Patent GB-1137183-A (GB)
Title: Carbodithioic acid derivaties of azabicyclononane
IPC: C07D295/26
Filed: 1966-01-18
Abstract: 1,137,183. 3 - Azabicyclo[3.2.2]nonane derivatives; chloroacetamido compounds. MONSANTO CO. 18 Jan., 1966 [18 Jan., 1965; 11 June, 1965], No. 2328/66. Heading C2C. [Also in Division C3] The invention comprises compounds of the formula where W is an ester- or salt-forming radical, or an -S.C.Cl 3  radical, Q is a 3-azabicyclo[3.2.2-] non-3-yl radical of formula X is a piperidino or hexahydro-azepin-1-yl radical, or another radical Q, and x is 0, 1, 2, or 3. A preferred class of compounds is that having the formula where A and B represent piperidino, hexahydroazepin-1-yl, or Q groups, where at least one of A and B is a Q group. Salt-forming radicals are ammonium, substituted ammonium, and metal, e.g. alkali or alkaline earth. Thus many suitable amine addition salts are included, e.g. that with 3-azabicyclo[3.2.2]nonane (Example 59). The ester-forming radicals are hydrocarbon radicals which may contain functional substituents except on the carbon attached to the sulphur, e.g. alkyl, isothiocyano ato-, cyano-, aminoalkyl, alkenyl, halo-alkenyl, other substituted alkenyl, chloro, bromo, nitro, and unsubstituted phenyl, and naphthyl, arylthioalkyl, aralkyl, furyl, pyranyl, 5-hydroxypyranonyl, 2-azolyl groups, e.g. 2-benzothiazolyl, chloro, alkoxy, alkoxycarbonyl, nitro, and carbamoyl-2- benzothiazolyl, pyrimidinyl, phthalazinyl, radicals of formula-CHYCOR<SP>1</SP>, or-CH 2 COR<SP>1</SP>, where R<SP>1</SP> is alkoxy or amino and Y is QCS-, and imidomethylene, e.g. phthalimidomethylene. Compounds of the Formula (I), or of the Formula (II) in which X is a Q radical, are prepared by either (i) reacting 3-azabicyclo- [3.2.2]nonane (QH) with CS 2  to produce a dithioic acid, and then reacting the product with a compound to replace the hydrogen of the acid with a W or group, or (ii) reacting QH with CSCl 2  (thiophosgene) to obtain the thiocarbonyl derivative, and reacting the product with a compound of formula WSH or Compounds of the formula (III) in which A is a Q radical and B is a piperidino or hexahydroazepin-1-yl radical are prepared by reacting a compound of this formula in which both A and B are Q radicals with hexamethyleneimine or piperidine. Thio - 3 - azabicyclo[3.2.2]nonane - 3 - carbonyl chloride is prepared by reacting QH with thiophosgene in ethyl ether and water, followed by separation and distilling off the ether (Example 24). Chloromethylcarbonyl - 3 - azabicyclo[3.2.2] nonane is prepared by reacting QH with Cl.CH 2 COCl in the presence of ethyl ether and triethylamine, followed by separation and distilling off the ether (Example 47). In like manner, N - hexamethylene - α - chloroacetamide (Example 48), N - chloroacetyl - N<SP>1</SP> phenyl - p-phenylenediamine (Example 49), and N- chloroacetyl - N - isopropyl - N<SP>1</SP> - phenyl - p - phenylenediamine (Example 50) are prepared. Hexahydro - azepin - 1 - yl - 3 - azabicyclo [3.2.2]nonane-3-carbodithioate is prepared by reacting (QCS) 2 S 2 , prepared as in method (i) above, with hexamethyleneimine, using NaOCI and Na 2 SO 3  (Example 54). (QCS) 2 S is prepared by reacting (QCS) 2 S 2  with KCN in the presence of water (Example 56). The compounds of the invention are useful as accelerators in the preparation of vulcanized rubber.