Patent GB-946397-A (GB)
Title: Production of halogenated n, n-disubstituted carbamyl halides
Inventor: KOENIG KARL-HEINZ
IPC: C07C271/02
Filed: 1962-07-10
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.