Patent GB-456894-A (GB)
Title: Improved method of vulcanizing rubber
IPC: C07D417/12
Filed: 1935-04-12
Abstract: The vulcanization of rubber is accelerated by incorporating in the mix compounds having the formula <FORM:0456894/IV/1> in which R is an arylene group, R1 is a group containing a hydrogenated furane ring and R2 is any monovalent organic radical other than an alicyclic group.  The compounds may be prepared by reacting a 2-halogen-arylthiazole with a secondary hydrogenated furyl or furfuryl dithiocarbamate. 2-Halogen-arylthiazoles specified are the 2-chlor-6-methoxy, 2-chlor, 2-chlor-4-methyl, 2-chlor-5-nitro, 2-chlor - 6 - nitro, 2 - chlor-6-ethoxy, 2 - chlor - 6-methyl, 2-chlor-dimethyl, 2-chlor - 4-phenyl, 2-chlor-5-chlor-6-nitro and 2 - chlor-4-methyl-6-nitro benzo thiazoles; the 2-chlor-naptho-thiazoles and their nitro derivatives.  The 2-chlorbenzo-thiazoles may be prepared by the process described in Specification 302,142, [Class 2 (iii)]. Other 2-chlor-aryl-thiazoles may be prepared similarly employing the desired mercaptoaryl thiazole.  Other 2-halogen-aryl-thiazoles may be prepared similarly employing the desired sulphur halide instead of chlorine.  Di-thiocarbamates specified are the potassium di-(tetrahydro-a -furfuryl), sodium di-(tetrahydro-a -furfuryl); sodium N-ethyl-tetrahydro-a -furyl, potassium N-isopropyl-tetrahydro-a -furfuryl, sodium N-methyl-tetrahydro-a -furfuryl, potassium N-phenyl tetrahydro-a -furfuryl, sodium N - isobutyl - tetrahydro - a  - furfuryl, ammonium N - n - propyl - tetrahydro - a  - furfuryl, sodium tetrahydro - a  - furfuryl - N - methyl, ammonium N - isoamyl - tetrahydro - a  - furfuryl, sodium tetrahydro-a -furfuryl-N-benzyl, sodium di - (2 - tetrahydro - a  - furfuryl ethyl), ammonium di-(tetrahydro - a  - furyl), ammonium N - n - butyl - tetrahydro - a  - furfuryl and sodium N-b -phenyl-ethylene-tetrahydroa -furfuryl dithiocarbamates; salts of calcium and barium are also referred to.  These dithiocarbamates may be prepared by condensing the desired secondary amine with carbon disulphide in the presence of an alkali, e.g. sodium, potassium or ammonium hydroxide.  The hydrogenated amines may be prepared by hydrogenating the furyl or furfuryl amines.  In an example 6-nitro-benzothiazyl-2-di-(tetrahydro-a -furfuryl) dithiocarbamate is produced by refluxing 2-chlor-6-nitro-benzothiazole, ditetrahydro-a -furfurylamine, carbon disulphide and sodium hydroxide in a solvent such as ethyl alcohol. Specification 454,863 also is referred to.  The Specification as open to inspection under Sect. 91 states that R2 may also be an alicyclic group and refers to the use of ammonium N-cyclohexyl-tetrahydro-a -furfuryl, sodium N - p - methoxy - cyclohexyl - tetrahydro-a -furfuryl, sodium N-decahydro-b -naphthyltetrahydro-a -furfuryl and potassium N-hexahydrotolytetrahydro - a  - furfuryl - dithiocarbamates in the preparation of the accelerator.  This subject-matter does not appear in the Specification as accepted.ALSO:The vulcanization of rubber is accelerated by incorporating in the mix compounds having the formula <FORM:0456894/V/1> in which R is an arylene group, R1 is a group containing a hydrogenated furane ring and R2 is any monovalent organic radical other than an alicyclic group.  The compounds may be prepared by reacting a 2-halogen-aryl-thiazole with a secondary hydrogenated furyl or furfuryl dithiocarbamate.  2 - Halogen - aryl - thiazoles specified are the 2-chlor-6-methoxy, 2-chlor, 2-chlor-4-methyl, 2-chlor-5-nitro, 2-chlor-6-nitro, 2 - chlor - 6 - ethoxy, 2 - chlor - 6 - methyl, 2-chlor-dimethyl, 2-chlor-4-phenyl, 2-chlor-5-chlor - 6 - nitro and 2 - chlor - 4 - methyl - 6 - nitro benzo-thiazoles; the 2-chlor naphtho-thiazoles and their nitro derivatives.  Dithiocarbamates specified are the potassium di-(tetrahydro-a -furfuryl), sodium di - (tetrahydro - a  - furfuryl) sodium N-ethyl tetrahydro-a -furyl, potassium N-isopropyl tetrahydro-a -furfuryl, sodium N-methyl tetrahydro furfuryl, potassium N-phenyltetrahydro-a -furfuryl, sodium N-isobutyl tetrahydro-a -furfuryl, ammonium N-n-propyl tetrahydro-a -furfuryl, sodium tetrahydro-a -furfuryl N-methyl, ammonium N-isoamyl tetrahydro-a -furfuryl, sodium tetrahydro-a -furfurll N-benzyl, sodium di - (2 - tetrahydro - a  - furyl ethyl), ammonium di-(tetrahydro-furyl), ammonium N-n-butyl tetrahydro-a -furfuryl and sodium N - b -phenyl ethylene tetrahydro-a -furfuryl dithiocarbamates; salts of calcium and barium are also referred to. In an example, 6-nitro-benzothiazyl-2-di-(tetrahydro-a -furfuryl) dithiocarbamate is produced by refluxing 2-chlor-6-nitro benzothiazole, ditetrahydro - a  - furfuryl amine, carbon disulphide and sodium hydroxide in a solvent such as ethyl alcohol. Specifications 302,142, [Class 70], and 454,863 are referred to.  The Specification as open to inspection under Sect. 91 states that R2 may also be an alicyclic group and refers to the use of ammonium N-cyclohexyl tetrahydro-a -furfuryl, sodium N-p-methoxy cyclohexyl tetrahydro-a -furfuryl, sodium N-decahydro-b -naphthyl tetrahydro-a -furfuryl and potassium N-hexahydrotolyltetrahydro-a -furfuryl dithiocarbamates in the preparation of the accelerator.  This subject-matter does not appear in the Specification as accepted.