Production of halogenated n, n-disubstituted carbamyl halides

    公开(公告)号:GB946397A

    公开(公告)日:1964-01-15

    申请号:GB2641962

    申请日:1962-07-10

    Applicant: BASF AG

    Abstract: Halogenated N, N-disubstituted carbamyl halides are obtained by reacting a compound R1R2N.COX, where R1 and R2 are aliphatic, cycloaliphatic or araliphatic radicals, or together represent members of a heterocyclic ring, and X is halogen, with a halogenating agent. "Halogen" means F, Cl or Br. Suitable halogenating agents are fluorine, chlorine bromine and sulphuryl halides. In preferred starting materials, R1 is C1-12 aliphatic hydrocarbon, C5-12 cycloaliphatic hydrocarbon, or C7-12 araliphatic hydrocarbon; R2 is as R1, but may also be C2-8 aliphatic hydrocarbon substituted by -NR3.COX, in which R3 is C1-4 alkyl and X is halogen (at least 2 carbon atoms being between the 2 nitrogen atoms); or R1 and R2 together are members of a 5-7-membered heterocyclic ring including the N atom, which ring is hydrocarbon or may contain one further O, N or S atom in the ring; or R1 and R2 together are members of a heterocyclic 6-membered ring containing the N atom and a further >NCOX group. In the above definitions R1 and R2 may be substituted by 1 or 2 halogen atoms, ether oxygen, thioether sulphur, carboxyl, carboxylic ester or nitrile groups. From one to all aliphatic hydrogen atoms may be replaced by halogen in the reaction. Novel compounds. The following types of compound are claimed as novel: R4R5NCOCl, XCH2N(R6)COX, (XCH2)2NCOX, CH3CHX. N(R6)COX and (CH3CHX)2NCOX, in which X is halogen; R4 is C1-4 alkyl; R5 is as R4, or is C2-8 alkyl substituted by -NR3.COX (in which R3 is C1-4 alkyl), there being at least 2 carbon atoms between the 2 nitrogen atoms; or R4 and R5 together represent members of a heterocyclic 5-7-membered ring including the nitrogen atom and possibly one further N, O or S atom, otherwise of hydrocarbon structure; or a heterocyclic 6-membered ring including the nitrogen atom and a further >NCOX group, otherwise of hydrocarbon structure; the radicals R4 and R5 containing at least one halogen atom in addition to X; and R6 is C1-4 alkyl. These novel compounds are fungicides. In examples (1) dimethylcarbamyl chloride and chlorine give methyl-chloromethyl-, bis(chloromethyl)-, dichloromethyl-chloromethyl carbamyl chlorides and a higher chlorinated product; (2) dimethylcarbamyl chloride and SOCl2 give methyl-chloromethylcarbamyl chloride; (3) bis(BETA-chloroethyl) carbamyl chloride and chlorine give bis(pentachloroethyl) carbamyl chloride; (4) diethylcarbamyl chloride and chlorine give the same product as in (3); (5) piperidyl carbamyl chloride and chlorine give chlorinated products up to pentachloropiperidylcarbamyl chloride; (6) dimethylcarbamyl chloride and chlorine give methyl-chloromethyl- and bis(chloromethyl) carbamyl chloride; (7) morpholylcarbamyl chloride and chlorine give chlorinated products up to tetrachloromorpohyl carbamyl chloride; (8) pyrrolidylcarbamyl chloride and chlorine give chlorinated products up to tetrachloropyrrolidylcarbamyl chloride; (9) N-isopropyl-N-benzyl carbamyl chloride and chlorine give a chlorinated product; (10) N-methyl-N-cyclohexylcarbamyl chloride and chlorine give a chlorinated product; (11) piperazine-dicarbamyl chloride and chlorine give a chlorinated product; (12) dimethylcarbamyl chloride and fluorine give a fluorinated product; and (13) diethylcarbamyl chloride and chlorine give N-ethyl-N-(a -chloroethyl) carbamyl chloride and N,N-bis(a -chloroethyl) carbamyl chloride. Other starting materials are listed.

    Benzyl phosphoric acid derivatives and improvements in the production of compounds of the 1,4-bis-(para-carboxystyryl)-benzene series

    公开(公告)号:GB929436A

    公开(公告)日:1963-06-26

    申请号:GB2607760

    申请日:1960-07-27

    Applicant: BASF AG

    Abstract: The invention comprises compounds of the general formula in which R represents hydrogen, an aliphatic or aralkyl radical, the R1 radicals, which may be identical or different, represent hydrogen, alkyl, aryl, halogen, alkoxy or carboxylic ester groups, R11 represents hydrogen or alkyl with one to four carbon atoms, R111 represents hydrogen or alkyl, RIV represents hydrogen or alkyl, or RIII and RIV, when taken together with , represent a heterocyclic ring and a process for the production of compounds of the 1,4-bis-(para-carboxystyryl)-benzene series wherein a benzylphosphonic acid, substituted in para-position by a carboxy group, the carbon atom attached to phosphorus of which bears at least one hydrogen atom, or an ester of such an acid, is reacted in the presence of a proton acceptor with a 1,4-diformyl-benzene with the replacement of each of the two carbonyl oxygen atoms in the 1,4-diformyl benzene by a benzal radical. Representative of the benzylphosphonic esters specified for use as starting materials are p-carbethoxybenzyl phosphonic diethyl ester, a -(p-carb-butoxy phenyl) butyl phosphonic diethyl ester, 2,5-dichlor-4-carbmethoxy-benzyl phosphonic diethyl ester, 3-methoxy-, 3-phenyl and 2-brom-4-carbmethoxy benzyl phosphonic diethyl ester and 2-fluor-4-carbethoxy-benzyl-phosphonic acid diethyl ester. Diformyl benzenes specified for use as starting materials include 1,4-diformyl benzene optionally further substituted with alkyl, aralkyl, halogen, alkoxy or sulphonic acid groups. Proton acceptors specified include alkali and alkali earth metal hydroxides, alcoholates and amides, strongly basic amines and ion exchange resins. Many solvents for use in the process are listed. The examples relate to the preparation of 1,4-bis(p-carbmethoxy-styryl)-benzene and 1,4-bis-(31,41-dicarbomethoxy-styryl)-benzene. The products are brightening and light protection agents. p-Carbomethoxy-benzyl phosphonic acid dimethyl ester is obtained by reacting p-chloromethylbenzoic acid methyl ester with triethyl phosphite. 3,4- Dicarbomethoxybenzene phosphonic acid diethyl ester is obtained by heating 3,4-dicarbomethoxybenzyl chloride with triethyl phosphite.

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