Spirotetrathiocarbamates and spirooxothiocarbamates

1. A compound of Formula I:

or Formula II:

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are independently O or S; and in compound of formula I at least two and up to all four of X 1 , X 2 , X 3 and X 4 are sulfur;

Z is —C m R 2 2m — wherein m=1 to 4; —C(R 2 ) 2 SC(R 2 ) 2 —, —C(R 2 ) 2 SSC(R 2 ) 2 —, or —C(R 2 ) 2 OC(R 2 ) 2 ;

n is 1 to 4 in compound of formula I and is 0 to 4 in compound of formula II;

M is selected from CH 2 Cl, CH 2 SC(O)R 1 , CH 2 SC(S)R 1 , CH 2 S(CH 2 CH 2 S) q H wherein q is 0, 1 or 2; —CR 2 ═CH 2 , —CH 2 OC(O)CR 2 ═CH 2 , CH 2 N═C═S, CH 2 N═C═O, CH 2 NR 2 H, CH 2 OH, CH 2 SCH 2 CH 2 CR 2 ═CH 2 , phenyl, C(R 2 ) 2 phenyl, furan, thiophene, halogen, C 3 -C 6 cycloalkyl, C 3 -C 6 heretocyclics, thiol,

A is O, S or phenyl and x is 0 or 1;

wherein R 1 is C 1 -C 22 alkyl; and

R 2 is H or C 1 -C 22 alkyl.

2. The compound of claim 1 , wherein in the compound of formula II at least two and up to all four of X 1 , X 2 , X 3 and X 4 , and at least two and up to all four of X 5 , X 6 , X 7 , and X 8 are sulfur.

3. The compound of claim 1 , further defined as having Formula II:

wherein n is 1, 2, 3 or 4.

4. The compound of claim 1 , further defined as:

2-(Mercaptomethyl)-1,4,6,9-tetrathiaspiro[4.4]nonane;

2,7-Bis(mercaptomethyl)-1,4,6,9-tetrathiaspiro[4.4]nonane;

2-(S-methyl)-7-vinyl-1,4,6,9-tetrathiaspiro[4.4]nonane thiolacetate;

2-(Mercaptomethyl)-7-vinyl-1,4,6,9-tetrathiaspiro[4.4]nonane;

7-(Mercaptomethyl)-2-(S-methyl)-1,4,6,9-tetrathiaspiro[4.4]nonane thiolacetate;

2-Mercaptomethyl-1-oxa-4,6,9-trithiaspiro[4.4]nonane; or

2,7-Bis(mercaptomethyl)-1-oxa-4,6,9-trithiaspiro[4.4]nonane.

5. The compound of claim 1 , further defined as:

2-(Chloromethyl)-1,4,6,9-tetrathiaspiro[4.4]nonane;

2-(S-Methyl)-1,4,6,9-tetrathiaspiro[4.4]nonane thiolacetate;

4-(S-Methyl)-1,3-dithiolane-2-thione thiolacetate;

2-(Chloromethyl)-7-(S-methyl)-1,4,6,9-tetrathiaspiro[4.4]nonane thiolacetate;

2,7-Bis(S-methyl)-1,4,6,9-tetrathiaspiro[4.4]nonane thiolacetate;

2-(S-methyl)-1-oxa-4,6,9-trithiaspiro[4.4]nonane thiolacetate;

2-(Mercaptomethyl)-1-oxa-4,6,9-trithiaspiro[4.4]nonane;

2-(Chloromethyl)-7-(S-methyl)-1-oxa-4,6,9-trithiaspiro[4.4]nonane thiolacetate; or

2,7-Bis(S-methyl)-1-oxa-4,6,9-trithiaspiro[4.4]nonane thiolacetate.

6. A method for manufacturing optical lenses comprising:

polymerizing a compound of Formula I:

or a compound of Formula II:

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 , are independently O or S; and in compound of formula I at least two and up to all four X 1 , X 2 , X 3 and X 4 are sulfur;

Z is —C m R 2 2m — wherein m=1-4; —C(R 2 ) 2 SC(R 2 ) 2 —, —C(R 2 ) 2 SSC(R 2 ) 2 —, or

—C(R 2 ) 2 OC(R 2 ) 2 ;

n is 1 to 4 in compound of formula I and is from 0 to 4 in compound of formula II; and

M is selected from CH 2 Cl, CH 2 SC(O)R 1 , CH 2 SC(S)R 1 , CH 2 S(CH 2 CH 2 S)qH wherein q is 0, 1 or 2, —CR 2 ═CH 2 , —CH 2 OC(O)CR 2 ═CH 2 , CH 2 N═C═S, CH 2 N═C═O, CH 2 NR 2 H, CH 2 OH, CH 2 SCH 2 CH 2 CR 2 ═CH 2 , phenyl, C(R 2 ) 2 phenyl, furan, thiophene, halogen, C 3 -C 6 cycloalkyl, C 3 -C 6 heretocyclics, thiol,

wherein A is S, O or phenyl and x is 0 or 1;

R 1 is C 1 -C 22 alkyl; and

R 2 is H or C 1 -C 22 alkyl to form a polymer,

forming all or part of the optical lens.

7. The method of claim 6 , wherein in compound of formula II at least two and up to all four of X 1 , X 2 , X 3 and X 4 and at least two and up to all four of four of X 5 , X 6 , X 7 , and X 8 are sulfur.

8. The method of claim 6 , wherein the polymer forms a body of the lens.

9. The method of claim 6 , wherein the polymer forms a coating of the lens.

10. A (co)polymer comprising (co)polymerized monomers of Formula I:

or Formula II:

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 , are independently O or S; and in compound of formula I at least two and up to all four X 1 , X 2 , X 3 and X 4 are sulfur,

Z is —C m R 2 2m — wherein m=1-4; —C(R 2 ) 2 SC(R 2 ) 2 —, —C(R 2 ) 2 SSC(R 2 ) 2 —, or

—C(R 2 ) 2 OC(R 2 ) 2 ;

n is from 1 to 4 in compound of formula I and n is 0 to 4 in compound of formula II; and

M is selected from CH 2 Cl, CH 2 SC(O)R 1 , CH 2 SC(S)R 1 , CH 2 S(CH 2 CH 2 S)qH wherein q is 0, 1 or 2; —CR 2 ═CH 2 , —CH 2 OC(O)CR 2 ═CH 2 , CH 2 N═C═S, CH 2 N═C═O, CH 2 NR 2 H, CH 2 OH, CH 2 SCH 2 CH 2 CR 2 ═CH 2 , phenyl, C(R 2 ) 2 phenyl, furan, thiophene, halogen, C 3 -C 6 cycloalkyl, C 3 -C 6 heretocyclics, thiol;

wherein A is S, O or phenyl and x is 0 or 1;

R 1 is C 1 -C 22 alkyl; and

R 2 is H or C 1 -C 22 alkyl.

11. The (co)polymer of claim 10 , wherein in compound of formula II at least two and up to all four of X 1 , X 2 , X 3 and X 4 and at least two and up to all four of X 5 , X 6 , X 7 and X 8 are sulfur.

12. The (co)polymer of claim 10 , further defined as comprised in an optical lens.

13. A method for preparing a bis-derivative of a spirotetrathiocarbonate or spirooxothiocarbonate, comprising using either one of the following reactions schemes:

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 are independently O or S; n′ is independently 0, 1 or 2;

n is 0 to 4,

Z is —C m R 2 2m — wherein m=1-4; —C(R 2 ) 2 SC(R 2 ) 2 —, —C(R 2 ) 2 SSC(R 2 ) 2 —, —C(R 2 ) 2 OC(R 2 ) 2 —;

M is independently selected from CH 2 Cl, CH 2 SH, CH 2 SC(O)R 1 , CH 2 SC(S)R 1 , CH 2 S(CH 2 CH 2 S)qH wherein q is 0, 1 or 2, —CR 2 ═CH 2 , —CH 2 OC(O)CR 2 ═CH 2 , CH 2 N═C═S, CH 2 N═C═O, CH 2 NR 2 H, CH 2 OH, CH 2 SCH 2 CH 2 CR 2 ═CH 2 , phenyl, C(R 2 ) 2 phenyl, furan, thiophene, halogen, C 3 -C 6 cycloalkyl, C 3 -C 6 heretocyclics, thiol,

wherein A is S, O or phenyl and x is 0 or 1;

R 1 is C 1 -C 22 alkyl; and

R 2 is H or C 1 -C 22 alkyl.

14. The method of claim 13 , comprising reacting a substituted ethylenetrithiocarbonate with a bis-methylthiirane sulfide or a bis-methylthiirane disulfide, in the presence of a catalytic amount of tetrafluoroboric acid to produce the bisSTOC as shown in the reaction below:

wherein M is selected from CR 2 SR′, CR 2 ═CH 2 ,

R═H, C 1 -C 4 alkyl; and

R′═H, acetyl, allyl, acrylate, or methacrylate and

n=1 or 2.

15. The method of claim 13 , comprising reacting a bis-ethylenetrithiocarbonate sulfide or a bis-ethylenetrithiocarbonate, with substituted thiirane in the presence of a catalytic amount of tetrafluoroboric acid to produce the bisSTOC according to the following reaction:

wherein M is CR 2 Cl, CR 2 SR′, or CR 2 ═CH 2 ,

R is H, C 1 -C 4 alkyl,

R′ is H, allyl, acrylate, or methacrylate and

n=1 or 2.

16. The method of claim 13 , comprising reacting a substituted ethylenedithiocarbonate with bis-methylthiirane sulfide or bis-methylthiirane disulfide in the presence of a catalytic amount of tetrafluoroboric acid to produce the compound of formula II according to the reaction:

wherein M=CR 2 SR′, CR 2 ═CH 2 ;

R═H, C 1 -C 4 alkyl;

R′═H, acetyl, allyl, acrylate, or methacrylate; and

n=1 or 2.

17. The method of claim 13 , further defined as a method wherein at least one of bis-ethylenetrithiocarbonate sulfide or bis-ethylenetrithiocarbonate is reacted with a substituted oxirane, in the presence of a catalytic amount of tetrafluoroboric acid to produce the compound of formula II according to the reaction:

wherein M=CR 2 Cl, CR 2 OR′ or CR 2 ═CH 2 ;

R═H, C 1 -C 4 alkyl;

R′═H, allyl, acrylate or methacrylate; and

n=1 or 2.

18. A method of preparing a polythiourethane polymer having a refractive index of 1.5 or greater, comprising reacting at least one polyisocyanate or prepolymer thereof with a compound having formula I or II in claim 1 or a mixture thereof, wherein said compound is further defined as having at least one SH bearing substituent.

19. The method of claim 18 , wherein the at least one polyisocyanate or prepolymer thereof is a diisocyanate or prepolymer thereof.

20. The method of claim 18 , wherein compound of formula I or formula II has at least two SH bearing substituents.

21. The method of claim 18 , further defined as comprising:

preparing a mixture of m-xylylene diisocyanate (m-XDI) and 2,7 bis(mercaptomethyl)-1,4,6,9-tetrathiaspiro[4.4]nonane;

adding a catalyst solution comprising KSCN and a crown-ether; and

curing the mixture at a temperature above 20° C.

22. The method of claim 18 , further defined as comprising:

Dissolving SnBu 2 Cl 2 in m-xylene diisocyanate (m-XDI);

adding 2,7-bis(mercaptomethyl)-1,4,6,9-tetrathiaspiro[4.4] nonane;

stirring; and

curing at a temperature above 30° C.

23. A method of preparing a polymer having a high refractive index which comprises reacting a monomer having at least one unsaturated reactive group or a mixture thereof and/or one or more polyepisulfides with a compound of formula I or formula II of claim 1 having at least one SH bearing substituent(s) or a mixture thereof.

24. The method of claim 23 , wherein the compound of formula I or formula II has at least two SH bearing substituents.

25. A method of preparing a polymer having a high refractive index which comprises reacting a monomer having at least one SH group or a mixture thereof and/or one or more polyepisulfides with a compound of formula I or of formula II of claim 1 having at least one, preferably two episulfide bearing substituent(s) or a mixture thereof.

26. The method of claim 25 , wherein the monomer has at least two SH groups.