Compounds, functionalised dioxaborolane or dioxaborinane derivatives, method for preparing same and uses thereof

Abstract

The invention relates to functionalised dioxaborolane or dioxaborinane derivatives of formula (I), wherein R.sub.1 is covalently bonded to the boron atom by a carbon atom; one of R.sub.2, R.sub.3, R′.sub.3 or R.sub.4 is a radical of formula —X; or one of R.sub.1, R.sub.2, R.sub.3, R′.sub.3 or R.sub.4 is a radical of formula —X; and X is a functionalised radical. The invention relates to the method for preparing same and the uses thereof.

Claims

1. A process for functionalizing a polymer, said process comprising the following steps: a. selecting a linear or branched polymer comprising functions that allow functionalization, b. selecting a molecule allowing the functionalization of the polymer with the molecule, wherein the molecule is a compound of formula (I) ##STR00085## with n=0 or 1, R.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted aryl group selected from a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings linked by a C.sub.1-C.sub.6 alkanediyl group, a pyridine ring, a pyrimidine ring and a triazine ring, R′.sub.3 represents a hydrogen atom R.sub.4 represents a hydrogen atom or a group selected from alkyl, aryl, cycloalkyl, heteroaryl, heteroalkyl and heterocycloalkyl group, R.sub.3 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, R.sub.2, R.sub.3, R.sub.4 are not substituted by a radical of formula (I′), ##STR00086## with n.sub.i=0 or 1 R.sub.2i, R.sub.3i, R′.sub.3i, R.sub.4i, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, R.sub.2, represents a radical of formula —X, X is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, or a methacrylamide, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, a methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.r—Y, where Y is a maleimide, thiol, —NH.sub.2, acrylamide, a methacrylamide, or a terminal alkene radical, r is an integer ranging from 1 to 12; ##STR00087## with Het=—O—CO— or ##STR00088## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00089## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00090## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00091## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00092## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00093## with R.sub.13 is a substituted or unsubstituted hydrocarbon.

2. The process according to claim 1, wherein in the compound of formula (I) the radical R.sub.1 represents aryl group selected from a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings linked by a C.sub.1-C.sub.6 alkanediyl group, a pyridine ring, a pyrimidine ring and a triazine ring, said ring being unsubstituted or substituted from 1 to 3 times.

3. The process according to claim 1, wherein in the compound of formula (I) radical R.sub.1 is substituted by functional groups selected from ester, amide, (meth)acrylate and styrene functions.

4. The process according to claim 1, wherein in the compound of formula (I) radical R.sub.1 is substituted by a halogen, an —Rz, —OH, —NHRz, —NRzR′z, —C(O)—OH, —C(O)—NRzR′z, —C(O)—O—Rz, —O—C(O)—Rz, —O—C(O)—O—Rz, —O—C(O)—N(H)—Rz, —N(H)—C(O)—O—Rz, —O—Rz, —S—Rz, —C(O)—N(H)—Rz, or —N(H)—C(O)—Rz group with Rz, R′z, identical or different, representing a C.sub.1-C.sub.50 alkyl radical.

5. The process according to claim 1, wherein in the compound of formula (I) R.sub.1 represents an unsubstituted benzene ring.

6. The process according to claim 1, wherein in the compound of formula (I) R.sub.4 represents H.

7. The process according to claim 1, wherein in the compound of formula (I) R.sub.3, represents H or —CH.sub.3.

8. The process according to claim 1, wherein in the compound of formula (I) R.sub.5 represents H or an unsubstituted hydrocarbon radical.

9. The process according to claim 1, wherein in the compound of formula (I) R.sub.6 represents a (hetero)alkanediyl, a (hetero)alkenediyl, a (hetero)aryl or a (hetero)cycloalkyl group.

10. The process according to claim 1, wherein in the compound of formula (I) r is an integer ranging from 1 to 4.

11. The process according to claim 1, wherein in the compound of formula (I) m is an integer ranging from 0 to 4.

12. The process according to claim 1, wherein in the compound of formula (I) the radical R.sub.1 is substituted by at least one radical of formula (I′), as defined in claim 1, R.sub.2i represents a radical of formula —X.sub.i, R′.sub.3i=H, X.sub.i is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2)—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00094## with Het=—O—CO— or ##STR00095## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00096## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00097## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00098## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00099## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00100## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical, X.sub.i is selected so that X and X.sub.i both bear the same functional group selected from Y, azide, alkoxysilane, alkoxyamine, azodicarbonyl or nitroxide terminal function.

13. The process according to claim 12, wherein in the compound of formula (I′) n.sub.i=1 and R.sub.4i each represents H.

14. The process according to claim 12, wherein in the compound of formula (I) radicals X and X.sub.i are identical.

15. The process according to claim 1, wherein in the compound of formula (I) the radical R.sub.1 is substituted by at least one radical of formula (I′), as defined in claim 1, R.sub.3i represents a radical of formula —X.sub.i, when n.sub.i=0 than R′.sub.3i represents H, X.sub.i is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.r—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00101## with Het=—O—CO— or ##STR00102## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00103## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00104## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00105## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00106## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00107## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical, X.sub.i is selected so that X and X.sub.i both bear the same functional group selected from Y, azide, alkoxysilane, alkoxyamine, azodicarbonyl or nitroxide terminal function.

16. The process according to claim 15, wherein in the compound of formula (I′) R.sub.2i, R.sub.4i each represents H.

17. The process according to claim 15, wherein in the compound of formula (I′) n.sub.i=1 and R′.sub.3i represents H or —CH.sub.3.

18. The process according to claim 15, wherein in the compound of formula (I) radicals X and X.sub.i are identical.

19. The process according to claim 1, wherein compound of formula (I) is selected from: ##STR00108## ##STR00109## ##STR00110## ##STR00111## m, R.sub.1, R.sub.2, R.sub.21, R.sub.3, R′.sub.3, R.sub.31, R′.sub.31, R.sub.4, R.sub.41, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R″.sub.2, R″.sub.3, R″.sub.4, Het, alk.sub.1, alk.sub.2, alk.sub.3, s and t being as defined in claim 1 with i=1, s′ is 0 or 1, t′ is 0 or 1, s′+t′=1 or 2, Q is a C.sub.1-C.sub.6 alkoxy radical, R.sub.51 has the same definition as that given for R.sub.5 in claim 1, R.sub.61 has the same definition as that given for R.sub.6 in claim 1, R.sub.71 has the same definition as that given for R.sub.7 in claim 1, R.sub.81 has the same definition as that given for R.sub.8 in claim 1, R.sub.91 has the same definition as that given for R.sub.9 in claim 1, R.sub.101 has the same definition as that given for R.sub.10 in claim 1, R.sub.131 has the same definition as that given for R.sub.13 in claim 1, Het.sub.1, Het.sub.2, identical or different, have the same definition as that given for Het in claim 1, alk.sub.11, alk.sub.21, alk.sub.31, identical or different, have the same definition as that given for alk.sub.1, alk.sub.2, alk.sub.3 in claim 1, m.sub.1 has the same definition as that given for m in claim 1.

20. A process for functionalizing a polymer, said process comprising the following steps: a. selecting a linear or branched polymer comprising functions that allow functionalization, b. selecting a molecule allowing the functionalization of the polymer with the molecule, wherein the molecule is a compound of formula (I) ##STR00112## with n=0 or 1, R.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted aryl group selected from a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings linked by a C.sub.1-C.sub.6 alkanediyl group, a pyridine ring, a pyrimidine ring and a triazine ring, R.sub.2, R.sub.4, identical or different, represent a hydrogen atom or a group selected from alkyl, aryl, cycloalkyl, heteroaryl, heteroalkyl and heterocycloalkyl group, R′.sub.3 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, and R′.sub.3 is H when n=0 R.sub.2, R′.sub.3, R.sub.4 are not substituted by a radical of formula (I′), ##STR00113## with n.sub.i=0 or 1 R.sub.2i, R.sub.3i, R′.sub.3i, R.sub.4i, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, R.sub.3 represents a radical of formula —X, X is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.r—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00114## with Het=—O—CO— or ##STR00115## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00116## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00117## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00118## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00119## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00120## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical.

21. The process according to claim 20, wherein in the compound of formula (I) radical R.sub.1 represents aryl group selected from a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings linked by a C1-C6 alkanediyl group, a pyridine ring, a pyrimidine ring and a triazine ring, said ring being unsubstituted or substituted from 1 to 3 times.

22. The process according to claim 20, wherein in the compound of formula (I) radical R1 is substituted by functional groups selected from ester, amide, (meth)acrylate and styrene functions.

23. The process according to claim 20, wherein in the compound of formula (I) radical R1 is substituted by a halogen, an —Rz, —OH, —NHRz, —NRzR′z, —C(O)—OH, —C(O)—NRzR′z, —C(O)—O—Rz, —O—C(O)—Rz, —O—C(O)—O—Rz, —O—C(O)—N(H)—Rz, —N(H)—C(O)—O—Rz, —O—Rz, —S—Rz, —C(O)—N(H)—Rz, or —N(H)—C(O)—Rz group with Rz, R′z, identical or different, representing a C.sub.1-C.sub.50 alkyl radical.

24. The process according to claim 20, wherein in the compound of formula (I) radical R.sub.1 represents an unsubstituted benzene ring.

25. The process according to claim 20, wherein in the compound of formula (I) R.sub.2, R.sub.4, each represents H.

26. The process according to claim 20, wherein in the compound of formula (I) R.sub.5 represents H or an unsubstituted hydrocarbon radical.

27. The process according to claim 20, wherein in the compound of formula (I) R.sub.6 represents a (hetero)alkanediyl, a (hetero)alkenediyl, a (hetero)aryl or a (hetero)cycloalkyl group.

28. The process according to claim 20, wherein in the compound of formula (I) r is an integer ranging from 1 to 4.

29. The process according to claim 20, wherein in the compound of formula (I) m is an integer ranging from 0 to 4.

30. The process according to claim 20, wherein in the compound of formula (I) the radical R.sub.1 is substituted by at least one radical of formula (I′), as defined in claim 20, R.sub.2i represents a radical of formula —X.sub.i, R′.sub.3i=H, X.sub.i is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.r—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00121## with Het=—O—CO— or ##STR00122## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00123## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00124## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00125## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00126## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00127## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical, X.sub.i is selected so that X and X.sub.i both bear the same functional group selected from Y, azide, alkoxysilane, alkoxyamine, azodicarbonyl or nitroxide terminal function.

31. The process according to claim 30, wherein in the compound of formula (I′) n.sub.i=1 and R.sub.4i each represents H.

32. The process according to claim 30, wherein in the compound of formula (I) radicals X and X.sub.i are identical.

33. The process according to claim 20, wherein in the compound of formula (I) the radical R.sub.1 is substituted by at least one radical of formula (I′), as defined in claim 20, R.sub.3i represents a radical of formula —X.sub.i, when n.sub.i=0 than R′.sub.3i represents H, X.sub.i is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide, methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.r—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00128## with Het=—O—CO— or ##STR00129## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00130## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00131## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00132## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00133## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00134## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical, X.sub.i is selected so that X and X.sub.i both bear the same functional group selected from Y, azide, alkoxysilane, alkoxyamine, azodicarbonyl or nitroxide terminal function.

34. The process according to claim 33, wherein in the compound of formula (I′) R.sub.2i, R.sub.4i each represents H.

35. The process according to claim 33, wherein in the compound of formula (I′) n.sub.i=1 and R′.sub.3i represents H or —CH.sub.3.

36. The process according to claim 33, wherein in the compound of formula (I) radicals X and X.sub.i are identical.

37. The process according to claim 20, wherein compound of formula (I) is selected from: ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## m, R.sub.1, R.sub.2, R.sub.21, R.sub.3, R′.sub.3, R.sub.31, R′.sub.31, R.sub.4, R.sub.41, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R″.sub.2, R″.sub.3, R″.sub.4, Het, alk.sub.1, alk.sub.2, alk.sub.3, s and t being as defined in claim 20 with i=1, s′ is 0 or 1, t′ is 0 or 1, s′+t′=1 or 2, preferentially s′+t′=1, Q is a C.sub.1-C.sub.6 alkoxy radical, R.sub.51 has the same definition as that given for R.sub.5 in claim 20, R.sub.61 has the same definition as that given for R.sub.6 in claim 20, R.sub.71 has the same definition as that given for R.sub.7 in claim 20, R.sub.81 has the same definition as that given for R.sub.8 in claim 20, R.sub.91 has the same definition as that given for R.sub.9 in claim 20, R.sub.101 has the same definition as that given for R.sub.10 in claim 20, R.sub.131 has the same definition as that given for R.sub.13 in claim 20, Het.sub.1, Het.sub.2, identical or different, have the same definition as that given for Het in claim 20, alk.sub.11, alk.sub.21, alk.sub.31, identical or different, have the same definition as that given for alk.sub.1, alk.sub.2, alk.sub.3 in claim 20, m.sub.1 has the same definition as that given for m in claim 20.

38. A process for functionalizing a polymer, said process comprises the following steps: a. selecting a linear or branched polymer comprising functions that allow functionalization, b. selecting a molecule allowing the functionalization of the polymer with the molecule, wherein the molecule is a compound of formula (I) ##STR00141## with n=0 or 1, R.sub.2, R.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted group selected from alkyl, aryl, cycloalkyl, heteroaryl, heteroalkyl and heterocycloalkyl group, R.sub.3, R′.sub.3, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, R.sub.2, R.sub.3, R′.sub.3, R.sub.4 are not substituted by a radical of formula (I′), ##STR00142## with n.sub.i=0 or 1 R.sub.2i, R.sub.3i, R′.sub.3i, R.sub.4i, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring, none or one of R.sub.2, R.sub.3, R′.sub.3 or R.sub.4 represents a radical of formula —X, X is selected from: —(CH.sub.2).sub.m—CH(R.sub.5)—Y where Y is a maleimide, thiol, —NH.sub.2, acrylamide or methacrylamide, or a terminal alkene radical, m is an integer ranging from 0 to 12, R.sub.5 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; —(CH.sub.2).sub.m—R.sub.6—Y where Y is as previously defined, m is an integer ranging from 0 to 12, R.sub.6 is a hydrocarbon radical, substituted at least by Y, which may include one or more heteroatoms or halogens; —CH.sub.2).sub.r—Y, where Y is as previously defined, r is an integer ranging from 1 to 12; ##STR00143## with Het=—O—CO— or ##STR00144## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; ##STR00145## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00146## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; ##STR00147## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00148## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″′.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00149## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical, R.sub.1 is covalently linked to the boron atom by a carbon atom and is selected from the group consisting of: ##STR00150## with Het=—O—CO— or ##STR00151## and R.sub.7 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, s is 0 or 1, t is 0 or 1, s+t=1 or 2; or ##STR00152## with alk.sub.1, alk.sub.2, alk.sub.3 each independently representing a linear or branched C.sub.1-C.sub.4 alkyl and R.sub.8 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; or ##STR00153## with R.sub.9 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens and R.sub.10 is a hydrogen atom, or a hydroxyl radical, or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens; or ##STR00154## the double bond is of cis or trans configuration, with R.sub.11 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, Z is a divalent group selected from —O—, —S—, or —NH—, Q is a C.sub.1-C.sub.6 alkoxy radical or ##STR00155## with Z′ is a divalent group selected from —O—, —S—, or —NH—, one of R″.sub.2, R″.sub.3, R″.sub.3, R″.sub.4, R″.sub.1 is missing depending on the substitution site, R.sub.12 is a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, R″.sub.1 is covalently linked to the boron atom by a carbon atom and represents a substituted or unsubstituted hydrocarbon group which may include one or more heteroatoms or halogens, R″.sub.2, R″.sub.3, R″′.sub.3, R″.sub.4, identical or different, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon radical which may include one or more heteroatoms or halogens, or together form, pairwise, an aliphatic or aromatic ring; ##STR00156## with R.sub.13 is a substituted or unsubstituted hydrocarbon radical.

39. The process according to claim 38, wherein in the compound of formula (I) none of R.sub.2, R.sub.3, R′.sub.3 or R.sub.4 represents a radical of formula —X.

40. The process according to claim 38, wherein in the compound of formula (I) R.sub.2, R.sub.3, R′.sub.3 or R.sub.4 each represents H.

41. The process according to claim 38, wherein in the compound of formula (I) R.sub.4 represents X, R.sub.2 represents H.

42. The process according to claim 38, wherein in the compound of formula (I) R.sub.3 represents X, R′.sub.3 represents H.

43. The process according to claim 38, wherein in the compound of formula (I) R.sub.5 represents H or an unsubstituted hydrocarbon radical.

44. The process according to claim 38, wherein in the compound of formula (I) R.sub.6 represents a (hetero)alkanediyl, a (hetero)alkenediyl, a (hetero)aryl or a (hetero)cycloalkyl group.

45. The process according to claim 38, wherein in the compound of formula (I) R.sub.6 represents a (hetero)alkanediyl, a (hetero)alkenediyl, a (hetero)aryl or a (hetero)cycloalkyl group.

46. The process according to claim 38, wherein in the compound of formula (I) r is an integer ranging from 1 to 4.

47. The process according to claim 38, wherein in the compound of formula (I) m is an integer ranging from 0 to 4.

48. The process according to claim 38, wherein said compound of formula (I) is selected from: ##STR00157## ##STR00158## ##STR00159## R.sub.2, R.sub.3, R′.sub.3, R.sub.4, R.sub.7, R.sub.8, R.sub.9, R.sub.11, R.sub.12, R.sub.13, R″.sub.2, R″.sub.3, R″.sub.4, Het, alk.sub.1, alk.sub.2, alk.sub.3, s and t being as defined in claim 38, s′ is 0 or 1, t′ is 0 or 1, s′+t′=1 or 2, Q is a C.sub.1-C.sub.6 alkoxy radical, R.sub.71 has the same definition as that given for R.sub.7 in claim 38, R.sub.81 has the same definition as that given for R.sub.8 in claim 38, R.sub.91 has the same definition as that given for R.sub.9 in claim 38, R.sub.131 has the same definition as that given for R.sub.13 in claim 38, Het.sub.1, Het.sub.2, identical or different, have the same definition as that given for Het in claim 38, alk.sub.11, alk.sub.21, alk.sub.31, identical or different, have the same definition as that given for alk.sub.1, alk.sub.2, alk.sub.3 in claim 38.

Description

EXAMPLES

(1) The following examples illustrate the synthesis of the boronic ester compounds of the invention.

Example 1: Synthesis of a boronic ester Bearing a maleimide Function

(2) Diol bearing a protected maleimide function in the form of furan/maleimide cycloadduct (1)

(3) ##STR00061##
Procedure:

(4) exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride (12 g, 72 mmol) is dissolved in ethanol (150 mL) then an ethanol solution (25 mL) of 3-amino-1,2-propanediol 2 (6.6 g, 72 mmol) is added dropwise to the mixture. The reaction mixture thus obtained is stirred at ethanol reflux for 5 hours. During this step, the reaction medium becomes orange-yellowish. The solution is then brought to a temperature of −5° C. and the crystals thus formed are isolated by filtration then dried under vacuum to give the target product 1 (mass=8.35 g, yield=48%).

(5) Boronic ester Bearing a maleimide Function

(6) ##STR00062##
Procedure:

(7) The diol bearing a protected maleimide function in the form of furan/maleimide cycloadduct (1) (5.5 g, 23.1 mmol) and phenylboronic acid (2.8 g, 23.1 mmol) are dissolved in toluene (80 mL) and the reaction mixture is heated at toluene reflux (oil bath temperature setpoint 130° C.) using a Dean-Stark apparatus to remove water formed during condensation. After 6 hours of reflux, the reaction mixture is cooled to room temperature then the solvent is removed under vacuum. The residue thus obtained is dissolved in ethanol then the mixture is placed in the freezer at −5° C. The yellow crystals thus formed are isolated by filtration then dried under vacuum to give the target boronic ester bearing a maleimide function (mass=4.8 g, yield=81%).

(8) .sup.1H NMR (DMSO-d6, 400 MHz): δ 7.66 (d, 2H, J=8 Hz), 7.51 (t, 1H J=7.2 Hz), 7.40 (t, 2H, J=7.6 Hz), 7.07 (s, 2H), 4.75 (ddt, 1H, 3J2,3a=8 Hz, 3J2,1=6 Hz, 3J2,3b=5.6 Hz), 4.39 (dd, 1H, 2J3a, 3b=9.6 Hz, 3J3a, 2=8 Hz), 4.11 (dd, 1H, 2J3b,3a=9.6 Hz, 3J3b,2 5.6 Hz), 3.67 (d, 2H, 3J1,2=6 Hz).

(9) ##STR00063##

(10) .sup.13C NMR (DMSO-d6, 400 MHz): δ 170.9, 134.6, 134.4, 131.5, 127.8, 74.4, 68.5, 41.3

(11) FT-IR (cm.sup.−1): 3467, 3098, 3082, 3055, 3027, 2973, 2943, 2908, 1701, 1602, 1500, 1481, 1439, 1398, 1363, 1330, 1315, 1216, 1164, 1095, 1071, 1028, 1001, 980, 894, 828, 801, 765, 695, 658, 644

Example 2: Synthesis of a Boronic Ester Bearing Two Maleimide Functions

(12) ##STR00064##
Procedure:

(13) The diol bearing a protected maleimide function in the form of furan/maleimide cycloadduct (1) (4 g, 16.7 mmol) and 1,4-benzenediboronic acid (1.38 g, 8.4 mmol) are dissolved in toluene (70 mL) and the reaction mixture is heated at toluene reflux for 6 hours (oil bath temperature setpoint 130° C.) using a Dean-Stark apparatus to remove water formed during condensation. During this heating period, a white precipitate and a yellow/orangish residue sticking to the flask walls appear. The solution and the white precipitate are separated from the yellow/orangish residue before being concentrated under vacuum. Proton NMR analysis in DMSO-d6 of the crude product indicates complete esterification but incomplete deprotection of the maleimide function. The crude product is re-dissolved in 1,2-dichlorobenzene (50 mL) and heated at 140° C. for 18 hours. The solvent is then removed under vacuum to give the target boronic ester containing two maleimide functions in the form of an off-white solid (mass=2.5 g; yield=69.9%).

(14) .sup.1H NMR (DMSO-d6, 400 MHz): δ 7.65 (s, 4H), 7.06 (s, 4H), 4.74 (ddt, 2H, 3J2,3a=7.6 Hz, 3J2,3b=6 Hz, 3J2,1=5.6 Hz), 4.38 (t, 2H, J=8.8 Hz), 4.1 (dd, 1H, 2J3b, 3a=9.6 Hz, 3J3b, 2=6 Hz), 3.67 (d, 2H, 3J1,2=5.6 Hz).

(15) ##STR00065##

(16) .sup.13C NMR (DMSO-d6, 400 MHz): δ 170.9, 134.6, 132.1, 74.4, 68.5, 41.3

(17) FT-IR (cm.sup.−1): 3456, 3097, 2980, 2950, 2912, 1698, 1519, 1433, 1403, 1357, 1330, 1312, 1206, 1167, 1102, 1064, 1021, 893, 832, 693, 655, 642

Example 3: Synthesis of a boronic ester Bearing a thiol Function

(18) ##STR00066##
Procedure:

(19) Thioglycerol (4.22 g, 39.0 mmol) and phenylboronic acid (5.0 g, 41.0 mmol) are dissolved in toluene (150 mL) and the reaction mixture is heated at toluene reflux (oil bath temperature setpoint 130° C.) using a Dean-Stark apparatus to remove water formed during condensation. After 3 hours of reflux, the reaction mixture is cooled to room temperature then the solvent is removed under vacuum. The residue thus obtained is introduced into pentane and the mixture is placed in the freezer at −18° C. for one hour. The reaction mixture is then filtered, then concentrated under vacuum to give the boronic ester in the form of a colourless oil (mass=3.08 g; yield=40.7%).

(20) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.82 (d, 2H, J=8 Hz), 7.49 (t, 1H, J=7.2 Hz), 7.39 (t, 2H, J=7.6 Hz), 4.73 (ddt, 1H, .sup.3J.sub.2,3a=8 Hz, .sup.3J.sub.2,3b=6.4 Hz, .sup.3J2, =5.6 Hz), 4.48 (dd, 1H, .sup.2J.sub.3a,3b=9.2 Hz, .sup.3J.sub.3a,2=8 Hz), 4.17 (dd, 1H, .sup.2J.sub.3b,3a=9.2 Hz, .sup.3J.sub.3b,2=6.4 Hz), 2.80 (dd, 2H, J=8.8 Hz, .sup.3J.sub.1,2=5.6 Hz), 1.48 (t, 1H, SH, J=8.8 Hz)

(21) ##STR00067##

(22) .sup.13C NMR (CDCl.sub.3, 400 MHz): δ 134.9, 131.6, 127.9, 69.8, 29.7

(23) FT-IR (cm.sup.−1): 3079, 3054, 3027, 2966, 2903, 2578, 1602, 1499, 1477, 1440, 1396, 1367, 1319, 1239, 1157, 1093, 1028, 984, 700, 644.

Example 4: Synthesis of a boronic ester Bearing Two thiol Functions

(24) ##STR00068##
Procedure:

(25) Thioglycerol (1.24 g, 11.5 mmol) and 1,4-benzenediboronic acid (1.0 g, 6.03 mmol) are dissolved in toluene (50 mL) and the reaction mixture is heated at toluene reflux (oil bath temperature setpoint 130° C.) using a Dean-Stark apparatus to remove water formed during condensation. After 3 hours of reflux, the reaction mixture is cooled to room temperature then the solvent is removed under vacuum to give the target boronic ester in the form of a white solid (mass=0.84 g; yield=45%).

(26) 1H NMR (CDCl3, 400 MHz): δ 7.83 (s, 4H), 4.74 (ddt, 2H, 3J2,3a=9.2 Hz, 3J2,3b=6.8 Hz, 3J2,1=5.2 Hz), 4.48 (dd, 2H, 2J3a,3b=9.2 Hz, 3J3a,2=8 Hz), 4.17 (dd, 2H, 2J3b,3a=9.2 Hz, 3J3b,2=6.4 Hz), 2.81 (dd, 4H, J=8.4 Hz, 3J1,2=5.2 Hz), 1.48 (t, 1H, SH, J=8.4 Hz)

(27) ##STR00069##

(28) 13C NMR (CDCl3, 400 MHz): δ 134.1, 77.6, 69.8, 29.7

(29) FT-IR (cm.sup.−1): 3072, 3035, 2961, 2906, 2578, 1515, 1477, 1402, 1385, 1352, 1316, 1215, 1099, 1021, 952, 867, 837, 656

(30) Examples 5 and 6 illustrate the functionalisation of polymers with the boronic ester compounds of the invention containing maleimide functions.

Example 5: Grafting of High-Density Polyethylene (HDPE) with a Boronic Ester Bearing a Maleimide Function (Molecule Described in Example 1

(31) The following example illustrates the possibility of grafting boronic ester functions onto high-density polyethylene by reactive extrusion.

(32) 3.28 g of high-density polyethylene (Sigma Aldrich item number 427985), 0.21 g of boronic ester bearing a maleimide function (molecule described in Example 1) and 13 microlitres of di-tert-butyl peroxide (CAS No. 110-05-4) are mixed at room temperature in a beaker using a spatula.

(33) The mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 200° C. with a screw rotation speed of 100 rpm, and a circulation time of 10 minutes.

(34) The grafting of the boronic ester functions is confirmed by Fourier transform infrared spectroscopy.

(35) To that end, the polymer obtained in the preceding step is dissolved in 1,2-dichlorobenzene by heating to 150° C. until a homogeneous solution is obtained. The polymer is then isolated by precipitation in acetone, then filtration and drying under vacuum until its mass remains constant. This step eliminates boronic esters with a maleimide function that was not grafted during reactive extrusion.

(36) The polymer is then analysed by Fourier transform infrared spectroscopy. This technique confirms the grafting of the boronic ester functions, notably via the presence of a band around 1690-1740 cm.sup.−1, characteristic of the carbonyl function of the maleimide groups of the boronic ester.

Example 6: Grafting and Cross-Linking of High-Density polyethylene (HDPE) with a boronic ester Bearing Two maleimide Functions (Molecule Described in Example 2

(37) The following example illustrates the possibility of grafting boronic ester functions and cross-linking a high-density polyethylene by reactive extrusion.

(38) 2.84 g of high-density polyethylene (Sigma Aldrich item number 547999), 0.121 g of boronic ester bearing two maleimide functions (molecule described in Example 2) and 0.01 g of dicumyl peroxide (CAS No. 80-43-3) are mixed at room temperature in a beaker using a spatula.

(39) The mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 200° C. with a screw rotation speed of 100 rpm, and a circulation time of 5 minutes.

(40) The grafting of the boronic ester functions and the cross-linking of the polyethylene are confirmed by dynamic mechanical analysis (DMA, frequency 1 Hz, maximum strain amplitude ⅙, heating 3° C./min) by monitoring the variations of the storage modulus E′ with temperature.

(41) The high-density polyethylene grafted and cross-linked by a boronic ester bearing two maleimide functions (molecule described in Example 2) has a storage modulus E′ comprised between 4 GPa and 50 MPa between −50° C. and 100° C., and comprised between 2 MPa and 0.4 MPa between 150° C. and 250° C. By comparison, the high-density polyethylene from Sigma Aldrich (item number 547999) also has a storage modulus E′ comprised between 4 GPa and 50 MPa between −50° C. and 100° C. However, the storage modulus E′ of the high-density polyethylene from Sigma Aldrich (item number 547999) drops below 2 Pa above 140° C. This value corresponds to a spreading of the material under its own weight and does not allow an analysis of the material by DMA above 140° C.

Example 7: Synthesis of a boronic ester Bearing a Terminal alkene Function

(42) Diol Bearing a Terminal Alkene Function, A1

(43) ##STR00070##
Procedure:

(44) 1,2-Epoxy-5-hexene (3.00 g, 30.6 mmol, 1 eq.) is added to an aqueous sodium hydroxide solution (61.0 mL, 2M, 4 eq.) and the reaction mixture is heated at 50° C. for 24 hours. Once the reaction mixture has returned to room temperature, the reaction is neutralised by adding an aqueous hydrochloric acid solution (1M). The reaction mixture is extracted with ethyl acetate. The organic phases are combined, washed with water before being dried over magnesium sulphate. The solvent is removed under vacuum and the product is purified by silica column chromatography using a 50 vol %/50 vol % ethyl acetate/hexane mixture as eluent. The diol bearing a terminal alkene function, A1, is thus obtained in the form of a colourless liquid (1.60 g, yield=46%).

(45) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ (ppm): 5.83 (m, 1H), 5.01 (m, 2H), 3.76-3.68 (m, 1H), 3.66-3.6 (m, 1H), 3.47-3.40 (m, 1H), 2.79 (d, 1H, J=4.40 Hz), 2.72 (t, 1H, J=5.67 Hz), 2.27-2.06 (m, 2H), 1.60-1.45 (m, 2H)

(46) .sup.13C NMR (CDCl3, 100 MHz): δ (ppm): 138.04, 114.99, 71.70, 66.61, 32.07, 29.74.

(47) Boronic Ester Bearing a Terminal Alkene Function A2

(48) ##STR00071##
Procedure:

(49) The diol bearing a terminal alkene function A1 (1.60 g, 13.77 mmol, 1 eq.) is dissolved in 10 mL of tetrahydrofuran (THF). Phenylboronic acid (1.76 g, 14.46 mmol, 1.05 eq.) is added to the reaction medium followed by 0.5 mL of water. The reaction mixture is stirred 20 minutes at room temperature before magnesium sulphate (about 5 g) is added. The reaction mixture is then stirred 16 h at room temperature, before being filtered. The solvent is then evaporated under vacuum to give the boronic ester bearing a terminal alkene function, A2, in the form of a colourless liquid (2.60 g, 94%).

(50) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ (ppm): 7.80 (m, 2H), 7.50-7.45 (m, 1H), 7.41-7.35 (m, 2H), 5.86 (m, 1H), 5.12-4.98 (m, 2H), 4.65-4.55 (m, 1H), 4.44 (dd, 1H, J=8.9 Hz, J=7.8 Hz), 3.97 (dd, 1H, J=8.9 Hz, J=7.0 Hz), 2.35-2.15 (m, 2H), 1.90-1.65 (m, 2H)

(51) .sup.13C NMR (CDCl3, 100 MHz): δ (ppm): 137.53, 134.78, 131.37, 127.76, 115.19, 76.85, 71.07, 35.31, 29.23.

Example 8: Synthesis of a boronic ester Bearing an azide Function

(52) Example of a Reaction Scheme for Preparing a boronic ester Bearing an azide Function

(53) ##STR00072##
Synthesis of Compound B1

(54) ##STR00073##
Procedure:

(55) 10 drops of BF.sub.3.Math.Et.sub.2O are added to 50 mL of anhydrous acetone at room temperature. Epibromohydrin (20.0 g, 146 mmol) is then added dropwise to the reaction medium at room temperature, then the reaction medium is stirred at room temperature for 15 hours. Compound B1 is then isolated by distillation under vacuum. 23.0 g (yield=82%) of a colourless liquid is thus obtained.

(56) .sup.1H NMR (CDCl3, 400 MHz): δ (ppm): 4.33 (m, 1H), 4.11 (ddd, 1H, J=8.7 Hz, J=6.1 Hz, J=0.6 Hz), 3.85 (dd, 1H, J=8.7 Hz, J=5.1 Hz), 3.40 (ddd, 1H, J=10.0 Hz, J=4.7 Hz, J=0.6 Hz), 3.29 (dd, 1H, J=10.0 Hz, J=8.1 Hz), 1.42 (s, 3H), 1.33 (s, 3H).

(57) Synthesis of Compound 12

(58) ##STR00074##
Procedure:

(59) KOH (40.27 g, 717.7 mmol, 20 eq.) is introduced into a hydroquinone solution (11.85 g, 107.7 mmol, 3 eq.) in 150 mL of dimethylsulphoxide (DMSO). Compound B1 (7.00 g, 35.89 mmol, 1 eq.) is then added dropwise at room temperature to the reaction mixture. After 3 days of stirring at room temperature, the reaction is neutralised by adding ammonium bicarbonate. Water is added to the reaction mixture which is then extracted with chloroform. The organic phases are combined, washed with water before being dried over MgSO.sub.4. The solvent is evaporated under vacuum and the crude reaction product is purified by silica column chromatography using chloroform then ether as eluents. Compound B2 (0.94 g, yield=12%) is thus obtained in the form of a colourless liquid.

(60) .sup.1H NMR (DMSO-d.sub.6, 400 MHz): δ (ppm): 8.91 (s, 1H), 6.76 (m, 2H), 6.66 (m, 2H), 4.34 (m, 1H), 4.06 (dd, 1H, J=8.3 Hz, J=6.6 Hz), 3.87 (m, 2H), 3.71 (dd, 1H, J=8.3 Hz, J=6.3 Hz), 1.34 (s, 3H), 1.29 (s, 3H).

(61) Synthesis of Compound B3

(62) ##STR00075##
Procedure:

(63) A solution of B2 (1.06 g, 4.72 mmol, 1 eq.) in 2.5 mL of dichloromethane (DCM) is added dropwise at 0° C. to a triphosgene solution (0.50 g, 1.69 mmol, 0.36 eq.) in 5 mL of DCM. A pyridine solution (0.37 g, 4.70 mmol, 1 eq.) in 2.5 mL of DCM is then added dropwise at 0° C. to the reaction mixture. Once returned to room temperature, the reaction mixture is stirred for an additional 20 h, still at room temperature, while monitoring the reaction by thin layer chromatography. The solvent is evaporated under vacuum to give compound B3 which is stored under inert atmosphere before being used as such to prepare compound B4.

(64) .sup.1H NMR (DMSO-d.sub.6, 400 MHz): δ (ppm): 6.74 (m, 2H), 6.68 (m, 2H), 4.34 (m, 2H), 4.06 (dd, 1H, J=8.3 Hz, J=6.6 Hz), 3.86 (m, 2H), 3.71 (dd, 2H, J=8.3 Hz, J=6.4 Hz), 1.34 (s, 3H), 1.29 (s, 3H).

(65) Synthesis of Compound B4

(66) ##STR00076##
Procedure:

(67) A solution of compound B3 (1.35 g, 4.72 mmol, 1 eq.) in 10 mL of acetone is added dropwise at 0° C. to a sodium azide solution (0.46 g, 7.12 mmol, 1.5 eq.) in 5 mL of water. Once returned to room temperature, the reaction mixture is stirred for an additional 16 h. The reaction mixture is then extracted with ethyl acetate. The organic phases are combined, washed with water then dried over MgSO.sub.4. The solvent is evaporated under vacuum and the crude reaction product is purified by silica column chromatography using diethyl ether as eluent. Compound B4 (0.60 g, yield=43%) is thus obtained in the form of a colourless liquid.

(68) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ (ppm): 7.08 (m, 2H), 6.91 (m, 2H), 4.47 (m, 1H), 4.16 (dd, 1H, J=8.5 Hz, J=6.4 Hz), 4.04 (dd, 1H, J=9.4 Hz, J=5.4 Hz), 3.92 (dd, 1H, J=9.4 Hz, J=5.8 Hz), 3.89 (dd, 1H, J=8.5 Hz, J=5.8 Hz), 1.46 (s, 3H), 1.40 (s, 3H).

(69) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ (ppm): 156.74, 156.59, 144.47, 121.77, 115.23, 109.81, 73.88, 69.22, 66.73, 26.75, 25.31.

(70) Synthesis of Compound B5

(71) ##STR00077##
Procedure:

(72) Compound B4 (250 mg, 0.85 mmol) is dissolved in 10 mL of THF at room temperature then 10 mL of 1M aqueous hydrochloric acid solution is added dropwise. The reaction mixture is stirred 48 h at room temperature before being extracted with DCM. The organic phases are combined, dried over MgSO.sub.4, then the solvent is evaporated under vacuum to give compound B5 (190 mg, yield=88%) in the form of a white solid.

(73) .sup.1H NMR (DMSO-d.sub.6, 400 MHz): δ (ppm): 7.18 (m, 2H), 6.98 (m, 2H), 4.95 (d, 1H, J=5.1 Hz), 4.66 (t, 1H, J=5.7 Hz), 4.00 (dd, 1H, J=9.8 Hz, J=4.1 Hz), 3.86 (dd, 1H, J=9.8 Hz, J=6.1 Hz), 3.79 (m, 1H), 3.44 (t, 2H, J=5.7 Hz).

(74) .sup.13C NMR (DMSO-d.sub.6, 100 MHz): δ (ppm): 156.85, 155.91, 143.67, 122.00, 115.04, 69.94, 69.79, 62.54, 39.43.

(75) Synthesis of the boronic ester Bearing an azide Function, B6

(76) ##STR00078##
Procedure:

(77) Compound B5 (0.51 g, 2.01 mmol, 1 eq.) is dissolved in 5 mL of THF. Phenylboronic acid (257 mg, 2.11 mmol, 1.05 eq.), then 0.5 mL of water, are added to the reaction mixture which is then stirred at room temperature 20 min. MgSO.sub.4 (728 mg, 3 eq.) is added to the reaction medium which is stirred at room temperature for an additional 16 hours. The reaction medium is filtered, then the solvent is removed under vacuum to give the boronic ester bearing an azide function B6 (0.58 g, yield=85%) in the form of a white solid.

(78) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ (ppm): 7.84 (m, 2H), 7.50 (m, 1H), 7.40 (m, 2H), 7.09 (m, 2H), 6.93 (m, 2H), 4.93 (m, 1H), 4.52 (dd, 1H, J=9.2 Hz, J=8.1 Hz), 4.32 (dd, 1H, J=9.2 Hz, J=6.3 Hz), 4.15 (dd, 1H, J=9.8 Hz, J=4.6 Hz), 4.09 (dd, 1H, J=9.8 Hz, J=5.2 Hz).

(79) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ (ppm): 156.68, 156.57, 144.58, 134.88, 131.62, 127.95, 127.83, 121.82, 115.36, 75.22, 70.00, 68.24.

Example 9: Synthesis of a boronic ester Bearing a nitroxide Function

(80) Example of a Reaction Scheme for Preparing a boronic ester Bearing a nitroxide Function

(81) ##STR00079##
Synthesis of Compound C1

(82) ##STR00080##
Procedure:

(83) Epichlorohydrin (20.68 g, 223.5 mmol, 5.5 eq.) is added dropwise at room temperature to an aqueous sodium hydroxide solution (35 mL, 50%). Tetrabutylammonium hydrogen sulphate (0.69 g, 2.0 mmol, 0.05 eq.) is added before 4-hydroxy-TEMPO (7.00 g, 40.6 mmol, 1 eq.) is introduced into the reaction mixture under rapid stirring. The reaction medium is stirred for an additional 24 hours at room temperature before being extracted with diethyl ether. The organic phases are combined, washed with brine, dried over MgSO.sub.4, filtered then concentrated under vacuum. The crude reaction product is then purified by silica column chromatography using a 95/5 vol/vol DCM/MeOH mixture as eluent. Compound C1 (7.13 g, yield=77%) is thus obtained in the form of a red oil.

(84) .sup.1H NMR (CDCl.sub.3 in the presence of phenylhydrazine, 400 MHz): δ (ppm): 7.19-7.13 (m), 6.76-6.70 (m), 3.65 (dd, 1H, J=11.1 Hz, J=3.1 Hz), 3.57 (tt, 1H, J=11.1 Hz, J=4.1 Hz), 3.33 (dd, 1H, J=11.1 Hz, J=5.8 Hz), 3.05 (m, 1H), 2.71 (dd, 1H, J=5.0 Hz, J=4.1 Hz), 2.53 (dd, 1H, J=5.0 Hz, J=2.7 Hz), 1.86 (m, 2H), 1.40 (m, 2H), 1.14 (s, 6H), 1.08 (s, 6H)

(85) .sup.13C NMR (CDCl.sub.3 in the presence of phenylhydrazine, 100 MHz): δ (ppm): 151.04, 129.11, 128.23, 119.36, 112.05, 71.10, 68.87, 59.46, 50.99, 44.38, 31.79, 20.60.

(86) Synthesis of Compound C2

(87) ##STR00081##
Procedure:

(88) A solution of compound C1 (3.50 g, 15.33 mmol, 1.0 eq.) in 5 mL of THF is added to an aqueous sodium hydroxide solution (30.0 mL, 2M, 4.0 eq.). The reaction mixture is heated at 50° C. under stirring for 24 hours. After the reaction medium has returned to room temperature, the reaction is neutralised by adding a 1M aqueous hydrochloric acid solution. The reaction mixture is extracted with dichloromethane. The organic phases are combined, washed with water, dried over MgSO.sub.4 then filtered. The solvent is evaporated under vacuum and the crude reaction product is purified by silica column chromatography using a 95/5 vol/vol CDCl.sub.3/MeOH mixture as eluent. Compound C2 (2.05 g, yield=54%) is thus obtained in the form of a red oil.

(89) .sup.1H NMR (CDCl.sub.3 in the presence of phenylhydrazine, 400 MHz): δ (ppm): 7.16-7.11 (m), 6.75-6.69 (m), 3.74 (s, 1H), 3.60 (dd, 1H, J=11.5 Hz, J=3.5 Hz), 3.55-3.49 (m, 2H), 3.45-3.40 (m, 2H), 1.90-1.80 (m, 2H), 1.45-1.35 (m, 2H), 1.13 (s, 6H), 1.06 (s, 6H).

(90) .sup.13C NMR (CDCl.sub.3 in the presence of phenylhydrazine, 100 MHz): δ (ppm): 124.08, 66.89, 66.75, 65.85, 65.28, 56.39, 39.64, 27.13, 16.81, 16.78.

(91) Synthesis of the boronic ester Bearing a nitroxide Function, C3

(92) ##STR00082##
Procedure:

(93) Compound C2 (0.34 g, 1.38 mmol, 1 eq.) is dissolved in 5 mL of THF. Phenylboronic acid (177 mg, 1.45 mmol, 1.05 eq.), then 0.5 mL of water, are added to the reaction mixture which is then stirred at room temperature for 20 min. MgSO.sub.4 (498 mg, 3 eq.) is added to the reaction medium which is stirred at room temperature for an additional 16 hours. The reaction medium is filtered, then the solvent is removed under vacuum to give the boronic ester bearing a nitroxide function C3 (0.39 g, yield=85%) in the form of a red oil.

(94) .sup.1H NMR (CDCl.sub.3, in the presence of phenylhydrazine 400 MHz): δ (ppm): 7.80-7.70 (m, 2H), 7.41-7.35 (m, 1H), 7.31-7.25 (m, 2H), 4.64-4.55 (m, 1H), 4.30 (dd, 1H, J=9.1 Hz, J=8.2 Hz), 4.07 (dd, 1H, J=9.1 Hz, J=6.4 Hz), 3.62-3.52 (m, 2H), 3.47 (dd, 1H, J=10.2 Hz, J=5.1 Hz), 1.95-1.75 (m, 2H), 1.50-1.35 (m, 2H), 1.20-1.00 (m, 12H).

(95) .sup.13C NMR (CDCl.sub.3, in the presence of phenylhydrazine 100 MHz): δ (ppm): 156.03, 134.79, 131.50, 129.50, 128.28, 127.78, 120.20, 115.40, 76.23, 71.19, 70.17, 68.30, 62.64, 43.01, 21.70.

(96) Examples 10 and 11 illustrate the functionalisation of polymers with the boronic ester compounds of the invention containing nitroxide functions.

Example 10: Grafting of polybutadiene with a boronic ester Bearing a nitroxide Function (Molecule C3 Described in Example 9

(97) The following example illustrates the possibility of grafting boronic ester functions onto a polybutadiene by reactive extrusion.

(98) Polybutadiene (Arlanxeo, item number Buna CB24, 96% cis, 87.7% by mass of the total mixture), the boronic ester bearing a nitroxide function (molecule C3 described in Example 9, 8.4% by mass of the total mixture) and lauryl peroxide (CAS No. 105-74-8, 3.9% by mass of the total mixture) are mixed at room temperature in a beaker using a spatula.

(99) 3 g of the mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 110° C. with a screw rotation speed of 100 rpm, and a circulation time of 10 minutes. The extrudate thus obtained is dissolved in anhydrous dichloromethane then precipitated in anhydrous methanol to remove the boronic ester bearing a nitroxide function C3 that has not been chemically grafted onto the polybutadiene. The polymer thus obtained is dried under vacuum overnight before being analysed by Fourier transform infrared spectroscopy. This analysis confirms the grafting of the boronic ester functions, notably via the presence of a band at 1097 cm.sup.−1, characteristic of the boronic ester bearing a nitroxide function C3.

Example 11: Grafting of High-Density polyethylene (HDPE) with a boronic ester Bearing a nitroxide Function (Molecule C3 Described in Example 9

(100) The following example illustrates the possibility of grafting boronic ester functions onto a polyethylene by reactive extrusion.

(101) High-density polyethylene (Sigma Aldrich item number 427985, 89.8% by mass of the total mixture), the boronic ester bearing a nitroxide function (molecule C3 described in Example 9, 7.7% by mass of the total mixture) and dicumyl peroxide (CAS No. 80-43-3, 2.5% by mass of the total mixture) are mixed at room temperature in a beaker using a spatula.

(102) 3 g of the mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 170° C. with a screw rotation speed of 100 rpm, and a circulation time of 10 minutes. The extrudate thus obtained is dissolved with heating in ortho-dichlorobenzene then precipitated in anhydrous acetone to remove the boronic ester bearing a nitroxide function C3 that was not chemically grafted onto the high-density polyethylene. The polymer thus obtained is dried under vacuum overnight before being analysed by Fourier transform infrared spectroscopy. This analysis confirms the grafting of the boronic ester functions, notably via the presence of a band at 1097 cm.sup.−1, characteristic of the boronic ester bearing a nitroxide function C3.

(103) Example 12 illustrates the functionalisation of polyisoprene with the boronic ester compounds of the invention containing azide functions.

Example 12: Grafting of polyisoprene with a boronic ester Bearing an azide Function (Molecule B6 Described in Example 8

(104) The following example illustrates the possibility of grafting boronic ester functions onto a polyisoprene by reactive extrusion.

(105) Polyisoprene (Zeon, item number IR2200, 97.6% by mass of the total mixture) and the boronic ester bearing an azide function (molecule B6 described in Example 8, 2.4% by mass of the total mixture) are mixed at room temperature in a beaker using a spatula.

(106) 3 g of the mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 120° C. with a screw rotation speed of 100 rpm, and a circulation time of 20 minutes. The extrudate thus obtained is dissolved in anhydrous chloroform then precipitated in anhydrous methanol to remove the boronic ester bearing an azide function B6 that was not chemically grafted onto the polyisoprene. The polymer thus obtained is dried under vacuum overnight before being analysed by proton NMR. This analysis confirms the grafting of the boronic ester functions, notably via the presence of peaks between 6.80 and 7.90 ppm, characteristic of the two aromatic rings of the boronic ester bearing an azide function, B6, as well as peaks between 4.0 and 4.6 ppm, characteristic of the dioxaborolane function of the boronic ester bearing an azide function, B6.

(107) Example 13 illustrates the functionalisation of polydimethylsiloxane containing thiol functions with boronic ester compounds of the invention containing alkene functions.

Example 13: Grafting of poly[(mercaptopropyl)methylsiloxane]dimethylsiloxane Copolymer with a boronic ester Bearing an alkene Function (Molecule A2 Described in Example 7

(108) The following example illustrates the possibility of grafting boronic ester functions onto a polydimethylsiloxane containing thiol functions by light irradiation.

(109) The polydimethylsiloxane containing thiol functions (poly[(mercaptopropyl)methylsiloxane]dimethylsiloxane, Gelest, item number SMS-142, 73.7% by mass of the total mixture), the boronic ester bearing an alkene function (molecule A2 described in Example 7, 25.4% by mass of the total mixture) and 2,2-dimethoxy-2-phenylacetophenone (CAS No. 24650-42-8, 0.9% by mass of the total mixture) are mixed at room temperature in a beaker using a spatula.

(110) This mixture is then spread in a petri dish to obtain a film with a thickness of between 1 and 3 mm. This film is then placed under UV irradiation (365 nm, 15 mW.Math.cm.sup.−2) for 5 minutes at room temperature.

(111) The polymer thus obtained is then analysed by proton NMR. This analysis confirms the grafting of the boronic ester functions, notably via the complete disappearance of peaks comprised between 4.90 and 5.90 ppm, corresponding to the alkene function of the boronic ester bearing an alkene function, A2, and the presence of peaks between 7.0 and 8.0 ppm, characteristic of the aromatic ring of the boronic ester bearing an alkene function, A2, as well as peaks between 3.9 and 4.7 ppm, characteristic of the dioxaborolane function of the boronic ester bearing an alkene function, A2.

(112) Example 14 below illustrates the functionalisation of high-density polyethylene with the boronic ester compounds of the invention containing maleimide functions.

Example 14: Grafting of High-Density polyethylene (HDPE) with a boronic ester Bearing a maleimide Function (Molecule Described in Example 1

(113) The following example illustrates the possibility of grafting boronic ester functions onto high-density polyethylene by reactive extrusion.

(114) High-density polyethylene (Sigma Aldrich item number 427985, 95.95% by mass of the total mixture), the boronic ester bearing a maleimide function (molecule described in Example 1, 4.0% by mass of the total mixture) and dicumyl peroxide (CAS No. 80-43-3, 0.05% by mass of the total mixture) are mixed at room temperature in a beaker using a spatula.

(115) 3 g of the mixture thus obtained is placed in a DSM Micro 5 cc twin-screw extruder. Extrusion is carried out at 170° C. with a screw rotation speed of 100 rpm, and a circulation time of 8 minutes.

(116) The grafting of the boronic ester functions is confirmed by Fourier transform infrared spectroscopy.

(117) To that end, the polymer obtained in the preceding step is dissolved in 1,2-dichlorobenzene by heating to 150° C. until a homogeneous solution is obtained. The polymer is then isolated by precipitation in anhydrous acetone, then filtration and drying under vacuum until its mass remains constant. This step eliminates boronic esters with a maleimide function that were not grafted during reactive extrusion.

(118) The polymer is then analysed by Fourier transform infrared spectroscopy. This analysis confirms the grafting of the boronic ester functions, notably via the presence of a band around 1690-1740 cm.sup.−1, characteristic of the carbonyl function of the maleimide groups of the boronic ester.

(119) Example 15 below illustrates the functionalisation of polybutadiene with the boronic ester compounds of the invention containing thiol functions.

Example 15: Grafting of polybutadiene with a boronic ester Bearing a thiol Function (Molecule Described in Example 3

(120) The following example illustrates the possibility of grafting boronic ester functions onto a polybutadiene containing predominantly repeating units obtained by 1,2-addition.

(121) Polybutadiene (Sigma-Aldrich, item number 466867, about 90/a 1,2-vinyl repeat units, 0.5 g, 7.57 mmol), the boronic ester bearing a thiol function (molecule described in Example 3) (0.147 g, 0.7 mmol) and AIBN (0.004 g, 0.0034 mmol) are dissolved in 3 mL of anisole. The reaction mixture is placed under argon atmosphere by bubbling argon for 30 min at room temperature. The reaction medium is then heated at 100° C. for 45 min while being maintained under argon atmosphere. Once the reaction mixture returns to room temperature, the polymer is precipitated in anhydrous methanol to remove the boronic ester bearing a thiol function (molecule described in Example 3) that was not chemically grafted onto the polybutadiene. The polymer thus obtained is dried under vacuum overnight before being analysed by proton NMR. This analysis confirms the grafting of the boronic ester functions, notably via the presence of peaks between 7.0 and 8.0 ppm, characteristic of the aromatic ring of the boronic ester bearing a thiol function (molecule described in Example 3), as well as peaks between 3.9 and 4.7 ppm, characteristic of the dioxaborolane function of the boronic ester bearing a thiol function (molecule described in Example 3).

Example 16: Synthesis of a boronic ester Bearing a maleimide Function

(122) 1,3-Diol Bearing a Protected maleimide Function in the Form of furan/maleimide Cycloadduct (D1)

(123) ##STR00083##
Procedure:

(124) exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (1.82 g, 11 mmol) and serinol (1 g, 11 mol) are dissolved in 50 mL of methanol. The reaction mixture thus obtained is stirred at methanol reflux for 48 hours during which a small amount of an orange precipitate is formed. Once the reaction mixture has returned to room temperature, the orange precipitate is removed by filtration then the solvent is evaporated under vacuum to give compound D1 in the form of a colourless liquid. The structure of compound D1 is confirmed by .sup.1H NMR and this product is used as such to prepare compound D2.

(125) Boronic ester Bearing a maleimide Function (D2)

(126) ##STR00084##
Procedure:

(127) The diol bearing a protected maleimide function in the form of furan/maleimide cycloadduct (D1) (2.63 g, 11 mmol) and phenylboronic acid (1.34 g, 23.1 mmol) are dissolved in 40 mL of toluene and the reaction mixture is heated at toluene reflux (oil bath temperature setpoint 130° C.) using a Dean-Stark apparatus to remove water formed during condensation. After 7 hours of reflux, the reaction mixture is cooled to room temperature, decanted to remove the yellow/orange solid that formed during the 7 hours of reflux, then the solvent is removed under vacuum. The residue thus obtained is dissolved in ethanol and the mixture is placed in the freezer at −5° C. The white crystals thus formed are isolated by filtration then dried under vacuum to give the target boronic ester bearing a maleimide function D2 (mass=1.03 g, yield=35% on the two steps of synthesis of D1 and D2).

(128) .sup.1H NMR (CDCl3, 400 MHz): δ 7.79 (m, 2H), 7.40 (m, 3H), 6.73 (s, 2H), 4.58 (m, 3H), 4.14 (m, 2H).