Functionalised polsulphide synthesis method

Abstract

Provided is process for the synthesis of at least one functionalized organic polysulfide.

1 . A process for synthesizing at least one functionalized organic polysulfide of formula (I):
   R 2 —X—(NR 1 R 7 )C*H—(CH 2 ) n —S a —(CH 2 ) n —C*H(NR 1 R 7 )—X—R 2   (I)
   wherein:
 R 1  and R 7  are a hydrogen or an aromatic or nonaromatic, or a linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon chain of 1 to 20 carbon atoms, which can comprise heteroatoms, wherein R 1  and R 7  are identical or different; 
 X is —C(═O)— or —CH 2 — or —CN; 
 R 2  is (i) nonexistent when X represents —CN, (ii) a hydrogen, (iii) —OR 3 , wherein R 3  is a hydrogen or an aromatic or nonaromatic, or a linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon chain of 1 to 20 carbon atoms, which can comprise heteroatoms, or (iv) —NR 4 R 5 , wherein R 4  and R 5  are a hydrogen or an aromatic or nonaromatic, or a linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon chain of 1 to 20 carbon atoms, which can comprise heteroatoms, and wherein R 4  and R 5  are identical or different; 
 n is 1 or 2; 
 a is an integer or decimal number between 2 and 10; and 
 C* represents an asymmetric carbon; 
   the process comprising:   (a) providing at least one compound of formula (II):
   G−(CH 2 ) n —C*H(NR 1 R 7 )—X—R 2   (II)
 
   wherein:
 n, R 1 , R 2 , R 7 , X and C* are as defined above, 
 G is (i) R 6 —C(═O)—O—, (ii) (R 8 O)(R 9 O)—P(═O)—O—, or (iii) R 8 O—SO 2 —O—; 
 R 6  is a hydrogen or an aromatic or nonaromatic, or a linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon chain of 1 to 20 carbon atoms, which can comprise heteroatoms; 
 R 8  and R 9  are H, an alkali metal, an alkaline earth metal or an ammonium, wherein R 8  and R 9 , are identical or different; 
   (b) providing at least one inorganic polysulfide;   (c) reacting the at least one compound of formula (II) with the at least one inorganic polysulfide in the presence of at least one enzyme chosen from sulfhydrylase;   (d) obtaining at least one functionalized organic polysulfide of formula (I);   (e) separating and isolating the at least one functionalized organic polysulfide of formula (I) and;   (f) optionally, further functionalizing the functionalized organic polysulfide of formula (I) obtained in stage (d) or (e);   wherein stages (a) and (b) are carried out simultaneously or sequentially.   
     
     
         2 . The process as claimed in  claim 1 , wherein the functionalized organic polysulfide of formula (I) is enantiomerically pure. 
     
     
         3 . The process as claimed in  claim 1 , wherein the functionalized organic polysulfide of formula (I) is chosen from dicysteine polysulfide and dihomocysteine polysulfide. 
     
     
         4 . The process as claimed in  claim 1 , wherein the compound of formula (II) is chosen from I-serine derivatives and I-homoserine derivatives. 
     
     
         5 . The process as claimed in  claim 4 , wherein the I-serine derivative is chosen from O-phospho-L-serine, O-succinyl-L-serine, O-acetyl-L-serine, O-acetoacetyl-L-serine, O-propio-L-serine, O-coumaroyl-L-serine, O-malonyl-L-serine, O-hydroxymethylglutaryl-L-serine, O-pimelyl-L-serine and O-sulfo-L-serine. 
     
     
         6 . The process as claimed in  claim 4 , wherein the I-homoserine derivative is chosen from O-phospho-L-homoserine, O-succinyl-L-homoserine, O-acetyl-L-homoserine, O-acetoacetyl-L-homoserine, propio-L-homoserine, O-coumaroyl-L-homoserine, O-malonyl-L-homoserine, O-hydroxymethylglutaryl-L-homoserine, O-pimelyl-L-homoserine and O-sulfo-L-homoserine. 
     
     
         7 . The process as claimed in  claim 4 , wherein the sulfhydrylase is chosen from sulfhydrylases associated with the L-serine derivatives and sulfhydrylases associated with the L-homoserine derivatives. 
     
     
         8 . The process as claimed in  claim 7 , wherein the sulfhydrylase associated with the L-serine derivative is chosen from O-phospho-L-serine sulfhydrylase, O-succinyl-L-serine sulfhydrylase, O-acetyl-L-serine sulfhydrylase, acetoacetyl-L-serine sulfhydrylase, O-propio-L-serine sulfhydrylase, O-coumaroyl-L-serine sulfhydrylase, O-malonyl-L-serine sulfhydrylase, O-hydroxymethylglutaryl-L-serine sulfhydrylase, O-pimelyl-L-serine sulfhydrylase and O-sulfo-L-serine. 
     
     
         9 . The process as claimed in  claim 7 , wherein the sulfhydrylase associated with the L-homoserine derivative is chosen from O-phospho-L-homoserine sulfhydrylase, O-succinyl-L-homoserine sulfhydrylase, O-acetyl-L-homoserine sulfhydrylase, O-acetoacetyl-L-homoserine sulfhydrylase, O-propio-L-homoserine sulfhydrylase, O-coumaroyl-L-homoserine sulfhydrylase, O-malonyl-L-homoserine sulfhydrylase, O-hydroxymethylglutaryl-L-homoserine sulfhydrylase, O-pimelyl-L-homoserine sulfhydrylase and O-sulfo-L-homoserine sulfhydrylase. 
     
     
         10 . The process as claimed in  claim 1 , wherein the inorganic polysulfide is chosen from alkali metal, alkaline earth metal and ammonium polysulfides. 
     
     
         11 . A functionalized organic polysulfide of formula (I) prepared according to the process described in  claim 1 . 
     
     
         12 . Dicysteine or dihomocysteine polysulfide prepared according to the process described in  claim 1 . 
     
     
         13 . A process for lubrication, vulcanization, sulfidation of catalysts or preparation of medicaments, comprising using a functionalized organic polysulfide as claimed in  claim 11 . 
     
     
         14 . The process as claimed in  claim 1 , wherein the sulfhydrylase is a sulfhydrylase associated with the compound of formula (II). 
     
     
         15 . The process as claimed in  claim 4 , wherein the L-serine derivative is selected from the group consisting of O-phospho-L-serine, O-succinyl-L-serine, O-acetyl-L-serine and O-sulfo-L-serine. 
     
     
         16 . The process as claimed in  claim 4 , wherein the L-homoserine derivative is selected from the group consisting of O-succinyl-L-homoserine, O-acetyl-L-homoserine, O-phospho-homoserine and O-sulfo-L-homoserine. 
     
     
         17 . The process as claimed in  claim 7 , wherein the sulfhydrylase associated with the L-serine derivative is selected from the group consisting of O-phospho-L-serine, O-succinyl-L-serine sulfhydrylase, O-acetyl-L-serine sulfhydrylase and O-sulfo-L-serine. 
     
     
         18 . The process as claimed in  claim 7 , wherein the sulfhydrylase associated with the L-homoserine derivative is selected from the group consisting of O-phospho-L-homoserine sulfhydrylase, O-succinyl-L-homoserine sulfhydrylase, O-acetyl-L-homoserine sulfhydrylase and O-sulfo-L-homoserine sulfhydrylase. 
     
     
         19 . The process as claimed in  claim 1 , wherein the inorganic polysulfide is selected from the group consisting of sodium polysulfide, potassium polysulfide, calcium polysulfide and ammonium polysulfide.