METHOD FOR THE PREPARATION OF SUBSTITUTED THIOLACTONES, NEW SUBSTITUTED THIOLACTONES AND USES THEREOF

Abstract

The invention relates to a method for preparing substituted thiolactones of formula (I), new substituted thiolactones of formula (I) that can be obtained by carrying out said method, and the use of substituted thiolactones of formula (I) or (I) for synthesizing polymers or functionalizing surfaces or polymers.

Claims

1. Process for preparing substituted thiolactones of the following formula (I): ##STR00050## wherein: A.sup.1 and A.sup.2, which are identical or different, represent a hydrogen atom or a fluorine atom, Y represents a hydrogen atom or a group selected from alkyl, hydroxyalkyl, aryl and cyano groups, or a polymer chain; L is a linker arm, m is an integer equal to 0 or 1, T represents CH.sub.2, O or NR.sup.6, in which R.sup.6 represents a hydrogen atom or an alkyl, aryl or aralkyl radical, optionally substituted by a group selected from the groups: maleimide, a group of formula: ##STR00051## in which the symbol # is the point of attachment of said group to R.sup.6 and in which Y has the same meaning as that chosen for the radical Y of the formula (I), OH; P(O)(OR.sup.7)(OR.sup.7) in which the radicals R.sup.7 and R.sup.7, which are identical or different, represent a hydrogen atom or an alkyl radical; C.sub.nF.sub.2n+1 in which n is an integer ranging from 1 to 20; SiR.sup.8.sub.p(OR.sup.9).sub.3-p, in which the radicals R.sup.8 and R.sup.9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF.sub.3M.sup.+, in which M=K or Na; B(OR.sup.10).sub.2, in which the two radicals R.sup.10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR.sup.11, in which R.sup.11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)R.sup.12, in which R.sup.12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)OR.sup.13, in which R.sup.13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N.sup.+R.sup.14R.sup.14R.sup.14A.sup., in which the radicals R.sup.14, R.sup.14 and R.sup.14, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR.sup.15(CO)R.sup.15, in which the radicals R.sup.15 and R.sup.15, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR.sup.16(CO)OR.sup.16, in which R.sup.16 et R.sup.16, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH.sub.2-epoxy; COOR.sup.17, in which R.sup.17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR.sup.18R.sup.18, in which R.sup.18 and R.sup.18, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO.sub.2R.sup.19, in which R.sup.19 represents an alkyl or aryl radical; azide N.sub.3 and alkyne, e is an integer equal to 0 or 1, wherein: 1) when A.sup.1=A.sup.2=H and e=0, then W represents a hydrogen atom and Z.sup.1 represents a group selected from the groups alkyl; aryl; P(O)(OR.sup.7)(OR.sup.7), in which the radicals R.sup.7 and R.sup.7, which are identical or different, represent a hydrogen atom or an alkyl radical; C.sub.nF.sub.2n+1 in which n is an integer ranging from 1 to 20; SiR.sup.8.sub.p(OR.sup.9).sub.3-p, in which the radicals R.sup.8 and R.sup.9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF.sub.3M.sup.+, in which M=K or Na; B(OR.sup.10).sub.2, in which the two radicals R.sup.10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR.sup.11, in which R.sup.11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)R.sup.12, in which R.sup.12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)OR.sup.13, in which R.sup.13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N.sup.+R.sup.14R.sup.14R.sup.14A.sup., in which the radicals R.sup.14, R.sup.14 and R.sup.14, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR.sup.15(CO)R.sup.15, in which the radicals R.sup.15 and R.sup.15, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR.sup.16(CO)OR.sup.16, in which R.sup.16 and R.sup.16, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH.sub.2-epoxy; COOR.sup.17, in which R.sup.17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR.sup.18R.sup.18, in which R.sup.18 and R.sup.18, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO.sub.2R.sup.19, in which R.sup.19 represents an alkyl or aryl radical; azide N.sub.3 and alkyne; and a thiolactone ring of formula ##STR00052## in which the symbol # is the point of attachment of the thiolactone ring to L and in which Y has the same meaning as that chosen for the radical Y of the formula (I), 2) when A.sup.1=A.sup.2=H, m=1 and e=0, then W represents a hydrogen atom and Z.sup.1 may also represent a hydrogen atom; 3) when A.sup.1=A.sup.2=H, e=1 and m=0, then Z.sup.1 and W are identical and represent CH.sub.2 or CO; 4) when A.sup.1=A.sup.2=H, e=1, m=1 and T=CH.sub.2, then Z.sup.1=W=CH.sub.2, 5) when A.sup.1=A.sup.2=F, e=0 and m=0, then W represents a fluorine atom and Z.sup.1=F or represents a linear or branched chain OC.sub.qF.sub.2q+1 in which q is an integer ranging from 1 to 5, [OCF.sub.2CF(CF.sub.3)].sub.rOC.sub.3F.sub.7, with r=an integer ranging from 0 to 20, OC.sub.2F.sub.4SO.sub.2F, OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4SO.sub.2F, or OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4CO.sub.2CH.sub.3; and 6) when A.sup.1=A.sup.2=F, e=1 and m=0, then W=Z.sup.1=CF.sub.2 and T=(CF.sub.2).sub.s, with s=an integer ranging from 1 to 5; 7) when A.sup.1=H, A.sup.2=F, and e=m=0, then W represents a hydrogen atom and Z.sup.1=F or C.sub.nF.sub.2n+1, in which n is an integer ranging from 1 to 20; wherein said process comprises at least the following steps: 1) a step during which, in the presence of a radical initiator, a xanthate of the following formula (II) is reacted: ##STR00053## wherein: R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which are identical or different, represent a hydrogen atom or a group chosen from saturated or unsaturated heterocycloalkyl, alkyl, acyl, aryl, alkene, alkyne, cycloalkyl, or heterocycloaryl groups and polymer chains, it being understood that the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may also form, together, a saturated, unsaturated or aromatic cycloalkyl or heterocycloalkyl group; it being understood that at least one of the radicals R.sup.1 and R.sup.3 is other than a hydrogen atom; Y has the same meaning as in the formula (I) above, X represents NR.sup.20, in which R.sup.20 represents a hydrogen atom or an alkyl radical or O, R.sup.5 is chosen from a saturated, unsaturated or aromatic heterocycloalkyl, alkyl, acyl, aryl, aralkyl or cycloalkyl group, with a monomer comprising an ethylenic unsaturation of the following formula (III): ##STR00054## wherein: A.sup.1 and A.sup.2, which are identical or different, represent a hydrogen atom or a fluorine atom, L, m, T and e have the same meaning as in the formula (I) above; wherein: 1) when A.sup.1=A.sup.2=H and e=0, then W represents a hydrogen atom and Z.sup.2 represents a group selected from the groups alkyl; aryl; P(O)(OR.sup.7)(OR.sup.7), in which the radicals R.sup.7 and R.sup.7, which are identical or different, represent a hydrogen atom or an alkyl radical; C.sub.nF.sub.2n+1, in which n is an integer ranging from 1 to 20; SiR.sup.8.sub.p(OR.sup.9).sub.3-p, in which the radicals R.sup.8 and R.sup.9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF.sub.3M.sup.+, in which M=K or Na; B(OR.sup.10).sub.2, in which the two radicals R.sup.10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR.sup.11, in which R.sup.11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)R.sup.12, in which R.sup.12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)OR.sup.13, in which R.sup.13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N.sup.+R.sup.14R.sup.14R.sup.14A.sup., in which the radicals R.sup.14, R.sup.14 and R.sup.14, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR.sup.15(CO)R.sup.15, in which the radicals R.sup.15 and R.sup.15, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR.sup.16(CO)OR.sup.16, in which R.sup.16 and R.sup.16, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH.sub.2-epoxy; COOR.sup.17, in which R.sup.17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR.sup.18R.sup.18, in which R.sup.18 and R.sup.18, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO.sub.2R.sup.19, in which R.sup.19 represents an alkyl or aryl radical; azide N.sub.3, alkyne and C.sub.2H.sub.3; 2) when A.sup.1=A.sup.2=H, m=1 and e=0, then W represents a hydrogen atom and Z.sup.2 may also represent a hydrogen atom, 3) when A.sup.1=A.sup.2=H, e=1 and m=0, then Z.sup.2 and W are identical and represent CH.sub.2 or CO; 4) when A.sup.1=A.sup.2=H, e=1, m=1 and T=CH.sub.2, then Z.sup.2=W=CH.sub.2, 5) when A.sup.1=A.sup.2=F, e=0 and m=0, then W represents a fluorine atom and Z.sup.2=F or represents a linear or branched chain OC.sub.qF.sub.2q+1 in which q is an integer ranging from 1 to 5, [OCF.sub.2CF(CF.sub.3)].sub.rOC.sub.3F.sub.7, with r=an integer ranging from 0 to 20, OC.sub.2F.sub.4SO.sub.2F, OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4SO.sub.2F, or OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4CO.sub.2CH.sub.3; and 6) when A.sup.1=A.sup.2=F, e=1 and m=0, then W=Z.sup.2=CF.sub.2 and T=(CF.sub.2).sub.s, with s=an integer ranging from 1 to 5; 7) when A.sup.1=H, A.sup.2=F, and e=m=0, then W represents a hydrogen atom and Z.sup.2=F or C.sub.nF.sub.2n+1, in which n is an integer ranging from 1 to 20; to form a monoadduct of the following formula (IV): ##STR00055## wherein: A.sup.1 and A.sup.2, which are identical or different, represent a hydrogen atom or a fluorine atom, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X and Y have the same meaning as in the formula (II) above, L, m, T and e have the same meaning as in the formula (I) above, wherein: 1) when A.sup.1=A.sup.2=H and e=0, then W represents a hydrogen atom and Z.sup.3 represents a group selected from the groups alkyl; aryl; P(O)(OR.sup.7)(OR.sup.7), in which the radicals R.sup.7 and R.sup.7, which are identical or different, represent a hydrogen atom or an alkyl radical; C.sub.nF.sub.2n+1, in which n is an integer ranging from 1 to 20; SiR.sup.8.sub.p(OR.sup.9).sub.3-p, in which the radicals R.sup.8 and R.sup.9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF.sub.3M.sup.+, in which M=K or Na; B(OR.sup.10).sub.2, in which the two radicals R.sup.10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR.sup.11, in which R.sup.11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)R.sup.12, in which R.sup.12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(CO)OR.sup.13, in which R.sup.13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N.sup.+R.sup.14R.sup.14R.sup.14A.sup., in which the radicals R.sup.14, R.sup.14 and R.sup.14, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR.sup.15(CO)R.sup.15, in which the radicals R.sup.15 and R.sup.15, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR.sup.16(CO)OR.sup.16, in which R.sup.16 and R.sup.16, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH.sub.2-epoxy; COOR.sup.17, in which R.sup.17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR.sup.18R.sup.18, in which R.sup.18 and R.sup.18, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO.sub.2R.sup.19, in which R.sup.19 represents an alkyl or aryl radical; azide N.sub.3, alkyne, and a group of the following formula (V): ##STR00056## in which the symbol # is the point of attachment of the group of formula (V) to L and Y has the same meaning as that chosen for the radical Y of formula (IV), 2) when A.sup.1=A.sup.2=H, m=1 and e=0, then W represents a hydrogen atom and Z.sup.3 may also represent a hydrogen atom, 3) when A.sup.1=A.sup.2=H, e=1 and m=0, then Z.sup.3 and W are identical and represent CH.sub.2 or CO; 4) when A.sup.1=A.sup.2=H, e=1, m=1 and T=CH.sub.2, then Z.sup.3=W=CH.sub.2, 5) when A.sup.1=A.sup.2=F, e=0 and m=0, then W represents a fluorine atom and Z.sup.3=F or represents a linear or branched chain OC.sub.qF.sub.2q+1 in which q is an integer ranging from 1 to 5, [OCF.sub.2CF(CF.sub.3)].sub.rOC.sub.3F.sub.7, with r=an integer ranging from 0 to 20, OC.sub.2F.sub.4SO.sub.2F, OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4SO.sub.2F, or OCF.sub.2CF(CF.sub.3)OC.sub.2F.sub.4CO.sub.2CH.sub.3; and 6) when A.sup.1=A.sup.2=F, e=1 and m=0, then W=Z.sup.3=CF.sub.2 and T=(CF.sub.2).sub.s, with s=an integer ranging from 1 to 5; 7) when A.sup.1=H, A.sup.2=F, and e=m=0, then W represents a hydrogen atom and Z.sup.3=F or C.sub.nF.sub.2n+1, in which n is an integer ranging from 1 to 20; then 2) a step of thermolysis of the monoadduct of formula (IV) obtained above in the preceding step, to form a corresponding substituted thiolactone of formula (I).

2. Process according to claim 1, wherein said process is carried out for the preparation of thiolactones of formula (I) in which: Z.sup.1 is a group chosen from the groups P(O)(OR.sup.7)(OR.sup.7); C.sub.nF.sub.2n+1; B(OR.sup.10).sub.2; OR.sup.11; SiR.sup.8.sub.p(OR.sup.9).sub.3-p; NR.sup.15(CO)R.sup.15, in which R.sup.15 is a hydrogen atom and NR.sup.16(CO)OR.sup.16, in which R.sup.16 is a hydrogen atom, and/or Y is a hydrogen atom or a group chosen from an alkyl radical.

3. Process according to claim 1, wherein said process is carried out for the preparation of substituted thiolactones of formula (I) in which: Z.sup.1 is a group chosen from the groups dimethylphosphonate and diethylphosphonate; C.sub.nF.sub.2n+1; B(OR.sup.10).sub.2, OR.sup.11, SiR.sup.8.sub.p(OR.sup.9).sub.3-p, NR.sup.15(CO)R.sup.15, in which R.sup.15 is a hydrogen atom and NR.sup.16(CO)OR.sup.16, in which R.sup.16 is a hydrogen atom, and/or Y is a hydrogen atom or a methyl or hydroxymethyl group.

4. Process according to claim 1, wherein said process leads to the formation of a thiolactone of formula (I), chosen from: dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate, diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, 3-methyl-5-pentyl-dihydrothiophen-2(3H)-one, 5-pentyl-dihydrothiophen-2(3H)-one, 3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one, 3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H, 5H)-trione, 3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one, (4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid, ((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid, (5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid, 3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one, 5-(trimethoxysilyl)dihydrothiophen-2(3H)-one, tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate, tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate, 3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one, 5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one, 3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one, (5-oxo-tetrahydrothiophen-2-yl)phosphonic acid, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one, 5-(perfluorooctyl)dihydrothiophen-2(3H)-one, 5-(perfluorobutyl)dihydrothiophen-2(3H)-one, dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one, 5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one, 5-(9-bromononyl).sub.3-methyldihydrothiophen-2(3H)-one, 5,5-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one, and 5,5-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one.

5. Process according to claim 1, wherein the step 1) of preparation of the monoadduct of formula (IV) is carried out without solvent, in water or in an organic solvent.

6. Process according to claim 1, wherein the radical initiator used during step 1) is chosen from organic peroxides, azo derivatives, redox couples that generate radicals and redox systems.

7. Process according to claim 6, wherein the organic peroxides are chosen from dilauroyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate, t-butyl peroxydodecanoate, t-butyl peroxyisobutyrate, t-amyl peroxypivalate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, potassium peroxydisulfate, sodium peroxydisulfate and ammonium peroxydisulfate.

8. Process according to claim 1, wherein the linker arm L is a linear alkyl chain, possibly interrupted by one or more heteroatoms, said hydrocarbon-based chain having from 1 to 100 carbon atoms.

9. Process according to claim 1, wherein the monomers of formula (III) are alkenes chosen from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, perfluorohexylethylene and perfluorooctylethylene.

10. Process according to claim 1, wherein the monomers of formula (III) are allylic compounds chosen from allylic alcohol, N-allyl benzamide, ethyl N-allyl carbamate, tert-butyl N-allyl carbamate, 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-allyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione, allylboronic acid, diethyl allylphosphonate, allyl phosphonic dichloride, dimethyl allylphosphonate, allyl cyanide, allyl isothiocyanate, allyl glycidyl ether, allyl benzyl ether, allyl phenyl ether, allyl butyl ether, allyl ethyl ether, allyl methylsulfone, allyl phenylsulfone, allyl chloride, allyl bromide and allyl fluoride.

11. Process according to claim 1, wherein step 1) is carried out at a temperature varying from 10 to 140 C.

12. Process according to claim 1, wherein step 2) of thermolysis is carried out without solvent.

13. Process according to claim 1, wherein at least one of the groups R.sup.1 or R.sup.3 is other than a hydrogen atom.

14. Substituted thiolactones of the following formula (I): ##STR00057## wherein: A.sup.1, A.sup.2, Y, Z, L, m, T and e may respectively assume the same meanings as those defined in claim 1 for A.sup.1, A.sup.2, Y, Z.sup.1, L, m, T and e for the thiolactones of formula (I), with the proviso that: when e=0 and W=H and m=0 and Y=hydrogen, then Z.sup.1 is other than a hydrogen atom, than a linear alkyl chain or than a phenyl ring; and when e=0 and W=H and m=0 and Y is a substituent having a nitrogen atom directly bonded to the thiolactone ring, then Z.sup.1 is other than a hydrogen atom.

15. Substituted thiolactones of formula (I) according to claim 14, wherein they are chosen from: dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate, diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, 3-methyl-5-pentyl-dihydrothiophen-2(3H)-one, 5-pentyl-dihydrothiophen-2(3H)-one, 3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one, 3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H, 5H)-trione, 3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one, (4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid, ((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid, (5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid, 3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one, 5-(trimethoxysilyl)dihydrothiophen-2(3H)-one, tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate, tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate, 3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one, 5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one, 3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one, (5-oxo-tetrahydrothiophen-2-yl)phosphonic acid, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one, 5-(perfluorooctyl)dihydrothiophen-2(3H)-one, 5-(perfluorobutyl)dihydrothiophen-2(3H)-one, dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one, 5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one, 5-(9-bromononyl).sub.3-methyldihydrothiophen-2(3H)-one, 5,5-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one, and 5,5-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one.

16. At least one substituted thiolactone of formula (I) obtained according to the process as defined in claim 1, said at least one substituted thiolactone configured for the synthesis of polymers or for surface functionalization or polymer functionalization.

17. least one thiolactone of formula (I) as defined in claim 14, said at least one substituted thiolactone configured for the synthesis of polymers or for surface functionalization or polymer functionalization.

Description

EXAMPLES

Example 1: Synthesis of dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1) According to the Process in Accordance with the Invention

[0207] In this example the thiolactone of the following formula was prepared (TL1):

##STR00017##

1) First Step: Preparation of O-1,2-dimethylpropyl S-methoxycarbonylmethyl xanthate (Xanthate of formula (II); (XA1))

[0208] ##STR00018##

1.1) Sub-Step 1: Preparation of potassium O-(1,2-dimethylpropyl)xanthogenate (XA0)

[0209] ##STR00019##

[0210] 100 g (1.13 mol) of 3-methylbutan-2-ol (Alfa Aesar), 63.65 g of potassium hydroxide (KOH, Sigma-Aldrich) and carbon disulfide (CS.sub.2, Sigma-Aldrich) were suspended in 500 ml of tetrahydrofuran (THF, Sigma-Aldrich) at room temperature for 24 hours.

[0211] After total dissolution of the KOH, the yellow emulsion was concentrated under reduced pressure then triturated with pentane (Sigma-Aldrich) and finally filtered to obtain 185 g of the expected product XA0 in the form of a yellow solid (185 g, yield 80%).

[0212] .sup.1H NMR (300.13 MHz, D.sub.2O, 298K) 5.31 (p, .sup.3J.sub.H,H=6.4 Hz, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 2.07-1.84 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.27 (d, .sup.3J.sub.H,H=6.4 Hz, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.96 (d, .sup.3J.sub.H,H=6.9 Hz, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0213] .sup.13C NMR{.sup.1H} (75.47 MHz, D.sub.2O, 298K) 232.6 (CS); 86.3 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 32.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.6 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 15.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3) ppm.

1.2) Sub-Step 2: Preparation of O-1,2-dimethylpropyl S-methoxycarbonylmethyl xanthate (XA1)

[0214] 0.21 mol (32.12 g) of methyl 2-bromoacetate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) in 200 ml of acetone (Sigma-Aldrich), in an ice bath. Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA1 in the form of a yellow oil (42 g, yield 89%) which will be used in the following step without purification.

2) Second Step: Preparation of O-1,2-dimethylpropyl S-(1-(dimethylphosphoryl)-3-(methoxycarbonyl))propyl xanthate (XA1VP: Monoadduct of Formula (IV))

[0215] ##STR00020##

[0216] 14.2 g (60 mmol) of the xanthate XA1 obtained above in the preceding step, 2.72 g (20 mmol) of dimethyl vinylphosphonate and 1.2 g (3 mmol) of dilauroyl peroxide (LPO: radical initiator) were mixed in a Schlenk tube. The mixture was subsequently degassed by 3 operations of freezing under vacuum. After 5 hours of heating at a temperature of 90 C., the crude reaction product was purified by silica chromatography (eluent ethyl acetate/petroleum ether (95:5, v:v) to recover the unreacted xanthate XA1, and with an eluent formed from a mixture of ethyl acetate/dichloromethane (1:4, v:v) to recover the monoadduct XA1VP (3.13 g, yield 42%, yellow oil).

[0217] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.53-5.33 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.31-4.11 (m, 1H, CHP); 3.75-3.65 (m, 6H, OP(OCH.sub.3).sub.2); 3.59 (s, 3H, CO.sub.2CH.sub.3); 2.56-2.44 (m, 2H, CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 2.43-1.87 (m, 2H, CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 2.02-1.87 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.25-1.21 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.89-0.86 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0218] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 211.8-211.5 (CS); 175.7 (CO.sub.2CH.sub.3); 87.3; 87.2 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 53.9-53.4 (OP(OCH.sub.3).sub.2); 51.7 (CO.sub.2CH.sub.3); 44.6-42.5 (CHP); 32.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 31.0-30.8 (CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 25.1-24.9 (CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 18.0-17.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 15.7; 15.6 ((CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0219] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 26.3; 26.2 ppm.

[0220] IR: 1738.5 cm.sup.1 (CO), 1035.1 cm.sup.1 (CS).

[0221] Molar mass: IC(CH.sub.4), MH.sup.+:

[0222] Found: 373.0916 g/mol

[0223] Calculated: 373.0908 g/mol.

3) Third Step: Preparation of dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1)

[0224] 3.70 g (10 mmol) of XA1VP obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 15 minutes. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL1 thus obtained in the form of a colourless oil (1.2 g, yield 57%) was subsequently purified on a silica chromatography column (eluent ethyl acetate/dichloromethane: 1:4 (v:v)).

[0225] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 3.87-3.76 (m, 1H, CHP); 3.72-3.57 (m, 6H, OP(OCH.sub.3).sub.2); 2.63-2.33 (m, 2H, CH.sub.2CH.sub.2CHP); 2.32-2.17 (m, 2H, CH.sub.2CH.sub.2CHP).

[0226] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 205.7-205.6 (CO); 53.2-53.1 (OP(OCH.sub.3).sub.2); 42.3-40.2 (CHP); 39.6-39.5 (CH.sub.2CH.sub.2CHP); 25.40-25.35 (CH.sub.2CH.sub.2CHP).

[0227] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 25.7 ppm.

[0228] IR: 1713.9 cm.sup.1 (CO).

[0229] Molar mass: IC(CH.sub.4), MH.sup.+

[0230] Found: 211.0198 g/mol

[0231] Calculated: 211.0194 g/mol.

Example 2: Synthesis of diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL2) According to the Process in Accordance with the Invention

[0232] ##STR00021##

1) First Step: Preparation of O-1,2-dimethylpropyl S-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate (Monoadduct of Formula (IV): XA2AP)

[0233] ##STR00022##

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropyl S-(1-methoxycarbonyl)ethyl xanthate (XA2)

[0234] 0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath. Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.

[0235] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.51 (p, .sup.3J.sub.H,H=6.3 Hz, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.42-4.30 (m, 1H, CH(CH.sub.3)CO.sub.2CH.sub.3); 3.73 (s, 3H, CO.sub.2CH.sub.3); 2.09-1.88 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.56-1.52 (m, .sup.3J.sub.H,H=7.4 Hz, 3H, CH(CH.sub.3)CO.sub.2CH.sub.3); 1.29-1.25 (m, .sup.3J.sub.H,H=6.4 Hz, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.02-0.91 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0236] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 211.4; 211.4 (CS); 172.0 (CO.sub.2CH.sub.3); 86.2-86.1 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.8 (CO.sub.2CH.sub.3); 46.5 (CH(CH.sub.3)CO.sub.2CH.sub.3); 32.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.2-17.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.0-16.9 (CH(CH.sub.3)CO.sub.2CH.sub.3); 15.8-15.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3) ppm.

[0237] IR: 1738.5 cm.sup.1 (CO); 1046.2 cm.sup.1 (CS)

1.2) Sub-Step 2: Preparation of O-1,2-dimethylpropyl S-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate (XA2AP)

[0238] 9.26 g (37 mmol) of the xanthate XA2 obtained above in step 1.1), 5.87 g (33 mmol) of diethyl allylphosphonate (DEAP, Alfa Aesar) and 2 g (5 mmol) of LPO were dissolved in 5 ml of toluene (Sigma-Aldrich). The solution thus obtained was transferred to a Schlenk tube and degassed by 3 successive operations of freezing under vacuum. After 18 hours of heating at 90 C., 10.1 g of crude reaction product were obtained in the form of a yellow oil (yield 79%) which was purified by silica chromatography (eluent ethyl acetate/dichloromethane: 1:4, v:v).

[0239] 12.7 g of XA2AP were thus obtained (yield 90%).

[0240] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.54-5.46 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.15-4.02 (m, 4H, OP(OCH.sub.2CH.sub.3).sub.2); 4.02-3.89 (m, 1H, CHS); 3.62 (s, 3H, CO.sub.2CH.sub.3); 2.75-1.63 (m, 6H, CH.sub.2P, (CH.sub.3).sub.2CHCH(O)CH.sub.3, CH.sub.2CHCO.sub.2CH.sub.3); 1.32-1.23 (m, 9H, OP(OCH.sub.2CH.sub.3).sub.2, CH.sub.3CHCO.sub.2CH.sub.3); 1.17-1.14 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.92-0.90 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0241] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 212.7-215.6 (CS); 176.2-176.0 (CO.sub.2CH.sub.3); 85.8-85.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 62.0-61.8 (OP(OCH.sub.2CH.sub.3).sub.2); 51.8 (CO.sub.2CH.sub.3); 43.8-43.6 (CHS); 37.8-36.6 (CH.sub.2P); 37.3-37.1 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 33.4-31.1 (CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 32.7 (CHCO.sub.2CH.sub.3); 18.3-17.9 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.3-17.8 (CH.sub.3CHCO.sub.2CH.sub.3); 16.6-165 (OP(OCH.sub.2CH.sub.3).sub.2); 15.9-15.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0242] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 26.7 ppm.

[0243] IR: 1736.9 cm.sup.1 (CO); 1043.6 cm.sup.1 (CS)

[0244] Molar mass: IC(CH.sub.4), MH.sup.+

[0245] Found: 429.1533 g/mol

[0246] Calculated: 429.1534 g/mol.

2) Second Step: Preparation of diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL2)

[0247] 4.28 g (10 mmol) of XA2AP obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 15 minutes. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL2 thus obtained in the form of a colourless oil (2.4 g, yield 90%) was subsequently purified on a silica chromatography column (eluent ethyl acetate/dichloromethane: 1:4 (v:v)).

[0248] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 4.18-4.05 (m, 4H, OP(OCH.sub.2CH.sub.3).sub.2); 4.05-3.90 (m, 1H, CHCH.sub.2P); 2.77-2.29 (m, 2H, CH.sub.2CH(CH.sub.3)); 2.28-2.07 (m, 2H, CHCH.sub.2P); 1.62-1.20 (m, 1H, CHCH.sub.2P); 1.35-1.29 (m, 6H, OP(OCH.sub.2CH.sub.3).sub.2); 1.19-1.14 (m, 3H, CH.sub.2CH(CH.sub.3)).

[0249] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 210.0-209.0 (CO); 62.2-62.1 (OP(OCH.sub.2CH.sub.3).sub.2); 48.7-45.4 (CHCH.sub.2P); 42.6-42.4 (CH.sub.2CH(CH.sub.3)); 41.0-40.9 (CH.sub.2CH(CH.sub.3)); 34.2-31.7 (CHCH.sub.2P); 16.6-16.5 (OP(OCH.sub.2CH.sub.3).sub.2); 15.2-14.3 (CH.sub.2CH(CH.sub.3)).

[0250] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 26.40, 26.36 ppm.

[0251] IR: 1700.5 cm.sup.1 (CO); 1245.7 cm.sup.1 (PO); 1025.4 cm.sup.1 (PO)

[0252] Molar mass: IC(CH.sub.4), MH.sup.+

[0253] Found: 267.0826 g/mol

[0254] Calculated: 267.0820 g/mol.

Example 3: Synthesis of diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3) According to the Process in Accordance with the Invention

[0255] ##STR00023##

1) First Step: Preparation of O-1,2-dimethylpropyl S-(1-(diethylphosphoryl)-4-(methoxycarbonyl))but-2-yl xanthate (Monoadduct of Formula (IV): XA3AP)

[0256] ##STR00024##

[0257] The monoadduct XA3AP was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above in step 1) of example 1, 5.88 g (33 mmol) of DEAP (Sigma-Aldrich) and 2 g (5 mmol) of LPO.

[0258] 12.31 g of XA3AP were thus obtained (yield 90%).

[0259] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.49-5.39 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.09-3.96 (m, 4H, OP(OCH.sub.2CH.sub.3).sub.2); 3.96-3.87 (m, 1H, CHS); 3.55 (s, 3H, CO.sub.2CH.sub.3); 2.48-1.84 (m, 7H, CH.sub.2P, (CH.sub.3).sub.2CHCH(O)CH.sub.3, CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 1.26-1.20 (m, 6H, OP(OCH.sub.2CH.sub.3).sub.2); 1.20-1.17 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.86-0.83 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0260] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 212.2 (CS); 172.8 (CO.sub.2CH.sub.3); 85.6 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 61.9-61.7 (OP(OCH.sub.2CH.sub.3).sub.2); 51.5 (CO.sub.2CH.sub.3); 44.5 (CHS); 32.5 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 32.5-30.5 (CH.sub.2P); 31.2-31.1 (CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 29.1-28.7 (CH.sub.2CH.sub.2CO.sub.2CH.sub.3); 18.1-17.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 16.4-16.3 (OP(OCH.sub.2CH.sub.3).sub.2); 15.6 ((CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0261] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 26.53; 26.51 ppm.

[0262] IR: 1738.8 cm.sup.1 (CO); 1044.9 cm.sup.1 (CS)

[0263] Molar mass: IC(CH.sub.4), MH.sup.+

[0264] Found: 415.1390 g/mol

[0265] Calculated: 415.1378 g/mol.

2) Second Step: Preparation of diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3)

[0266] The thiolactone TL3 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 4.14 g (10 mmol) of the monoadduct XA3AP prepared above in the preceding step instead of the monoadduct XA2AP.

[0267] 2.3 g of TL3 were thus obtained in the form of a colourless oil (yield 91%).

[0268] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 4.15-4.00 (m, 5H, CHCH.sub.2P, OP(OCH.sub.2CH.sub.3).sub.2); 2.63-2.45 (m, 3H, CH.sub.2CH.sub.2CO, CH.sub.2CH.sub.2CO); 2.29-2.08 (m, 2H, CHCH.sub.2P); 2.05-1.89 (m, 1H, CH.sub.2CH.sub.2CO); 1.32-1.25 (m, 6H, OP(OCH.sub.2CH.sub.3).sub.2).

[0269] .sup.13C{.sup.1H} .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 207.4 (CO); 62.1-62.0 (OP(OCH.sub.2CH.sub.3).sub.2); 44.44-44.39 (CHCH.sub.2P); 41.8 (CH.sub.2CH.sub.2CO); 33.7-31.8 (CHCH.sub.2P); 33.4-33.3 (CH.sub.2CH.sub.2CO); 16.5-16.4 (OP(OCH.sub.2CH.sub.3).sub.2).

[0270] .sup.31P NMR{.sup.1H} (121.49 MHz, CDCl.sub.3, 298K) 26.2 ppm.

[0271] IR: 1704.4 cm.sup.1 (CO); 1250.5 cm.sup.1 (PO); 1025.2 cm.sup.1 (PO)

[0272] Molar mass: IC(CH.sub.4), MH.sup.+

[0273] Found: 253.0667 g/mol

[0274] Calculated: 253.0663 g/mol.

Example 4: Synthesis of 3-methyl-5-pentyl-dihydrothiophen-2(3H)-one (TL4) According to the Process in Accordance with the Invention

[0275] ##STR00025##

1) First Step: Preparation of O-1,2-dimethylpropyl S-2-(methoxycarbonyl)non-4-yl xanthate (Monoadduct of Formula (IV): XA4H)

[0276] ##STR00026##

[0277] The monoadduct XA4H was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 9.26 g (37 mmol) of the xanthate XA2 prepared in step 1.1) of example 2, 3.24 g (33 mmol) of 1-heptene (Sigma-Aldrich) and 2 g (5 mmol) of LPO.

[0278] 10.7 g of XA4H were thus obtained (yellow oil; eluent ethyl acetate/petroleum ether (95:5; v:v), in the form of a racemate (yield 92%).

[0279] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.59-5.46 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.78-3.64 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 3.64-3.61 (m, 3H, CO.sub.2CH.sub.3); 2.73-2.54 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 2.13-1.87 (m, 2H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 1.75-1.47 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3, CH.sub.2(CH.sub.2).sub.3CH.sub.3); 1.47-1.31 (m, 2H, CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 1.31-1.18 (m, 7H, CH(CH.sub.3)CO.sub.2CH.sub.3, (CH.sub.2).sub.2(CH.sub.2).sub.2CH.sub.3); 1.18-1.09 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.97-0.87 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.87-0.79 (m, 3H, (CH.sub.2).sub.4CH.sub.3).

[0280] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 213.8-213.7 (CS); 176.3-176.3 (CO.sub.2CH.sub.3); 85.2-85.0 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 51.6 (CO.sub.2CH.sub.3); 49.1-48.6 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 38.1-37.5 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 37.2-37.1 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 35.2-34.7 (CH.sub.2(CH.sub.2).sub.3CH.sub.3); 32.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 31.6 ((CH.sub.2).sub.2CH.sub.2CH.sub.2CH.sub.3); 26.3-26.2 (CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 22.4 ((CH.sub.2).sub.3CH.sub.2CH.sub.3); 18.1-17.0 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.9-17.8 (CH(CH.sub.3)CO.sub.2CH.sub.3); 15.71-15.69 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 13.9 (SCH(CH.sub.2).sub.4CH.sub.3) ppm.

[0281] IR: 1738.5 cm.sup.1 (CO); 1047.2 cm.sup.1 (CS).

[0282] Molar mass: IC(CH.sub.4), MH.sup.+

[0283] Found: 349.1861 g/mol

[0284] Calculated: 349.1871 g/mol.

2) Second Step: Preparation of 3-methyl-5-pentyl-dihydrothiophen-2(3H)-one (TL4)

[0285] The thiolactone TL4 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 3.48 g (10 mmol) of the monoadduct XA4H prepared above in the preceding step instead of the monoadduct XA2AP.

[0286] 1.73 g of thiolactone TL4 were thus obtained (yield 93%) in the form of a colourless liquid (eluent: ethyl acetate/petroleum ether: 9:1; v:v).

[0287] .sup.1H NMR (300 MHz, CDCl.sub.3, 298K) 3.79-3.64 (m, 1H, SCHCH.sub.2CH); 2.76-2.46 (m, 2H, SCHCH.sub.2CH); 2.20-1.97 (m, 1H, SCHCH.sub.2CH); 1.83-1.62 (m, 2H, CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 1.55-1.35 (m, 2H, CH.sub.2(CH.sub.2).sub.3CH.sub.3); 1.35-1.21 (m, 4H, (H.sub.2).sub.2(CH.sub.2).sub.2CH.sub.3); 1.20-1.13 (m, 3H, CHCH.sub.3); 0.92-0.84 (m, 3H, (CH.sub.2).sub.4CH.sub.3).

[0288] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 211.2-210.0 (CO); 48.92-47.89 (SCHCH.sub.2CH); 47.5-456 (SCHCH.sub.2CH); 415-39.7 (SCHCH.sub.2CH); 36.8-36.5 (CH.sub.2(CH.sub.2).sub.3CH.sub.3); 31.7-31.6 ((CH.sub.2).sub.2CH.sub.2CH.sub.2CH.sub.3); 28.2-28.0 (CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 22.60-22.56 ((CH.sub.2).sub.3CH.sub.2CH.sub.3); 15.5-14.6 (CHCH.sub.3); 14.1 ((CH.sub.2).sub.4CH.sub.3) ppm.

[0289] IR: 1700.9 cm.sup.1 (CO).

[0290] Molar mass: IE

[0291] Found: 186.1075 g/mol

[0292] Calculated: 186.1078 g/mol.

Example 5: Synthesis of 5-pentyl-dihydrothiophen-2(3H)-one (TL5) According to the Process in Accordance with the Invention

[0293] ##STR00027##

1) First Step: Preparation of O-1,2-dimethylpropyl S-1-(methoxycarbonyl)oct-3-yl xanthate (Monoadduct of Formula (IV): XA5H)

[0294] ##STR00028##

[0295] The monoadduct XA5H was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above in step 1.2) of example 1, 3.24 g (33 mmol) of 1-heptene and 2 g (5 mmol) of LPO.

[0296] 10 g of thiolactone XA5H were thus obtained in the form of a yellow oil (eluent: ethyl acetate/petroleum ether: 95:5; v:v) in the form of a racemate (yield 90%).

[0297] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.53 (p, .sup.3J.sub.H,H=6.3 Hz, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.78-3.66 (m, 1H, SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 3.64 (s, 3H, CO.sub.2CH.sub.3); 2.49-2.36 (m, 2H, SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 2.12-1.94 (m, 2H, CH.sub.2(CH.sub.2).sub.3CH.sub.3); 1.93-1.77 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.69-1.52 (m, 2H, SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 1.52-1.33 (m, 2H, CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 1.33-1.16 (m, 7H, (CH.sub.2).sub.2(CH.sub.2).sub.2CH.sub.3; (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.93 (d, J=6.8 Hz, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.89-0.79 (m, 3H, (CH.sub.2).sub.4CH.sub.3).

[0298] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 214.0-213.9 (CS); 173.5-173.5 (CO.sub.2CH.sub.3); 85.4-85.4 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 51.7 (CO.sub.2CH.sub.3); 50.3-50.2 (SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 34.6-34.3 (CH.sub.2(CH.sub.2).sub.3CH.sub.3); 32.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 31.7 ((CH.sub.2).sub.2CH.sub.2CH.sub.2CH.sub.3); 31.5-31.4 (SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 29.7-29.3 (SCHCH.sub.2CH.sub.2CO.sub.2CH.sub.3); 26.6-26.5 (CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 22.6 ((CH.sub.2).sub.3CH.sub.2CH.sub.3); 18.3-18.0 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 15.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 14.1 ((CH.sub.2).sub.4CH.sub.3) ppm.

[0299] IR: 1740.9 cm.sup.1 (CO); 1048.6 cm.sup.1 (CS).

[0300] Molar mass: IC(CH.sub.4), MH.sup.+

[0301] Found: 335.1701 g/mol

[0302] Calculated: 335.1715 g/mol

2) Second Step: Preparation of 5-pentyl-dihydrothiophen-2(3H)-one (TL5)

[0303] The thiolactone TL5 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 3.34 g (10 mmol) of the monoadduct XA5H prepared above in the preceding step instead of the monoadduct XA2AP.

[0304] 1.55 g of TL5 were thus obtained in the form of a colourless liquid (eluent: ethyl acetate/petroleum ether: 9:1; v:v) (yield 90%).

[0305] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 3.82 (tt, .sup.3J.sub.H,H=8.5; 5.8 Hz, 1H, SCHCH.sub.2CH.sub.2); 2.66-2.44 (m, 2H, SCHCH.sub.2CH.sub.2); 2.43-1.79 (m, 2H, SCHCH.sub.2CH.sub.2); 1.79-1.62 (m, 2H, CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 1.47-1.33 (m, 2H, CH.sub.2(CH.sub.2).sub.3CH.sub.3); 1.32-1.19 (m, 4H, (CH.sub.2).sub.2(CH.sub.2).sub.2CH.sub.3); 0.86 (t, .sup.3J.sub.H,H=7.0 Hz, 3H, (CH.sub.2).sub.4CH.sub.3).

[0306] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 208.6 (CO); 51.4 (SCHCH.sub.2CH.sub.2); 42.1 (SCHCH.sub.2CH.sub.2); 36.5 (CH.sub.2(CH.sub.2).sub.3CH.sub.3); 32.3 ((CH.sub.2).sub.2CH.sub.2CH.sub.2CH.sub.3); 31.5 (SCHCH.sub.2CH.sub.2); 28.0 (CH.sub.2CH.sub.2(CH.sub.2).sub.2CH.sub.3); 22.5 ((CH.sub.2).sub.3CH.sub.2CH.sub.3); 14.0 ((CH.sub.2).sub.4CH.sub.3) ppm.

[0307] IR: 1704.6 cm.sup.1 (CO)

[0308] Mass: IE

[0309] Found: 172.0910 g/mol

[0310] Calculated: 172.0922 g/mol.

Example 6: Synthesis of 3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6) According to the Process in Accordance with the Invention

[0311] ##STR00029##

1) First Step: Preparation of Methyl 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafiuoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)dodecanoate (Monoadduct of Formula (IV): XA6DF)

[0312] ##STR00030##

[0313] The monoadduct XA6DF was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 3.09 g (1.2310.sup.2 mol) of xanthate XA2 as prepared above in step 1.1) of example 2, 5 g (1.1210.sup.2 mol) of 1H,1H,2H-perfluoro-1-decene (Aldrich), 0.67 g of LPO, and a reaction solvent composed of 4 ml of toluene and 3 ml of trifluorotoluene.

[0314] The monoadduct XA6DF obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 9:1, v:v).

[0315] 3.2 g of XA6DF were thus obtained (yield 41%).

[0316] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 5.58-5.47 (s, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.87-4.67 (m, 1H, SCHCH.sub.2CH(CH.sub.3)); 3.70-3.68 (m, 3H, CO.sub.2CH.sub.3); 2.92-2.68 (1H, m, SCHCH.sub.2CH(CH.sub.3)); 2.14-1.92 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.58-1.53 (m, 2H, SCHCH.sub.2CH(CH.sub.3)); 1.32-1.20 (m, 6H; (CH.sub.3).sub.2CHCH(O)CH.sub.3 et SCHCH.sub.2CH(CH.sub.3)); 0.97-0.93 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0317] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K): (ppm) 209.33 (CS); 175.54 (CO.sub.2CH.sub.3); 129.01-115.52 (CH(CF.sub.2).sub.7CF.sub.3); 87.48 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.71-51.79 (CO.sub.2CH.sub.3); 46.50 (CH(CF.sub.2).sub.3CF.sub.3); 36.48 (SCHCH.sub.2CH(CH.sub.3)); 32.71 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.30-15.44 ((CH.sub.3).sub.2CHCH(O)CH.sub.3 et (SCHCH.sub.2CH(CH.sub.3)).

[0318] NMR .sup.19F{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 80.83 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 105.65-116.25 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 118.87-119.33 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 121.69-121.91 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 122.72 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 126.16 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)).

2) Second Step: Preparation of 3-Methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6)

[0319] 2 g (2.87 mmol) of XA6DF obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL6 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).

[0320] 0.8 g of TL6 were thus obtained in the form of a white powder (yield 52%).

[0321] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 4.49-4.36 (m, 1H, CHCF.sub.2); 2.75-2.59 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.99-1.87 (q, 1H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.26-1.23 (d, 3H, C(O)CH(CH.sub.3)).

[0322] NMR .sup.19F{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 81.03 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 112.13-119.71 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 121.08 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 121.96 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 122.86 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 126.29 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)).

Example 7: Synthesis of 3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione (TL7) According to the Process in Accordance with the Invention

[0323] ##STR00031##

1) First Step: Preparation of XA7MAL (Monoadduct of Formula (IV))

[0324] ##STR00032##

[0325] The monoadduct XA7MAL was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.77 g (1.9110.sup.2 mol) of the xanthate XA2 as prepared above in step 1.1) of example 2, 3 g (1.7310.sup.2 mol) of N-phenylmaleimide (Aldrich) and 1.03 g of LPO.

[0326] The monoadduct XA7MAL obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 7:3, v:v).

[0327] 4.9 g of XA7MAL were thus obtained (yield 68%).

[0328] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 7.47-7.30 (m, 5H, NC.sub.6H.sub.5); 5.57-5.48 (s, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 5.22-4.07 (m, 1H, SCH(CO)CH); 3.76-3.66 (m, 3H, CO.sub.2CH.sub.3); 3.55-3.21 (m, 2H, SCH(CO)CH(CO)CH(CH.sub.3)); 2.07-1.92 (1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.56-1.39 (m, 3H, CH(CO)CH(CH.sub.3)); 1.39-1.26 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.98-0.92 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0329] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K): (ppm) 209.77 (CS); 175.59-171.71 (C(O)NC(O) et CO.sub.2CH.sub.3); 131.38-126.36 (NC.sub.6H.sub.5); 87.27 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.42 CO.sub.2CH.sub.3); 50.47-46.87 (SCH(CO)CH(CO)CH(CH.sub.3)); 39.71-38.99 (SCH(CO)CH(CO)CH(CH.sub.3)); 32.82 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.34-17.84 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 15.81-15.21 (SCH(CO)CH(CO)CH(CH.sub.3)).

2) Second Step: Preparation of 3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione (TL7)

[0330] 1 g (2.36 mmol) of XA7MAL obtained above in the preceding step was placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL7 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).

[0331] 0.4 g of TL7 were thus obtained (yield 65%).

[0332] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 7.55-7.30 (m, 5H, NC.sub.6H.sub.5); 4.86-4.75 (s, 1H, SCH(CO)CH); 3.46-3.44 (m, 1H, CH(CH.sub.3)CHC(O)); 3.34-3.25 (m, 1H, C(O)CH(CH.sub.3)); 1.49-1.47 (d, 3H, C(O)CH(CH.sub.3)).

[0333] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K): (ppm) 205.25 (SCO); 174.5-173.49 (C(O)NC(O)); 129.21-126.39 (NC.sub.6H.sub.5) 49.54 (SCH(CO)); 49.03 (C(O)CH(CH.sub.3)); 46.81 (C(O)CH(CH.sub.3)CH(CO); 18.41 (C(O)CH(CH.sub.3)CH.sub.2).

Example 8: Synthesis of 3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8) According to the Process in Accordance with the Invention

[0334] ##STR00033##

1) First Step: Preparation of methyl 5,5,6,6,7,7,8,8,8-nonafluoro-2-methyl-4-((((3-mthylbutan-2-yl)oxy)carbonothioyl)thio)octanoate (Monoadduct of Formula (IV): XA8HF)

[0335] ##STR00034##

[0336] The monoadduct XA8HF was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.47 g (1.7810.sup.2 mol) of the xanthate XA2 as prepared above in step 1.1) of example 2, 4 g (1.6210.sup.2 mol) of 1H,1H,2H-perfluoro-1-hexene (Aldrich) and 0.969 g of LPO.

[0337] The monoadduct XA8HF obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 9:1, v:v).

[0338] 3.73 g of XA8HF were thus obtained (yield 46%).

[0339] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 5.59-5.48 (s, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.92-4.66 (m, 1H, SCHCH.sub.2CH(CH.sub.3)); 3.73-3.67 (m, 3H, CO.sub.2CH.sub.3); 2.91-2.61 (1H, m, SCHCH.sub.2CH(CH.sub.3)); 2.16-1.88 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.60-1.52 (m, 2H, SCHCH.sub.2CH(CH.sub.3)); 1.32-1.20 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3 et SCHCH.sub.2CH(CH.sub.3)); 0.96-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0340] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K): (ppm) 209.30 (CS); 175.35 (CO.sub.2CH.sub.3); 129.01-127.51 (CH(CF.sub.2).sub.3CF.sub.3); 87.49 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.70-51.91 (CO.sub.2CH.sub.3); 46.48 CH(CF.sub.2).sub.3CF.sub.3); 36.46 (SCHCH.sub.2CH(CH.sub.3)), 32.64 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.32-14.08 ((CH.sub.3).sub.2CHCH(O)CH.sub.3 et (SCHCH.sub.2CH(CH.sub.3)).

[0341] NMR .sup.19F{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 80.80 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.3)), 105.96-116.42 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.3)), 119.86-120.36 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.3)), 125.60-126.30 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.3)).

2) Second Step: Preparation of 3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8)

[0342] 2 g (4.03 mmol) of XA8HF obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL8 thus obtained in the form of a colourless oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 5:95 (v:v)).

[0343] 0.8 g of TL8 were thus obtained in the form of a white powder (yield 52%).

[0344] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 4.49-4.36 (m, 1H, CHCF.sub.2); 2.75-2.59 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.99-1.87 (q, 1H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.26-1.23 (d, 3H, C(O)CH(CH.sub.3)).

[0345] NMR .sup.19F{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 81.03 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 112.13-119.71 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 121.08 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 121.96 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 122.86 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)); 126.29 (CH(CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3)).

Example 9: Functionalization of Polymers by a Thiolactone According to the Invention

1) Example 9.1: Functionalization of bis(3-aminopropyl)-poly(dimethylsiloxane) by TL4

[0346] ##STR00035##

[0347] The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g.Math.mol.sup.1, 500 mg, 210.sup.4 mol, Aldrich), TL4 (52.1 mg, 2.810.sup.4 mol) and benzyl acrylate (45.4 mg, 2.810.sup.4 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50 C. .sup.1H NMR analysis and MALDI-TOF analysis showed total functionalization of the bis(3-aminopropyl)-poly(dimethylsiloxane).

2) Example 9.2: Functionalization of Methoxypolyethylene Glycol Amine by TL4

[0348] ##STR00036##

[0349] The following were successively introduced into a 25 ml round-bottomed flask: methoxypolyethylene glycol amine (2000 g.Math.mol.sup.1, 200 mg, 110.sup.4 mol, Aldrich), TL4 (16.7 mg, 910.sup.5 mol) and benzyl acrylate (14.6 mg, 910.sup.5 mol, Aldrich). The reaction mixture was stirred for 20 hours at 60 C. .sup.1H NMR analysis and MALDI-TOF analysis showed total functionalization of the methoxypolyethylene glycol amine.

3) Example 9.3: Functionalization of bis(3-aminopropyl)-poly(dimethylsiloxane) by TL2

[0350] ##STR00037##

[0351] The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g.Math.mol.sup.1, 500 mg, 210.sup.4 mol, Aldrich), TL2 (74.5 mg, 2.810.sup.4 mol) and benzyl acrylate (45.4 mg, 2.810.sup.4 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50 C. .sup.1H NMR analysis showed total functionalization of the bis(3-aminopropyl)-poly(dimethylsiloxane).

4) Example 9.4: Functionalization of methoxypolyethylene glycol amine by TL2

[0352] ##STR00038##

[0353] The following were successively introduced into a 25 ml round-bottomed flask: methoxypolyethylene glycol amine (2000 g.Math.mol.sup.1, 200 mg, 110.sup.4 mol, Aldrich), TL2 (23.9 mg, 910.sup.5 mol) and benzyl acrylate (14.6 mg, 910.sup.5 mol, Aldrich). The reaction mixture was stirred for 20 hours at 60 C. .sup.1H NMR analysis showed total functionalization of the methoxypolyethylene glycol amine.

5) Example 9.5: Polymerization of bis(3-aminopropyl)-poly(dimethylsiloxane) with TL2 and poly(ethylene glycol) diacrylate

[0354] ##STR00039##

[0355] The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g.Math.mol.sup.1, 500 mg, 2.0104 mol, Aldrich), TL2 (74.5 mg, 2.810.sup.4 mol) and poly(ethylene glycol) diacrylate (575 g.Math.mol.sup.1, 80.5 mg, 1.4104 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50 C. H and .sup.31P NMR analysis showed total consumption of the monomers, and size exclusion chromatography confirmed the formation of the polymer. Mn.sub.(PS)=8100 g.Math.mol.sup.1 Mw.sub.(PS)=14 500 g.Math.mol.sup.1.

Example 10: Synthesis of dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one (TL23) According to the Process in Accordance with the Invention

[0356] ##STR00040##

1) First Step: Preparation of the Monoadduct of Formula (IVa); XA23OD

[0357] ##STR00041##

[0358] The monoadduct XA23OD was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.77 g (1.9010.sup.2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 1 g (0.9010.sup.2 mol) of 1,7-octadiene (Aldrich), 0.54 g of LPO, and a reaction solvent composed of 2 ml of toluene.

[0359] The monoadduct XA23OD obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 95:5, v:v).

[0360] 2.49 g of XA23OD were thus obtained (yield 45%).

[0361] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 5.47-5.46 (s, 2H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.77-3.78 (m, 2H, SCHCH.sub.2CH(CH.sub.3)); 3.66-3.64 (m, 6H, CO.sub.2CH.sub.3); 2.73-2.61 (2H, m, SCHCH.sub.2CH(CH.sub.3)); 2.15-1.91 (m, 4H, SCHCH.sub.2CH(CH.sub.3)); 1.73-1.49 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3 et SCH(CH.sub.2CH.sub.2)CH.sub.2CH(CH.sub.3)); 1.49-1.34 (m, 4H, SCH(CH.sub.2CH.sub.2)CH.sub.2CH(CH.sub.3)); 1.28-1.23 (d, 3H, SCHCH.sub.2CH(CH.sub.3)); 1.17-1.15 (d, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.94-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

2) Second Step: Preparation of dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one (TL23)

[0362] 2.49 g (4.1 mmol) of XA23OD obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL9 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 8:2 (v:v)).

[0363] 0.877 g of TL23 were thus obtained in the form of a white powder (yield 75%).

[0364] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 2.20-1.99 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.84-1.63 (m, 4H, CH.sub.2CH.sub.2CH.sub.2); 1.56-1.38 (m, 5H, CHCH.sub.2CH.sub.2, CHCH.sub.2CH.sub.2); 1.17-1.13 (m, 6H, CH.sub.3).

[0365] .sup.13C NMR{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 210.74-209.61 (CO); 48.78-45.42 ((CH.sub.3)CHCH.sub.2CH.sub.2CHS); 41.30-39.48 ((CH.sub.3)CHCH.sub.2CH.sub.2CHS); 36.59-36.13 (CHCH.sub.2CH.sub.2CH.sub.2); 28.26-27.94 (CHCH.sub.2CH.sub.2CH.sub.2); 15.38-14.45 (CH.sub.3).

Example 11: Synthesis of 5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL 24) According to the Process in Accordance with the Invention

[0366] ##STR00042##

1) First Step: Preparation of methyl 13-hydroxy-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate (Xanthate XA2HN)

[0367] ##STR00043##

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropyl S-(1-methoxycarbonyl)ethyl xanthate (XA2)

[0368] 0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.

[0369] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.51 (p, .sup.3J.sub.H,H=6.3 Hz, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.42-4.30 (m, 1H, CH(CH.sub.3)CO.sub.2CH.sub.3); 3.73 (s, 3H, CO.sub.2CH.sub.3); 2.09-1.88 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.56-1.52 (m, .sup.3J.sub.H,H=7.4 Hz, 3H, CH(CH.sub.3)CO.sub.2CH.sub.3); 1.29-1.25 (m, .sup.3J.sub.H,H=6.4 Hz, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.02-0.91 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0370] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 211.4; 211.4 (CS); 172.0 (CO.sub.2CH.sub.3); 86.2-86.1 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.8 (CO.sub.2CH.sub.3); 46.5 (CH(CH.sub.3)CO.sub.2CH.sub.3); 32.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.2-17.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.0-16.9 (CH(CH.sub.3)CO.sub.2CH.sub.3); 15.8-15.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3) ppm.

[0371] IR: 1738.5 cm.sup.1 (CO); 1046.2 cm.sup.1 (CS)

1.2) Sub-step 2: Preparation of methyl 13-hydroxy-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate (XA2HN)

[0372] The xanthate XA2HN was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the xanthate XA2AP, but using 5.01 g (20 mmol) of the xanthate XA2 prepared in the preceding step, 3.05 g (18 mmol) of undecene-1-ol (Sigma-Aldrich) and 1 g (26 mmol) of LPO.

[0373] 5.8 g of XA2HN were thus obtained (yellow oil; eluent hexane/ethyl acetate (7:3; v:v), in the form of a racemate (yield 77%).

[0374] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) =5.57-5.48 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.75-3.71 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 3.66-3.64 (m, 3H, CO.sub.2CH.sub.3); 3.62,-3.57 (t, 2H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 2.72-2.65 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 2.12-1.91 (m, 2H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 1.80 (s, 1H, OH); 1.73-1.48 (m, 5H, (CH.sub.3).sub.2CHCH(O)CH.sub.3; CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 1.38-1.24 (m, 15H, CH(CH.sub.3)CO.sub.2CH.sub.3; CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 1.17-1.15 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.94-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0375] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) =213.80-213.70 (CS); 176.65 (CO.sub.2CH.sub.3); 85.40 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 62.90 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 51.58 (CO.sub.2CH.sub.3); 49.14-48.59 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 38.16-37.54 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 37.50-37.13 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 32.70-32.69 ((CH.sub.3).sub.2CHCH(O)CH.sub.3; CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 29.48-25.72 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 18.25-18.23 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.02-15.79 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); CH(CH.sub.3)CO.sub.2CH.sub.3).

2) Second Step: Preparation of 5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL24)

[0376] The thiolactone TL24 was prepared according to the same procedure as that used above in example 2, step 3) for the preparation of the thiolactone TL2, but using 3.4 g (8 mmol) of the xanthate XA2HN prepared above in the preceding step instead of the xanthate XA2AP.

[0377] 1.89 g of thiolactone TL24 were thus obtained (yield 91%) in the form of a colourless liquid (eluent: hexane/ethyl acetate: 5:5; v:v).

[0378] .sup.1H NMR (300 MHz, CDCl.sub.3, 298K) =3.74-3.63 (m, 1H, SCHCH.sub.2CH); 3.58-3.53 (t, 2H, SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 2.72-2.43 (m, 1.5H, C(O)CH(CH.sub.3)CH.sub.2); 2.24 (s, 1H, OH); 2.15-1.95 (m, 1H, SCHCH.sub.2CH); 1.74-1.60 (m, 2H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 1.52-1.42 (m, 2.5H, SCHCH.sub.2CH, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 1.37-1.20 (m, 12H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 1.12-1.09 (m, 3H, C(O)CH(CH.sub.3)CH.sub.2).

[0379] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) =211.34-210.18 (CO); 62.78 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 48.81-45.50 (SCHCH.sub.2CH, C(O)CH(CH.sub.3)CH.sub.2); 41.37-39.52 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 36.71-36.36 (C(O)CH(CH.sub.3)CH.sub.2); 32.70 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 29.45-25.73 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2OH); 15.38-14.42 (C(O)CH(CH.sub.3)CH.sub.2).

Example 12: Synthesis of 5-(9-bromononyl)-3-methyldihydrothiophen-2(3H)-one (TL25) According to the Process in Accordance with the Invention

[0380] ##STR00044##

1) First Step: Preparation of methyl 13-bromo-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate (Xanthate XA2BN)

[0381] ##STR00045##

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropyl S-(1-methoxycarbonyl)ethyl xanthate (XA2)

[0382] 0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.

[0383] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) 5.51 (p, .sup.3J.sub.H,H=6.3 Hz, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 4.42-4.30 (m, 1H, CH(CH.sub.3)CO.sub.2CH.sub.3); 3.73 (s, 3H, CO.sub.2CH.sub.3); 2.09-1.88 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.56-1.52 (m, .sup.3J.sub.H,H=7.4 Hz, 3H, CH(CH.sub.3)CO.sub.2CH.sub.3); 1.29-1.25 (m, .sup.3J.sub.H,H=6.4 Hz, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.02-0.91 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0384] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) 211.4; 211.4 (CS); 172.0 (CO.sub.2CH.sub.3); 86.2-86.1 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 52.8 (CO.sub.2CH.sub.3); 46.5 (CH(CH.sub.3)CO.sub.2CH.sub.3); 32.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 18.2-17.8 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.0-16.9 (CH(CH.sub.3)CO.sub.2CH.sub.3); 15.8-15.7 ((CH.sub.3).sub.2CHCH(O)CH.sub.3) ppm.

[0385] IR: 1738.5 cm.sup.1 (CO); 1046.2 cm.sup.1 (CS)

1.2) Sub-Step 2: Preparation of methyl 13-bromo-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate (XA2BN)

[0386] The xanthate XA2BN was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the xanthate XA2AP, but using 1.01 g (4 mmol) of the xanthate XA2 prepared in the preceding step, 0.86 g (3.7 mmol) of bromo-11-undecene (Alfa-Aesar) and 0.22 g (0.5 mmol) of LPO.

[0387] 1.41 g of XA2BN were thus obtained (yellow oil; eluent hexane/ethyl acetate (95:5; v:v), in the form of a racemate (yield 80%).

[0388] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K) =5.59-5.52 (m, 1H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.78-3.77 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 3.66-3.64 (m, 3H, CO.sub.2CH.sub.3); 3.41-3.36 (t, 2H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 2.70-2.63 (m, 1H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 2.08-1.91 (m, 2H, SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 1.73-1.48 (m, 5H, (CH.sub.3).sub.2CHCH(O)CH.sub.3; CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 1.38-1.24 (m, 15H, CH(CH.sub.3)CO.sub.2CH.sub.3, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 1.17-1.15 (m, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.94-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

[0389] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) =213.80-213.70 (CS); 176.65 (CO.sub.2CH.sub.3); 85.40 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 51.58 (CO.sub.2CH.sub.3); 49.14-48.59 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 38.16-37.54 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 37.50-37.13 (SCHCH.sub.2CH(CH.sub.3)CO.sub.2CH.sub.3); 34.90 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 32.70-32.69 ((CH.sub.3).sub.2CHCH(O)CH.sub.3; CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 29.48-25.72 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 18.25-18.23 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); 17.02-15.79 ((CH.sub.3).sub.2CHCH(O)CH.sub.3); CH(CH.sub.3)CO.sub.2CH.sub.3).

2) Second Step: Preparation of 5-(9-bromononyl)-3-methyldihydrothiophen-2(3H)-one (TL25)

[0390] The thiolactone TL25 was prepared according to the same procedure as that used above in example 2, step 3) for the preparation of the thiolactone TL2, but using 0.59 g (1.2 mmol) of the xanthate XA2BN prepared above in the preceding step instead of the xanthate XA2AP.

[0391] 0.202 g of thiolactone TL25 were thus obtained (yield 52%) in the form of a colourless liquid (eluent: hexane/ethyl acetate: 9:1; v:v).

[0392] .sup.1H NMR (300 MHz, CDCl.sub.3, 298K) =3.79-3.66 (m, 1H, SCHCH.sub.2CH); 3.42-3.38 (t, 2H, SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 2.74-2.49 (m, 1.5H, C(O)CH(CH.sub.3)CH.sub.2); 2.18-2.02 (m, 1H, SCHCH.sub.2CH); 1.89-1.59 (m, 4H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 1.37-1.20 (m, 13H, CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 1.12-1.09 (m, 3H, C(O)CH(CH.sub.3)CH.sub.2).

[0393] .sup.13C NMR{.sup.1H} (75.47 MHz, CDCl.sub.3, 298K) =211.05-209.91 (CO); 48.82-45.0 (SCHCH.sub.2CH, C(O)CH(CH.sub.3)CH.sub.2); 41.40 (CH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 39.56-39.52 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 36.76-36.40 (C(O)CH(CH.sub.3)CH.sub.2); 32.70 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 29.45-25.73 (SCHCH.sub.2(CH.sub.2).sub.6CH.sub.2CH.sub.2Br); 15.38-14.42 (C(O)CH(CH.sub.3)CH.sub.2).

Example 13: Synthesis of 5,5-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL 26) According to the Process in Accordance with the Invention

[0394] ##STR00046##

1) First Step: Preparation of the Monoadduct of Formula (IVa); XA2ED

[0395] ##STR00047##

[0396] The monoadduct XA2ED was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.01 g (3.210.sup.2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 1.25 g (1.510.sup.2 mol) of 1,5-hexadiene (Aldrich), 1.77 g of LPO, and a reaction solvent composed of 6 ml of toluene.

[0397] The monoadduct XA2ED obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 95:5, v:v).

[0398] 3.79 g of XA2ED were thus obtained (yield 73%).

[0399] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 5.47-5.46 (s, 2H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.77-3.78 (m, 2H, SCHCH.sub.2CH(CH.sub.3)); 3.66-3.64 (m, 6H, CO.sub.2CH.sub.3); 2.73-2.61 (2H, m, SCHCH.sub.2CH(CH.sub.3)); 2.15-1.91 (m, 4H, SCHCH.sub.2CH(CH.sub.3)); 1.73-1.49 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3 et SCH(CH.sub.2CH.sub.2)CH.sub.2CH(CH.sub.3)); 1.28-1.23 (d, 3H, SCHCH.sub.2CH(CH.sub.3)); 1.17-1.15 (d, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.94-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

2) Second Step: Preparation of 5,5-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL26)

[0400] 3.36 g (5.7 mmol) of XA2ED obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL26 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 6:4 (v:v)).

[0401] 1.2 g of TL26 were thus obtained in the form of a white powder (yield 84%).

[0402] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 2.20-1.99 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.56-1.38 (m, 5H, CHCH.sub.2CH.sub.2, CHCH.sub.2CH.sub.2); 1.17-1.13 (m, 6H, CH.sub.3).

[0403] .sup.13C NMR{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 210.74-209.61 (CO); 48.78-45.42 ((CH.sub.3)CHCH.sub.2CH.sub.2CHS); 41.30-39.48 ((CH.sub.3)CHCH.sub.2CH.sub.2CHS); 36.59-36.13 (CHCH.sub.2CH.sub.2CH.sub.2); 15.38-14.45 (CH.sub.3).

Example 14: Synthesis of 5,5-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL 27) According to the Process in Accordance with the Invention

[0404] ##STR00048##

1) First Step: Preparation of a Monoadduct of Formula (IVa); XA2HD

[0405] ##STR00049##

[0406] The monoadduct XA2HD was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 9.07 g (3.610.sup.2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 2.38 g (1.510.sup.2 mol) of 1,9-decadiene (Aldrich), 2.03 g of LPO, and a reaction solvent composed of 7 ml of toluene.

[0407] The monoadduct XA2HD obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 90:10, v:v). 7.37 g of XA2HD were thus obtained (yield 68%).

[0408] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 5.58-5.49 (s, 2H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 3.77-3.78 (m, 2H, SCHCH.sub.2CH(CH.sub.3)); 3.66-3.64 (m, 6H, CO.sub.2CH.sub.3); 2.73-2.61 (2H, m, SCHCH.sub.2CH(CH.sub.3)); 2.15-1.91 (m, 4H, SCHCH.sub.2CH(CH.sub.3)); 1.73-1.28 (m, 14H, (CH.sub.3).sub.2CHCH(O)CH.sub.3 et SCH(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)CHSH) et (CH.sub.3).sub.2CHCH(O)CH.sub.3); 1.28-1.23 (d, 3H, SCHCH.sub.2CH(CH.sub.3)); 1.17-1.15 (d, 3H, (CH.sub.3).sub.2CHCH(O)CH.sub.3); 0.94-0.92 (m, 6H, (CH.sub.3).sub.2CHCH(O)CH.sub.3).

2) Second Step: Preparation of 5,5-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL27)

[0409] 6.56 g (10.2 mmol) of XA2HD obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190 C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL27 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 7:3 (v:v)).

[0410] 2.48 g of TL27 were thus obtained in the form of a white powder (yield 77%).

[0411] .sup.1H NMR (300.13 MHz, CDCl.sub.3, 298K): (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 2.20-1.99 (m, 2H, C(O)CH(CH.sub.3)CH.sub.2CH); 1.78-1.64 (m, 4H, SCH(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)CHSH) 1.53-1.38 (m, 9H, CHCH.sub.2CH.sub.2, SCH(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)CHSH); 1.17-1.13 (m, 6H, CH.sub.3).

[0412] .sup.13C NMR{.sup.1H} (282.38 MHz, CDCl.sub.3, 298K): (ppm) 210.74-209.61 (CO); 48.78-45.42 ((CH.sub.3)CHCH.sub.2CHS); 41.30-39.48 ((CH.sub.3)CHCH.sub.2CHS); 36.71-36.36 (SCH(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)CHSH); 28.34-28.16 (SCH(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)CHCHSH); 15.38-14.45 (CH.sub.3).