2% Example 2 19.8 g (0.2 mol) of the ketimine are dissolved in 200 ml of chlorobenzene and reacted as in Example 1 with a solution of 23.2 g (0.22 mol) of N-chlorocarbonyl isocyanate in 50 ml of chlorobenzene. However, because of the strongly exothermic reaction, the components are initially combined with cooling at 5 to 100 ° C. Only part of the reaction product precipitates out (9 g). By stripping off the solvent and recrystallizing the residue from benzene, another 7 g of identical substance are obtained. This corresponds to a yield of 47.5% of theory. M.p .: 164 ° C Analysis: Calc .: C: 57.1% H: 7.15% O: 19.1% N: 16.65% Found: C: 56.6% H: 7.1 * 0: 19.3% N: 16.7% Example 3 35.8 g (0.2 mol) of the ketimine from cyclohexanone and cyclohexylamine are reacted as in Example 2, but in ether as the solvent. The ether is distilled off under normal pressure and the residue is heated to 125 ° until HCl is no longer split off.

The residue is recrystallized from benzene and 18 g (36.3% of theory) of the uracil derivative are obtained Example 4 Analogously to Example 3, the corresponding uracil derivative with a melting point of 280-2840C is obtained from the ketimine of cyclohexanone and aniline Analysis: Calc .: C 69.4% H 5.78% O 13.2% N 11.55% Found: C 68.5% H 5.7% O 13.2% N 11.6% Analogous to the above Examples are the following compounds:

Claims (1)

A process for the preparation of uracil derivatives, characterized in that compounds of the general formula where R1, R2 and R3 are an optionally substituted, aliphatic, araliphatic, aryl or heterocyclic radical and where R2 and R3 together with the carbon atoms they carry can be part of an optionally substituted ring system and where R2 and R3 are also hydrogen, can be reacted with N-chlorocarbonyl isocyanate, optionally in the presence of an inert solvent, in the temperature range from about 0 to + 2000C.