Patent GB-1388280-A (GB)
Title: Di- and poly-sulphides
IPC: C08L1/00
Filed: 1972-11-17
Abstract: 1388280 Polysulphides MONSANTO CO 17 Nov 1972 [19 Nov 1971] 32030/73 Divided out of 1388279 Headings C2C and C2P The invention comprises compounds offormula where x is 1 or 2, n is 1, 2 or 3, and each Acc-S is individually (1) an azole radical of the formula where the valences on the vicinal carbon atoms are satisfied independently by hydrogen, chlorine, C 1-5  alkyl, C 1-5  hydroxyalkyl, C 1-5  alkoxy, hydroxy, amino, benzyl, acetyl, acetoxy-C 1-5  alkyl, carboalkoxy, carbamoyl, carbanilino or phenyl, by one on each carbon together forming a double bond or by said carbon atoms being members of an unsubstituted aromatic or alicyclic ring or aromatic ring substituted by C 1-5  alkyl, halo, nitro, hydroxy, carboalkoxy, acetyl, C 1-5  alkoxy or phenyl, and X<SP>1</SP> is S, O or NH, (2) a radical of the formula where R 1  and R 2  independently are hydrogen, alkyl, cycloalkyl, aralkyl, phenyl or substituted phenyl, or R 1  and R 2  along with the nitrogen atom form a heterocycle of 4-8 carbon atoms and X<SP>11</SP> is O or S (3) a radical of the formula where R 3  and R 4  independently are alkyl, cycloalkyl, aralkyl phenyl or alkyl substituted phenyl (4) a radical of the formula where R 5  is alkyl, cycloalkyl, aralkyl, phenyl or substituted phenyl, and X<SP>11</SP> is O or S, (5) a radical of the formula where R 6 , R 7  and R 8  independently are hydrogen, lower alkyl, lower alkoxy, phenyl, nitro, chloro, lower alkylthio, lower alkylamino, lower dialkylamino, lower dialkenylamino, heterocyclic amino, or R 7  and R 8  along with the adjacent carbon atoms to which they are attached form ortho arylene; and the corresponding dihydro and tetrahydro radicals, (6) a radical of the formula where R 6  and R 7  are independent and independently have the same meaning as before, (7) a radical of the formula where R 9  is acetamido, lower alkyl, phenyl, chloro or bromo, and R 10  is lower alkyl or phenyl, (8) a radical of the formula (9) a radical of the formula (10) a radical of the formula where each R 11  independently is hydrogen or lower alkyl, or (11) a radical of the formula and R is an organic bridging group containing 1-24 carbon atoms and is (a) a divalent radical of the formula (X) n , where n<SP>1</SP> is 1 to 24, each X is the same or different and is where Z and Z<SP>1</SP> independently are hydrogen, alkyl, cycloalkyl, benzyl or phenyl, (b) a divalent radical of the formula where each n<SP>11</SP> independently is 1 to 23, m is zero, 1 or 2, X has the same meaning as before and Y is oxygen, sulphur, -SO 2 -, HN<, C 6 H 5 N<, lower alkyl-N<, -C(O)O-, a divalent cyclic radical of group (c) below or a divalent aromatic radical of group (e) below, (c) a divalent cyclic radical each valence of which is on a ring carbon atom of an alicyclic ring said radical being a radical derived from removal of hydrogen from carbon in a monocyclic, bi(monocyclic), bicyclic or tricyclic hydrocarbon or by such removal from a compound derived from any such hydrocarbon by the replacement of up to two ring carbon atoms by oxygen, (d) a divalent acyclic olefinically unsaturated radical, (e) a divalent aromatic radical selected from anthrylene and radicals derived by removal of hydrogen from two ring carbon atoms of a compound of one of the formulµ where each Z<SP>11</SP> independently is hydrogen, lower alkyl, hydroxy, lower alkoxy, acetyl, phenyl, chloro or nitro, Y<SP>1</SP> is oxygen, sulphur, -SO 2 -, -CO-, lower alkylene or lower alkylidene and x<SP>1</SP> is 1 to 4, (f) a combination of the formula -T-T<SP>1</SP>- where one valence is linked to cyclic carbon and the other to acyclic carbon, T being selected from radicals of the types (a), (b), (c), (d) and (e) and T<SP>1</SP> being a radical selected from a different one of the said types, (g) a straight or branched chain alkylene radical substituted by one or more oxo, hydroxy, alkoxy, hydroxy-substituted alkoxy, alkoxysubstituted alkoxy, carboxy, carboxy substituted alkoxy, carboalkoxy or acyloxy radicals, (h) a trivalent radical being a radical derived by removal of one hydrogen atom from a radical of the type (a), (b), (c), (d), (e), (f) or (g), or a radical of the formula where A is lower alkyl and each A<SP>1</SP> is independently lower alkylene, (i) a tetravalent radical being a radical derived by removal of two hydrogen atoms from a radical of the type (a), (b), (c), (d), (e), (f) or (g), a radical of formula or a radical of the formula where each A<SP>1</SP> is independently lower alkylene: with the exception of (i) compounds in which x is 1, n is 1, R is an organic bridging group of type (a), and both Acc-S radicals are radicals of type (3), and (ii) the compound in which x is 1, n is 1, R is a divalent pentylene radical and both Acc-S radicals are morpholinothiocarbonylthio radicals. The invention also includes a composition comprising a mixture of and Acc 1 S-S-R-S-SAcc 1  where AccS- is a radical of type (1), (2) or (3) above and Acc 1 S- is a different radical of type (1), (2) or (3) and R is a radical of type (a) above or of (b) above where Y is O, S or phenylene. The above compounds and compositions may be prepared by reacting one or more compounds of formula AccSH or salts thereof with (ClS x ) n RS x Cl or, in appropriate cases by reacting (ZS) n RZS where Z is a heterocycle attached at a N atom to the S atom with CS 2 . 1,2 - Bis - (morpholinothio)ethane is prepared from morpholine and 1,2-ethane-disulphenyl chloride.