LOW TEMPERATURE SYNTHESIS OF CARBONYL-CONTAINING MOLECULES BY DEPOLYMERIZATION OF BISPHENOL A-BASED POLYCARBONATES

Abstract

The present invention refers to a process for preparing carbonyl-containing compounds of formula (Ia), (Ib) or (Ic):

##STR00001##

from Bisphenol A-based Polycarbonate and appropriate nucleophiles in the presence of imidazole or a derivative thereof as catalyst and an organic solvent.

Claims

1. A process for preparing carbonyl-containing compounds of formula (Ia), (Ib) or (Ic): ##STR00037## wherein: X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, S, and N(R.sub.11); R.sub.1-R.sub.11 and X.sub.1 are independently selected from: hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; C.sub.5-C.sub.10 cycloalkyl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; C.sub.5-C.sub.10 heterocyclyl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; C.sub.6-C.sub.10 aryl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; C.sub.5-C.sub.10 heteroaryl optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.7)cycloalkyl (C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl (C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; Y is a single bond or a group (CH.sub.2).sub.pO(CH.sub.2).sub.q, wherein indexes p and q are independently selected from 0, 1 and 2; n is 0 or 1; comprising the reaction of BPA-PC of formula (II): ##STR00038## wherein; m is between 10 and 1000 with a compound of formula (IIIa), (IIIb) or (IIIc): ##STR00039## wherein X.sub.1, X.sub.2, X.sub.3, X.sub.4, R.sub.1-R.sub.10, Y, Z.sub.1 and n are as defined above; in the presence of a catalyst selected from imidazole, 1,2,3-triazole, 1,2,4-triazole, benzimidazole and 1H-benzotriazole; and in the presence of an organic solvent, and wherein the process is carried out at a temperature from 25 to 60 C.

2. The process according to claim 1, wherein X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH and N(C.sub.6 aryl) wherein the aryl is optionally substituted with at least one halogen or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

3. The process according to claim 2, wherein X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are O.

4. The process according to claim 1, wherein R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

5. The process according to claim 1, wherein R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

6. The process according to claim 1, wherein in the compound of formula (Ia) n is 0.

7. The process according to claim 6, wherein R.sub.1, R.sub.2 and R.sub.3 are hydrogen; and R.sub.4 is hydrogen or a C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

8. The process according to aclaim 1, wherein in the compound of formula (Ia) n is 1.

9. The process according to claim 8, wherein R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are hydrogen and R.sub.3 and R.sub.4 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

10. The process according to claim 8, wherein R.sub.3 and R.sub.4 are hydrogen; and R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are independently selected from hydrogen and C.sub.1-C.sub.6 alkyl.

11. The process according to claim 1, wherein in the compounds of formula (Ib), n is 0; R.sub.1, R.sub.3, R.sub.4 and R.sub.7 are hydrogen; and R.sub.2 and R.sub.8 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group.

12. The process according to claim 1, wherein in the compounds of formula (Ib), n is 1; R.sub.1-R.sub.10 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group.

13. The process according to claim 1, wherein in the compound of formula (Ic), X.sub.1 is O or NH.

14. The process according to claim 1, wherein Z.sub.1 is a C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

15. The process according to claim 13, wherein X.sub.1 is O and Z.sub.1 is a C.sub.1-C.sub.4 alkyl.

16. The process according to claim 13, wherein X.sub.1 is NH and Z.sub.1 is a C.sub.6-C.sub.10 aryl optionally substituted with at least a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

17. The process according to claim 1, wherein the organic solvent is selected from 1-methyl imidazole, tetrahydrofuran, chloroform and 1-methyl tetrahydrofuran.

18. The process according to claim 1, which is carried out at a temperature from 30 to 50 C.

19. The process according to claim 3, wherein R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

20. The process according to claim 4, wherein R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; or in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0052] In the context of the present invention, the following terms found in the described formulas have the meaning indicated below:

[0053] The term alkyl refers to a group formed by a linear or branched hydrocarbon chain consisting of carbon and hydrogen atoms, which contains no unsaturation and is linked to the rest of the molecule through a single bond. Specific examples include, without limitation, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, etc. C.sub.1-C.sub.6 and C.sub.1-C.sub.4 alkyl, when mentioned, refer to said group having between 1 and 6 carbon atoms, and between 1 and 4 carbon atoms, respectively.

[0054] The term C.sub.2-6 alkenyl refers to a linear or branched hydrocarbon chain consisting of carbon and hydrogen atoms having at least one double bond, and from 2 to 6 carbon atoms. In a preferred embodiment, they refer to linear hydrocarbons having a single double bond.

[0055] The term C.sub.5-10 cycloalkyl refers to a saturated or partially saturated mono- or bicyclic aliphatic group having between 3 and 7, preferably between 3 and 6 carbon atoms (C.sub.3-C.sub.6 cycloalkyl), which is bound to the rest of the molecule by means of a single bond, including for example and in a non-limiting sense, cyclopropyl, cyclohexyl or cyclopentyl.

[0056] The term C.sub.5-C.sub.10 heterocyclyl refers to a monocyclic or bicyclic system which can be partially or fully saturated containing 5 to 10, preferably 5 or 6, ring atoms containing one or more, specifically one, two or three ring heteroatoms independently selected from N, O, and S, preferably one or two, and the remaining ring atoms being carbon. Examples of heterocyclyl groups include, but are not limited to, pyrrolidine, piperidine, tetrahydropyridine, piperazine, morpholine, thiomorpholine, azepane, diazepane, tetrahydrofuran, tetrahydropyran, octahydro-pyrrolopyrazine.

[0057] The term C.sub.6-10 aryl refers to an aromatic group having between 6 and 10, more preferable having 6 carbon atoms, comprising 1 or 2 aromatic nuclei, including for example and in a non-limiting sense, phenyl, biphenyl or naphthyl. Preferably, aryl refers to phenyl (Ph) or biphenyl.

[0058] The term C.sub.5-C.sub.10 heteroaryl refers to a monocyclic or bicyclic system which is aromatic and contains 5 to 10, preferably 5 or 6, ring atoms containing one or more, specifically one, two or three ring heteroatoms independently selected from N, O, and S, preferably one or two, and the remaining ring atoms being carbon. Examples of such heteroaryl include, but are not limited to, thiophene, furan, pyrrole, thiazole, oxazole, isothiazole, isoxazole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, tetrazole, tetrazole oxide, oxadiazolone, pyridine, pyrimidine, pyrazine, dihydroindolone, benzimidazole, isoindole, benzothiazole, benzofuran, indole, purine, quinolone, isoquinoline.

[0059] The term (C.sub.5-C.sub.10)cycloalkyl(C.sub.1-C.sub.4)alkyl, refers to a C.sub.5-C.sub.10 cycloalkyl group as defined above which is attached to the rest of the molecule through a C.sub.1-C.sub.4 alkyl group as defined above. Preferably, the (C.sub.1-C.sub.4)alkyl(C.sub.5-C.sub.10)cycloalkyl is a (C.sub.1-C.sub.3)alkyl(C.sub.5-C.sub.6)cycloalkyl.

[0060] Examples of these groups include cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.

[0061] The term (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl refers to a C.sub.6-C.sub.10 aryl group as defined above which is attached to the rest of the molecule through a C.sub.1-C.sub.4 alkyl group as defined above. Preferably, the (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl is a (C.sub.6)aryl(C.sub.1-C.sub.3)alkyl. Examples of these groups include benzyl, phenylethyl, phenylpropyl, naphthylmethyl. Preferably, it refers to benzyl (Bn).

[0062] The term (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl refers to a C.sub.5-C.sub.10 heteroaryl group as defined above which is attached to the rest of the molecule through a C.sub.1-C.sub.4 alkyl group as defined above. Preferably, the (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl is a (C.sub.5-C.sub.6)heteroaryl (C.sub.1-C.sub.3)alkyl.

[0063] The term (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl refers to a C.sub.6-C.sub.10 aryl group as defined above which is attached to the rest of the molecule through a C.sub.2-C.sub.6 alkenyl group as defined above. Preferably, the (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl is (C.sub.6)aryl(C.sub.2-C.sub.4)alkenyl. Examples of these groups include (C.sub.6)aryl(C.sub.2)alkenyl (styryl), (Cia)aryl(C.sub.2)alkenyl (vinylnaphthalene). Preferably, it refers to styryl.

[0064] The term halogen refers to F, Cl, Br or I.

[0065] As used herein, the terms optional or optionally means that the subsequent described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase optionally substituted for an alkyl group means that the alkyl group may or may not be substituted and that the description includes both substituted and unsubstituted alkyl groups.

[0066] As mentioned above, the main aspect of the present invention relates to a process for preparing carbonyl-containing cyclic compounds of formula (Ia), (Ib) or (Ic):

##STR00006## [0067] wherein: [0068] X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, S and N(R.sub.11); [0069] R.sub.1-R.sub.11 and Z.sub.1 are independently selected from: [0070] hydrogen; [0071] linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; [0072] linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; [0073] C.sub.5-C.sub.10 cycloalkyl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0074] C.sub.5-C.sub.10 heterocyclyl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.10 and R.sub.11 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0075] C.sub.6-C.sub.10 aryl, optionally substituted with at least one C.sub.1-C.sub.4 alkyl, at least one fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.10 and R.sub.11 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0076] C.sub.5-C.sub.10 heteroaryl optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.10 and R.sub.11 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0077] a (C.sub.5-C.sub.7)cycloalkyl (C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; [0078] a (C.sub.5-C.sub.10)aryl (C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; [0079] a (C.sub.5-C.sub.10)aryl(C.sub.2-C.sub.5)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; [0080] a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; [0081] C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.10)aryl; [0082] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0083] or [0084] in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, each pair together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; [0085] in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl. [0086] Y is a single bond or a group (CH.sub.2).sub.pO(CH.sub.2).sub.q, wherein indexes p and q are independently selected from 0, 1 and 2; [0087] n is 0 or 1; [0088] comprising the reaction of BPA-PC of formula (II):

##STR00007## [0089] m is from 10 to 1000; [0090] with a compound of formula (IIIa), (IIIb) or (IIIc):

##STR00008## [0091] wherein X.sub.1, X.sub.2, X.sub.3, X.sub.4, R.sub.1-R.sub.11, Y, Z.sub.1 and n are as defined above; [0092] in the presence of a catalyst of formula (IV):

##STR00009## [0093] or any tautomeric form thereof; [0094] wherein: [0095] Z and W are independently selected from C and N, provided that Z and W are not simultaneously N; [0096] R.sub.15, R.sub.16, R.sub.17 and R.sub.18 are independently selected from H and a C.sub.1-C.sub.4 alkyl group or R.sub.17 and R.sub.18 can form a C aryl group when Z is C; [0097] and in the presence of an organic solvent, [0098] and wherein the process is carried out at a temperature from 25 to 60 C.

[0099] In a particular embodiment, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(C.sub.1-C.sub.4 alkyl) and N(C.sub.6 aryl), wherein the C aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl, a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl; hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl). Preferably, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride, or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl group. More preferably, at least one of X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is O, and even more preferably X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are all O.

[0100] In another particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0101] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0102] or [0103] in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; [0104] in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0105] In a more particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0106] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0107] or [0108] in the compounds of formula (Ia), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; [0109] in the compounds of formula (Ib), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0110] Even in a more particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0111] In a particular embodiment, the process of the invention refers to a process for preparing carbonyl-containing cyclic compounds of formula (Ia) or (Ib).

[0112] In a particular embodiment, in the compounds of formula (Ia), X.sub.1 and X.sub.2 are independently selected from O, NH, N(C.sub.1-C.sub.4 alkyl) and N(C.sub.6 aryl), wherein the C aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl). Preferably, X.sub.1 and X.sub.2 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride. More preferably, at least one of X.sub.1 and X.sub.2 is O, and even more preferably X.sub.1 and X.sub.2 are all O.

[0113] In another particular embodiment, in the compound of formula (Ia) n is 0.

[0114] Within this particular embodiment wherein n is 0, it is preferred that R.sub.1, R.sub.2 and R.sub.3 are hydrogen; and R.sub.4 is hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group. It is more preferred that R.sub.4 is a linear or branched C.sub.1-C.sub.6 alkyl group, even more preferably a C.sub.1-C.sub.3 alkyl, optionally substituted with a hydroxyl.

[0115] Within this particular embodiment wherein n is 0, it is also preferred that R.sub.1 and R.sub.3 are hydrogen; and R.sub.2 and R.sub.4 together form a C.sub.5-C.sub.7 cycloalkyl group.

[0116] It is also preferred that when n is 0, the carbonyl-containing cyclic compound of formula (Ia) is selected from:

##STR00010##

[0117] In another particular embodiment, in the compound of formula (Ia) n is 1.

[0118] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0119] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0120] or R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0121] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0122] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0123] or R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0124] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0125] Within the particular embodiment wherein n is 1, R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are hydrogen and R.sub.3 and R.sub.4 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0126] Within the particular embodiment where n is 1, R.sub.3 and R.sub.4 are hydrogen; and R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are independently selected from hydrogen and C.sub.1-C.sub.6 alkyl.

[0127] It is preferred that when n is 1, the carbonyl-containing cyclic compound of formula (Ia) is selected from:

##STR00011##

[0128] In another particular embodiment, in the compound of formula (Ib), X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride. More preferably, at least one of X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is O, and even more preferably X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are all O.

[0129] In another preferred embodiment, in the compound of formula (Ib), Y is a single bond.

[0130] In another preferred embodiment, in the compound of formula (Ib), Y is (CH.sub.2).sub.pO(CH.sub.2).sub.q, and more preferably index p and/or q is 1.

[0131] In a particular embodiment, in the compound of formula (Ib) n is 0.

[0132] Within this particular embodiment wherein n is 0 in the compounds of formula (Ib), R.sub.1-R.sub.4 and R.sub.7-R.sub.8 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0133] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0134] More preferably, in the compounds of formula (Ib), R.sub.3 and R.sub.4 are H.

[0135] It is more preferred that in the compounds of formula (Ib) when n is 0, R.sub.3 and R.sub.4 are hydrogen; and R.sub.1, R.sub.2, R.sub.7 and R.sub.3 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0136] Even more preferably, in the compounds of formula (Ib) when n is 0, R.sub.1, R.sub.3, R.sub.4 and R.sub.7 are hydrogen; and R.sub.2 and R.sub.3 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.5-C.sub.10 aryl group, more preferably a phenyl group.

[0137] It is also preferred that in the compounds of formula (Ib) when n is 0, R.sub.1, R.sub.3, R.sub.4 and R.sub.7 are hydrogen; and one of R.sub.2 and R.sub.3 is hydrogen, and the other a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.5-C.sub.10 aryl group, more preferably a phenyl group.

[0138] Even in a more preferred embodiment, in the compounds of formula (Ib), R.sub.1-R.sub.4 and R.sub.7-R.sub.3 are hydrogen.

[0139] Within this particular embodiment when n is 0, it is preferred that the carbonyl-containing cyclic compound of formula (Ib) is selected from:

##STR00012##

[0140] In a particular embodiment, in the compound of formula (Ib) n is 1.

[0141] Within this particular embodiment wherein n is 1 in the compounds of formula (Ib), R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0142] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0143] It is more preferred that in the compounds of formula (Ib) when n is 1, R.sub.1-R.sub.10 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0144] Even in a more preferred embodiment, in the compounds of formula (Ib) when n is 1, R.sub.1-R.sub.10 are hydrogen or a linear or branched C.sub.1-C.sub.6 alkyl group. Most preferably, R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.3, R.sub.9 and R.sub.10 are hydrogen and R.sub.3 and R.sub.4 are hydrogen or a linear or branched C.sub.1-C.sub.4 alkyl group.

[0145] Within this particular embodiment when n is 1, it is preferred that the carbonyl-containing cyclic compound of formula (Ib) is selected from:

##STR00013##

[0146] In another particular embodiment, the process of the invention refers to a process for preparing carbonyl-containing linear compounds of formula (Ic).

[0147] Within this particular embodiment, it is preferred that X.sub.1 is O or N(R.sub.11), wherein R.sub.11 is H, a C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

[0148] In a preferred embodiment, X.sub.1 is O.

[0149] In another preferred embodiment, X.sub.1 is NH.

[0150] In another preferred embodiment, Z.sub.1 is selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0151] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0152] In a more particular embodiment, Z.sub.1 is selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0153] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0154] Even in a more particular embodiment, Z.sub.1 is selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0155] In a preferred embodiment, Z.sub.1 is H, C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl, more preferably Z.sub.1 is C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

[0156] In another preferred embodiment, X.sub.1 is O and Z.sub.1 is C.sub.1-C.sub.4 alkyl.

[0157] In another preferred embodiment, X.sub.1 is NH and Z.sub.1 is a C aryl optionally substituted with at least a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

[0158] It is preferred that the carbonyl-containing linear compound of formula (Ic) is selected from:

##STR00014##

[0159] The process of the invention uses, as a starting source, BPA-PC of formula (II) as defined above. This polycarbonate may come from a material synthesized for this purpose but, in a preferred and advantageous embodiment, the BPA-PC employed is a waste material so that the reaction can be considered as a recycling reaction.

[0160] In fact, in a preferred embodiment, the source of the bisphenol based polycarbonate of formula (II) is a waste material having poly(bisphenol A carbonate).

[0161] In a particular embodiment, the bisphenol based polycarbonate of formula (II) can be a mixture or combination of a waste material having poly(bisphenol A carbonate) and a synthetic poly(bisphenol A carbonate).

[0162] The use of BPA-PC as a reagent for the synthesis of carbonyl-containing compounds is highly beneficial because of the simplicity and low cost impaired to the process of the invention.

[0163] In a preferred embodiment, the BPA-PC of formula (II) has a weight average molecular weight (Mw) of 10 000 to 100 000 g.Math.mol.sup.1 as measured by gel permeation chromatography (GPC) using polystyrene standard.

[0164] BPA-PC can be used in the process of the invention in the form of pellets, flakes, powder or in any other solid form.

[0165] The process of the invention requires a reagent which provides the different substituents to the carbonyl-containing cyclic compound of formula (I). This reagent is the compound of formula (IIIa), (IIIb) or (IIIc):

##STR00015## [0166] wherein X.sub.1, X.sub.2, X.sub.3, X.sub.4, R.sub.1-R.sub.10, Y, Z.sub.1 and n are as defined above.

[0167] Said compound is selected depending on the compound of formula (Ia), (Ib) or (Ic) to be obtained, respectively.

[0168] The particular and preferred embodiments for X.sub.1, X.sub.2, X.sub.3, X.sub.4, R.sub.1-R.sub.10, Y, Z.sub.1 and index n in the compounds of formula (IIIa), (IIIb) and (IIIc) are the same as those mentioned above for the carbonyl-containing compounds of formula (Ia), (Ib) and (Ic).

[0169] Thus, in a particular embodiment, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(C.sub.1-C.sub.4 alkyl) and N(C.sub.6 aryl), wherein the C aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl, a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl. Preferably, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride. More preferably, at least one of X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is O, and even more preferably X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are all O.

[0170] In another particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0171] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0172] or [0173] in the compounds of formula (IIIa), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; [0174] in the compounds of formula (IIIb), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0175] In a more particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0176] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0177] or

[0178] in the compounds of formula (IIIa), R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 when n is 1, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl; [0179] in the compounds of formula (IIIb), R.sub.1 and R.sub.3 or R.sub.3 and R.sub.5, and/or R.sub.4 and R.sub.7 or R.sub.4 and R.sub.9, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0180] Even in a more particular embodiment, R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0181] In a particular embodiment, in the compounds of formula (IIIa), X.sub.1 and X.sub.2 are independently selected from O, NH, N(C.sub.1-C.sub.4 alkyl) and N(C.sub.6 aryl), wherein the C aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl, hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl). Preferably, X.sub.1 and X.sub.2 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride. More preferably, at least one of X.sub.1 and X.sub.2 is O, and even more preferably X.sub.1 and X.sub.2 are all O.

[0182] In another particular embodiment, in the compound of formula (IIIa), n is 0.

[0183] Within this particular embodiment wherein n is 0, it is preferred that R.sub.1, R.sub.2 and R.sub.3 are hydrogen; and R.sub.4 is hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group. It is more preferred that R.sub.4 is a linear or branched C.sub.1-C.sub.6 alkyl group, even more preferably a C.sub.1-C.sub.3 alkyl, optionally substituted with a hydroxyl.

[0184] Within this particular embodiment wherein n is 0, it is also preferred that R.sub.1 and R.sub.3 are hydrogen; and R.sub.2 and R.sub.4 together form a C.sub.5-C.sub.7 cycloalkyl group.

[0185] It is also preferred that when n is 0, the compound of formula (IIIa) is selected from:

##STR00016##

[0186] In another particular embodiment, in the compound of formula (IIIa), n is 1.

[0187] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; a (C.sub.5-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, wherein the cycloalkyl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.6-C.sub.10)aryl(C.sub.2-C.sub.6)alkenyl, wherein the aryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; a (C.sub.5-C.sub.10)heteroaryl(C.sub.1-C.sub.4)alkyl, wherein the heteroaryl is optionally substituted with at least one C.sub.1-C.sub.4 alkyl; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0188] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0189] or R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5 together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0190] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0191] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; [0192] or R.sub.1 and R.sub.3, or R.sub.4 and R.sub.5, together can form a C.sub.5-C.sub.7 cycloalkyl or C.sub.5-C.sub.6 heterocyclyl group optionally substituted with C.sub.1-C.sub.4 alkyl.

[0193] Within the particular embodiment wherein n is 1, R.sub.1-R.sub.6 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0194] Within the particular embodiment wherein n is 1, R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are hydrogen and R.sub.3 and R.sub.4 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl.

[0195] Within the particular embodiment where n is 1, R.sub.3 and R.sub.4 are hydrogen; and R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are independently selected from hydrogen and C.sub.1-C.sub.6 alkyl.

[0196] In a preferred embodiment, when n is 1, the compound of formula (IIIa) is selected from:

##STR00017##

[0197] In another particular embodiment, in the compound of formula (IIIb), X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from O, NH, N(CH.sub.3) and N(C.sub.6 aryl), wherein the aryl is optionally substituted with at least one halogen, preferably fluoride. More preferably, at least one of X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is O, and even more preferably X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are all O.

[0198] In another preferred embodiment, in the compound of formula (IIIb), Y is a single bond.

[0199] In another preferred embodiment, in the compound of formula (IIIb), Y is (CH.sub.2).sub.pO(CH.sub.2).sub.q, and more preferably index p and/or q is 1.

[0200] In a particular embodiment, in the compound of formula (IIIb) n is 0.

[0201] Within this particular embodiment wherein n is 0 in the compounds of formula (IIIb), R.sub.1-R.sub.4 and R.sub.7-R.sub.8 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.5-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0202] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0203] More preferably, in the compounds of formula (IIIb) when n is 0, R.sub.3 and R.sub.4 are H.

[0204] It is more preferred that in the compounds of formula (IIIb) when n is 0, R.sub.3 and R.sub.4 are hydrogen; and R.sub.1, R.sub.2, R.sub.7 and R.sub.8 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0205] Even more preferably, in the compounds of formula (IIIb), R.sub.1, R.sub.3, R.sub.4 and R.sub.7 are hydrogen; and R.sub.2 and R.sub.3 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0206] It is also preferred that in the compounds of formula (IIIb) when n is 0, R.sub.1, R.sub.3, R.sub.4 and R.sub.7 are hydrogen; and one of R.sub.2 and R.sub.3 is hydrogen, and the other a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0207] Even in a more preferred embodiment, in the compounds of formula (IIIb) when n is 0, R.sub.1-R.sub.4 and R.sub.7-R.sub.3 are hydrogen.

[0208] Within this particular embodiment when n is 0, it is preferred that the compound of formula (IIIb) is selected from:

##STR00018##

[0209] In a particular embodiment, in the compound of formula (IIIb) n is 1.

[0210] Within this particular embodiment wherein n is 1 in the compounds of formula (IIIb), R.sub.1-R.sub.10 are independently selected from hydrogen; linear or branched C.sub.1-C.sub.6 alkyl optionally containing at least one heteroatom intercalated in the alkyl chain; linear or branched C.sub.2-C.sub.6 alkenyl optionally containing at least one heteroatom intercalated in the alkenyl chain; and C(O)OR.sub.14, wherein R.sub.14 is a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.10 aryl or a (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl; [0211] and wherein any of the C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl group can be optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13) wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl.

[0212] It is more preferred that in the compounds of formula (IIIb) when n is 1, R.sub.1-R.sub.10 are hydrogen; a linear or branched C.sub.1-C.sub.6 alkyl group optionally substituted with an hydroxyl, halogen or amine group N(R.sub.12)(R.sub.13), wherein R.sub.12 and R.sub.13 are independently selected from H and C.sub.1-C.sub.4 alkyl; or a C.sub.6-C.sub.10 aryl group, more preferably a phenyl group.

[0213] Even in a more preferred embodiment, in the compounds of formula (IIIb) when n is 1, R.sub.1-R.sub.10 are hydrogen or a linear or branched C.sub.1-C.sub.6 alkyl group. Most preferably, R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.3, R.sub.9 and R.sub.10 are hydrogen and R.sub.3 and R.sub.4 are hydrogen or a linear or branched C.sub.1-C.sub.4 alkyl group.

[0214] Within this particular embodiment when n is 1, it is preferred that the carbonyl-containing cyclic compound of formula (IIIb) is selected from:

##STR00019##

[0215] In another particular embodiment, in the compound of formula (IIIc), X1 is selected from O, NH, N(CH3) and N(C6 aryl), wherein the aryl is optionally substituted with at least a C1-C4 alkyl or a fluorinated or perfluorinated C1-C4 alkyl. More preferably X1 is O or NH.

[0216] In another particular embodiment, Z1 is H, C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl, more preferably Z.sub.1 is C.sub.1-C.sub.4 alkyl or a C.sub.6-C.sub.10 aryl optionally substituted with at least a C.sub.1-C.sub.4 alkyl or a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

[0217] In another preferred embodiment, X.sub.1 is O and Z.sub.1 is C.sub.1-C.sub.4 alkyl.

[0218] In another preferred embodiment, X.sub.1 is NH and Z.sub.1 is a C.sub.6 aryl optionally substituted with at least a fluorinated or perfluorinated C.sub.1-C.sub.4 alkyl.

[0219] It is preferred that the carbonyl-containing linear compound of formula (IIIc) is selected from:

##STR00020##

[0220] By means of a transesterification reaction between BPA-PC of formula (II) and the compound of formula (IIIa), which acts as a nucleophile, Bisphenol A (BPA) is obtained along with the corresponding cyclic carbonyl-containing compound of formula (Ia), according to the following reaction:

##STR00021##

[0221] In the same way, a transesterification reaction between BPA-PC of formula (II) and the compound of formula (IIIb) leads to Bisphenol A (BPA) along with the corresponding cyclic carbonyl-containing compound of formula (Ib), according to the following reaction:

##STR00022##

[0222] Similarly, a transesterification reaction between BPA-PC of formula (II) and the compound of formula (IIIc) leads to Bisphenol A (BPA) along with the corresponding linear carbonyl-containing compound of formula (Ic), according to the following reaction:

##STR00023##

[0223] Accordingly, the process of the invention allows the production of a large variety of carbonyl-containing compounds, both cyclic and linear, either unsubstituted or substituted with different functionalities, which can be used as monomers for the synthesis of the corresponding polymers by polymerization reactions. In the particular case when carbonyl-containing cyclic compounds are obtained, the corresponding polymers can be prepared by ring-opening polymerization reactions. Depending on the substituents present in the carbonyl-containing cyclic compound, polymers with different properties can be obtained, such as biocompatibility, biodegradability, conductivity, antimicrobial and antifungal properties, resistance to heat, etc.

[0224] On the other hand, the process of the invention provides not only a carbonyl-containing compound of formula (Ia), (Ib) or (Ic), but also BPA, which can also be used as monomer to produce further BPA-PC.

[0225] The process of the invention is carried out in the presence of a catalyst, namely an imidazole or a derivative thereof.

[0226] The imidazole or derivative thereof can be represented by formula (IV):

##STR00024## [0227] or any tautomeric form thereof; [0228] wherein: [0229] Z and W are independently selected from C and N, provided that Z and W are not simultaneously N; [0230] R.sub.15, R.sub.16, R.sub.17 and R.sub.18 are independently selected from H and a C.sub.1-C.sub.4 alkyl group or R.sub.17 and R.sub.13 can form a C aryl group when Z is C.

[0231] In a preferred embodiment, R.sub.15-R.sub.18 are independently selected from hydrogen and C.sub.1-C.sub.4 alkyl, more preferably from hydrogen and methyl.

[0232] In a more preferred embodiment, R.sub.15-R.sub.13 are hydrogen.

[0233] In another preferred embodiment, Z is C.

[0234] In another preferred embodiment, Z is N.

[0235] In another preferred embodiment, the catalyst has formula (IVa):

##STR00025## [0236] wherein: [0237] R.sub.15, R.sub.16, R.sub.17 and R.sub.18 are independently selected from H and a C.sub.1-C.sub.4 alkyl group or R.sub.17 and R.sub.13 can form a C aryl group; [0238] Z is C or N, provided that when Z is N then R.sub.17 does not exist;

[0239] In another preferred embodiment, R.sub.16 is H. In another preferred embodiment, R.sub.15-R.sub.18 are hydrogen.

[0240] In a more preferred embodiment, the catalyst is selected from imidazole, 1,2,3-triazole, 1,2,4-triazole, benzimidazole and 1H-benzotriazole:

##STR00026##

[0241] Even more preferably, the catalyst is imidazole.

[0242] The process of the invention is also performed in the presence of an organic solvent. A skilled person could easily recognise the suitable organic solvent to be used in the process of the invention depending on the reactants and the catalyst used.

[0243] In a preferred embodiment, the organic solvent is selected from methyl imidazole, tetrahydrofuran, chloroform and 2-methyl-tetrahydrofuran. Even more preferable is the use of methyl imidazole as organic solvent.

[0244] In a particular embodiment, the compound of formula (IIIa), (IIIb) or (IIIc), the catalyst of formula (IV) or (Iva) and BPA-PC of formula (II) are mixed in the organic solvent in any order.

[0245] In a preferred embodiment, the BPA-PC and the catalyst are added in equimolar amounts, whereas the compound of formula (III) is added slightly in excess. For example, between 1.02 and 1.2 equivalents of compound of formula (III) are added per equivalent of BPA-PC and catalyst.

[0246] A significant advantage of the process of the invention is the use of imidazole or a derivative thereof of formula (IV) or (IVa) as catalyst in combination with an organic solvent since they allow the carbonyl-containing compound of formula (Ia), (Ib) or (Ic) to be obtained at low temperatures without requiring a protective atmosphere.

[0247] Thus, in a particular embodiment, the process of the invention is carried out at a temperature below 80 C., more preferably from 25 to 60 C., even more preferably from 25 to 55 C., and most preferably from 30 to 50 C.

[0248] In another particular embodiment, the process of the invention is carried out in less than 5 hours, even more preferably in less than 2 hours.

[0249] In another particular embodiment, the process of the invention is performed under a non-protective atmosphere, i.e., an atmosphere containing oxygen.

[0250] Furthermore, the process is preferably conducted under atmospheric pressure.

[0251] The compounds of formula (Ia), (Ib) or (Ic) resulting from the process of the invention can be further purified once obtained using conventional techniques, such as column chromatography and liquid-liquid extraction.

EXAMPLES

Abbreviations

[0252] BPA: Bisphenol A [0253] BPA-PC: Bisphenol A polycarbonate [0254] TMC: trimethylene carbonate [0255] DMSO: dimethylsulfoxide

Example 1. Synthesis of [1,3]dioxan-2-one (TMC) Using Imidazole as Catalyst and 1-methyl Imidazole as Solvent

##STR00027##

[0256] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 1,3-propanediol (0.31 g, 4.14 mmol, 1.05 eq.), imidazole (0.27 g, 3.94 mmol, 1 eq.) and 1-methyl imidazole (3.23 g, 39.4 mmol, 10 eq.) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 50 C.

[0257] After 2 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product.

[0258] After a flash column in acetone/hexane 80/20, 0.31 g (78% yield) of 1,3-dioxan-2-one (TMC) were recovered as white powder, while 0.83 g (92% yield) of Bisphenol A were recovered as white powder.

[0259] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of TMC: 4.38 (t, 4H), 2.02 (qq, 2H)

[0260] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 2. Synthesis of 5-((allyloxy)methyl)-5-ethyl-1,3-dioxan-2-one using Imidazole as Catalyst and 1-Methylimidazole as Solvent

##STR00028##

[0261] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 2-((allyloxy)methyl)-2-ethylpropane-1,3-diol (0.72 g, 4.14 mmol, 1.05 eq.), imidazole (0.27 g, 3.94 mmol, 1 eq.) and 1-methyl imidazole (3.23 g, 39.4 mmol, 10 eq.) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 50 C.

[0262] After 1 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product.

[0263] After a flash column in acetone/hexane 70/30, 0.71 g (91% yield) of 5-((allyloxy)methyl)-5-ethyl-1,3-dioxan-2-one were recovered as white powder, while 0.85 g (94% yield) of Bisphenol A were recovered as white powder.

[0264] .sup.1H NMR (400 MHz, DMSO-d6) d (ppm) of 5-((allyloxy)methyl)-5-ethyl-1,3-dioxan-2-one: 5.94-5.82 (m, 1H), 5.30-5.16 (m, 2H), 4.25 (q, 4H), 3.97 (d, 2H), 3.38 (s, 2H), 1.40 (q, 2H), 0.85 (t, 3H)

[0265] .sup.1H NMR (400 MHz, DMSO-d6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 3. Synthesis of 5,5-dimethyltetra Hydropyrimidin-2-one Using Imidazole as Catalyst and 2-methyltetrahydrofuran as Solvent

##STR00029##

[0266] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 2,2-dimethylpropane-1,3-diamine (0.42 g, 4.14 mmol, 1.05 eq.), imidazole (0.54 g, 7.88 mmol, 2 eq.) and 2-methyltetrahydrofuran (4 mL 3.39 g, 39.4 mmol, 10 eq.) were charged in a vial which was immersed in an oil bath.

[0267] Reaction was carried out under stirring and under atmospheric pressure at room temperature.

[0268] After 30 min, the crude product was filtered to remove the eventual polymeric side-product and 2-methyltetrahydrofuran was removed through rotary evaporation.

[0269] The resulting product was precipitated in diethyl ether and filtrated on Bchner prior to be collected and dried, 0.41 g (82% yield) of 5,5-dimethyltetra hydropyrimidin-2-one were recovered as white powder, after evaporation of diethyl ether and precipitation in chloroform, 0.82 g (91% yield) of Bisphenol A were recovered as white powder.

[0270] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of 5,5-dimethyltetra hydropyrimidin-2-one: 6.05 (s, 2H), 2.77 (s, 4H), 0.95 (s, 6H)

[0271] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.13 (s, 2H), 6.98 (d, 4H), 6.67 (d, 4H), 1.52 (s, 3H).

Example 4. Synthesis of [1,3]dioxan-2-one (TMC) Using Triazole as Catalyst and 1-methylimidazole as Solvent

##STR00030##

[0272] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 1,3-propanediol (0.31 g, 4.14 mmol, 1.05 eq.), 1,2,4-1H-triazole (0.272 g, 3.94 mmol, 1 eq.) and 1-methyl imidazole (3.23 g, 39.4 mmol, 10 eq.) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 50 C.

[0273] After 3 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product.

[0274] After a flash column in acetone/hexane 80/20, 0.28 g (70% yield) of 1,3-dioxan-2-one (TMC) were recovered as white powder, while 0.75 g (83% yield) of Bisphenol A were recovered as white powder.

[0275] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of TMC: 4.38 (t, 4H), 2.02 (qq, 2H)

[0276] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 5. Synthesis of [1,3]dioxan-2-one (TMC) Using Imidazole as Catalyst and Chloroform as Solvent

##STR00031##

[0277] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 1,3-propanediol (0.31 g, 4.14 mmol, 1.05 eq.), imidazole (0.54 g, 7.88 mmol, 2 eq.), and chloroform (4 mL 5.96 g, 49.5 mmol, 12.56 eq.) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 50 C.

[0278] After 1 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product.

[0279] After a flash column in acetone/hexane 80/20, 0.19 g (49% yield) of 1,3-dioxan-2-one (TMC) were recovered as white powder, while 0.59 g (65% yield) of Bisphenol A were recovered as white powder.

[0280] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of TMC: 4.38 (t, 4H), 2.02 (qq, 2H)

[0281] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 6. Synthesis of 5,5-(oxybis(methylene))bis(5-ethyl-1,3-dioxan-2-one) Using Imidazole as Catalyst and 1-methylimidazole as Solvent

##STR00032##

[0282] BPA-PC pellets (1 g, 3.94 mmol, 1 eq.), 2,2-Oxybis(methylene)bis(2-ethyl-1,3-propanediol) (0.51 g, 2.06 mmol, 1.05 eq.), imidazole (0.266 g, 3.921 mmol, 1 eq.) and 1-Methylimidazole (3.219 g, 39.21 mmol, 10 eq.) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 50 C.

[0283] After 3 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product.

[0284] After a flash column in acetone/hexane 80/20, 0.454 g (73% yield) of 5,5-(oxybis(methylene))bis(5-ethyl-1,3-dioxan-2-one) were recovered as white powder, while 0.644 g (71% yield) of Bisphenol A were recovered as white powder.

[0285] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of 5,5-(oxybis(methylene))bis(5-ethyl-1,3-dioxan-2-one): 4.29 (d, 4H), 4.23 (d, 4H), 3.41 (s, 4H), 1.39 (q, 4H), 0.84 (t, 6H).

[0286] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 7. Synthesis of Dimethyl Carbonate Using Imidazole as Catalyst and Chloroform as Solvent

##STR00033##

[0287] BPA-PC pellets (20 g, 78.4 mmol, 1 eq.), methanol (7.5 g, 235 mmol, 3 eq.), imidazole (5.3 g, 78.4 mmol, 1 eq.), triethylamine (1.58 g 15.68 mmol) and chloroform (40 mL) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 60 C.

[0288] After 30 min, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product. The crude was kept in a freezer at 0 C. degrees overnight to precipitate the bisphenol A. The so formed bisphenol A crystals were filtrated, washed with 30 ml Chloroform and dried prior to be collected (13.41 g, 75% yield. The solution was distillated to obtain 4.94 g of dimethyl carbonate (70% yield) and recover the chloroform, triethylamine and imidazole used in the process.

[0289] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of dimethyl carbonate: 3.7 (s, 6H)

[0290] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 8. Synthesis of Diethyl Carbonate Using Imidazole as Catalyst and Chloroform as Solvent

##STR00034##

[0291] BPA-PC pellets (20 g, 78.4 mmol, 1 eq.), ethanol (10.8 g, 235 mmol, 3 eq.), imidazole (5.3 g, 78.4 mmol, 1 eq.), triethylamine (1.58 g 15.68 mmol) and chloroform (40 mL) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 60 C.

[0292] After 1 h, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product. The crude was kept in a freezer at 0 C. degrees overnight to precipitate the bisphenol A. The so formed bisphenol A crystals were filtrated, washed with 30 ml Chloroform and dried prior to be collected (13.41 g, 75% yield. The solution was distillated in order to obtain 6.67 g of diethyl carbonate (72% yield) and recover the chloroform, triethylamine and imidazole used in the process.

[0293] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of diethyl carbonate: 4.11 (q, 4H) 1.21 (q, 6H).

[0294] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 9. Synthesis of 1,3-diphenyl Urea Using Imidazole as Catalyst and 1-methyl Imidazole as Solvent

##STR00035##

[0295] BPA-PC pellets (10 g, 39.2 mmol, 1 eq.), aniline (3.8 g, 41.2 mmol, 1.05 eq.), imidazole (2.6 g, 39.2 mmol, 1 eq.), and 1-Methylimidazole (15 mL) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 40 C.

[0296] After 30 min, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product. Then methanol, 40 ml were added to the solution and it was introduced in a freezer at 0 C. degrees to precipitate the 1,3-diphenylurea. The so formed 1,3-diphenylurea crystals were filtrated, and dried prior to be collected (6.90 g, 83% yield.

[0297] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of diphenyl urea: 8.66 (s, 2H), 7.46 (d, 2H), 7.28 (t, 4H), 6.97 (t, 2H).

[0298] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).

Example 10. Synthesis of 1,3-bis(3,5-bis(trifluoromethyl)phenyl)urea Using Imidazole as Catalyst and 1-methyl Imidazole as Solvent

##STR00036##

[0299] BPA-PC pellets (10 g, 39.2 mmol, 1 eq.), 3,5-bis(trifluoromethyl)aniline (9.4 g, 41.2 mmol, 1.05 eq.), imidazole (2.6 g, 39.2 mmol, 1 eq.), and 1-Methylimidazole (15 mL) were charged in a vial which was immersed in an oil bath. Reaction was carried out under stirring and under atmospheric pressure at 40.

[0300] After 15 min, the crude product was cooled to room temperature and filtered to remove the eventual polymeric side-product. Then 40 ml of ethyl acetate were added to the crude to precipitate the product. After the addition the solution was kept in a freezer at 0 C. for 7 hours. The so formed crystals were filtrated, dried and collected (11.5 g 61% yield).

[0301] .sup.1H NMR (400 MHz, 298 K, DMSO-d.sub.6) d (ppm) of 1,3-bis(3,5-bis(trifluoromethyl) phenyl)urea: 9.53 (s, 2H), 7.97 (s, 4H), 7.48 (s, 2H).

[0302] .sup.1H NMR (400 MHz, DMSO-d.sub.6) d (ppm) of BPA: 9.12 (s, 2H), 6.96 (d, 4H), 6.65 (d, 4H), 1.53 (s, 3H).