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1. (WO2018197325) PROCÉDÉ DE PRÉPARATION DE CÉTONES FONCTIONNALISÉES EN ALPHA
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C L A I M S

1 . A process for the preparation of an a-functionalized ketone of the general

formula I,


wherein Ri and R2 are the same or different and are independently selected from H, linear or branched Ci-Cs-alkyl, Cs-Cs-cycloalkyl, linear or branched C2-C8- alkenyl, Cs-Cs-cycloalkenyl, linear or branched C2-C8-alkynyl, C6-Ci4-aryl or form C3-Ci2-cycloalkyl or C5-Ci2-cycloalkenyl together with the connecting C atom; R3, R4, R5, R6 and R7 are the same or different and are independently selected from H, linear or branched Ci-Cs-alkyl, linear or branched C2-C8-alkenyl, Ci-Cs- alkoxy, C2-C8-alkenyloxy, Cs-Cs-cycloalkyl, C6-Ci4-aryl, C3-Cs-cycloalkoxy, C7- Ci5-arylalkoxy, C9-Ci5-alkenylarylalkoxy, N(Rs)2 or SRs with Rs being selected from linear or branched Ci-Cs-alkyl, linear or branched C2-C8-alkenyl, C6-Ci4- aryl, Ci-Cs-alkoxy, C2-C8-alkenyloxy, Cs-Cs-cycloalkyl, C3-Cs-cycloalkoxy, C7-C15- arylalkoxy, C9-Ci5-alkenylarylalkoxy, or Rs form a C3-C9-alicyclic system together with the connecting N atom, optionally one or more carbon atoms are replaced with O, or two adjacent R form an aromatic system together with the benzene ring of formula I;

Z is selected from OR9, NHR9 and NR10R11 with R9, R10 and Rn being

independently selected from H, linear or branched Ci-Cs-alkyl, linear or branched C2-C8-alkenyl, Ci-Cs-alkoxy, C2-C8-alkenyloxy, Cs-Cs-cycloalkyl, C3-C8- cycloalkoxy, C6-Ci4-aryl, Cz-Cis-arylalkyl, C7-Cis-arylalkoxy, C9-C15- alkenylarylalkoxy, C9-Ci5-alkenylarylalkyl; or R10 and Rn form a C3-C9-alicyclic system together with the connecting N or C atom, optionally one or more carbon atoms are replaced with O;

characterized in that a ketone of the general formula II


wherein Ri , R2, R3, R4, R5, R6 and R7 are as defined above, is contacted under phase-transfer conditions with an at least partially halogenated C2-C8-alkane and/or C2-C8-alkene, and a base selected from the group comprising alkali metal hydroxide, earth alkali metal hydroxide, alkali metal Ci-Cs-alkoxide, earth alkali metal Ci-Cs-alkoxide and mixtures thereof, or a base selected from the group comprising alkali metal hydroxide, earth alkali metal hydroxide, alkali metal Ci- Cs-alkoxide, earth alkali metal Ci-Cs-alkoxide and mixtures thereof together with the protonated form of Z as defined above.

2. The process according to claim 1 , characterized in that Ri and R2 are the same.

3. The process according to claim 2, characterized in that Ri and R2 are selected from H and linear or branched Ci-Cs-alkyl, preferably linear or branched C1-C6- alkyl, more preferably linear or branched Ci-C4-alkyl and most preferably linear Ci-Cs-alkyl.

4. The process according to claim 1 , characterized in that Ri and R2 are different and are independently selected from H and linear or branched Ci-Cs-alkyl, preferably linear or branched Ci-C6-alkyl, more preferably linear or branched Ci- C4-alkyl and most preferably linear Ci-C3-alkyl.

5. The process according to claim 1 , characterized in that Ri and R2 form C4-Cio- cycloalkyl, preferably C4-C8-cycloalkyl, and most preferably C6-cycloalkyl, together with the connecting C atom.

6. The process according to any one of claims 1 to 5, characterized in that R3, R4, R5, R6 and R7 are the same.

7. The process according to claim 6, characterized in that R3, R4, R5, R6 and R7 are selected from H and linear or branched Ci-Cs-alkyl, preferably linear or branched Ci-C6-alkyl, more preferably linear or branched Ci-C4-alkyl and most preferably linear Ci-C3-alkyl.

8. The process according to any one of claims 1 to 5, characterized in that R3, R4, R5, R6 and R7 are different and at least one of them is selected from linear or branched Ci-Cs-alkyl, linear or branched C2-C8-alkenyl, Ci-Cs-alkoxy, C2-C8- alkenyloxy, Cg-Cis-alkenylarylalkoxy or N(Rs)2 or SRs with Rs being selected from linear or branched Ci-Cs-alkyl or linear or branched C2-Cs-alkenyl or Rs form a

C3-C9-alicyclic system together with the connecting N atom.

9. The process according to any one of claims 1 to 5 or 8, characterized in that one of R3, R4, Rs, R6 and R7 is linear or branched C2-Cs-alkenyl, preferably C2-C6- alkenyl and most preferably C2-C3-alkenyl; Ci-Cs-alkoxy, preferably Ci-C6-alkoxy and most preferably Ci-C3-alkoxy; C2-Cs-alkenyloxy, preferably C2-C6-alkenyloxy and most preferably C3-Cs-alkenyloxy; Cg-Cis-alkenylarylalkoxy, preferably Cg- Ci2-alkenylarylalkoxy and most preferably Cg-Cio-alkenylarylalkoxy; or N(Rs)2 or SRs with Rs being selected from linear or branched Ci-Cs-alkyl or linear or branched C2-Cs-alkenyl or Rs form a C3-Cg-alicyclic system together with the connecting N atom; and the remaining ones are independently selected from H and linear or branched Ci-Cs-alkyl, preferably linear or branched Ci-C6-alkyl, more preferably linear or branched Ci-C4-alkyl and most preferably linear C1-C3- alkyl.

10. The process according to any one of claims 1 to 5 or 8, characterized in that two or three of R3, R4, R5, R6 and R7 are linear or branched C2-Cs-alkenyl, preferably C2-C6-alkenyl and most preferably C2-C3-alkenyl; Ci-Cs-alkoxy, preferably C1-C6- alkoxy and most preferably Ci-C3-alkoxy; C2-Cs-alkenyloxy, preferably C2-C6- alkenyloxy and most preferably C3-Cs-alkenyloxy; and Cg-Cis-alkenylarylalkoxy, preferably Cg-Ci2-alkenylarylalkoxy and most preferably Cg-Cio-alkenylarylalkoxy, and the remaining ones are independently selected from H and linear or branched Ci-Cs-alkyl, preferably linear or branched Ci-C6-alkyl, more preferably linear or branched Ci-C4-alkyl and most preferably linear Ci-C3-alkyl.

1 1 .The process according to any one of claims 1 to 5, characterized in that R3 and R4 or R4 and R5 form an aromatic system together with the benzene ring of formula I, preferably a bicyclic, tricyclic or tetracyclic aromatic system, more preferably an aromatic system selected from a naphthyl, anthracenyl and phenanthrenyl system.

12. The process according to claim 1 1 , characterized in that one of the remaining R is linear or branched C2-C8-alkenyl, preferably C2-C6-alkenyl and most preferably C2-C3-alkenyl; C2-C8-alkenyloxy, preferably C2-C6-alkenyloxy and most preferably

C3-C5-alkenyloxy; and Cg-Cis-alkenylarylalkoxy, preferably C9-C12- alkenylarylalkoxy and most preferably Cg-Cio-alkenylarylalkoxy; and the remaining ones are independently selected from H and linear or branched Ci-Cs- alkyl, preferably linear or branched Ci-C6-alkyl, more preferably linear or branched Ci-C4-alkyl and most preferably linear Ci-C3-alkyl.

13. The process according to any one of claims 1 to 12, characterized in that Z is ORg with R9 being selected from H, linear or branched Ci-Cs-alkyl, linear or branched C2-C8-alkenyl, Ci-Cs-alkoxy, C2-C8-alkenyloxy, Cs-Cs-cycloalkyl, C3-C8- cycloalkoxy, Cz-Cis-arylalkoxy and Cg-Cis-alkenylarylalkoxy, preferably R9 is H or

Z is NR10R11 with R10 and Rn being independently selected from H, linear or branched Ci-Cs-alkyl, Cs-Cs-cycloalkyl, C6-Ci4-aryl, or R10 and Rn form a C3-C6- alicyclic system together with the connecting N atom, optionally one or more carbon atoms are replaced with O, preferably R10 and Rn form a Cs-C6-alicyclic system together with the connecting N atom and one or more carbon atoms are replaced with O.

14. The process according to any one of claims 1 to 13, characterized in that the at least partially halogenated C2-C8-alkane and/or C2-Cs-alkene is fully

halogenated, preferably the at least partially halogenated C2-Cs-alkane and/or

C2-C8-alkene is selected from hexachloroethane, tetrachoroethylene and mixtures thereof.

15. The process according to any one of claims 1 to 14, characterized in that the base is selected from the group comprising sodium hydroxide; lithium hydroxide; potassium hydroxide; sodium Ci-C6-alkoxide, preferably sodium Ci-C4-alkoxide and most preferably sodium Ci-C2-alkoxide; lithium Ci-C6-alkoxide, preferably lithium Ci-C4-alkoxide and most preferably lithium Ci-C2-alkoxide; potassium Ci- C6-alkoxide, preferably potassium Ci-C4-alkoxide and most preferably potassium Ci-C2-alkoxide; and mixtures thereof; or the base is selected from sodium C1-C6- alkoxide, preferably sodium Ci-C4-alkoxide and most preferably sodium C1-C2- alkoxide; potassium Ci-C6-alkoxide, preferably potassium Ci-C4-alkoxide and most preferably potassium Ci-C2-alkoxide, together with the protonated form of Z as defined above.

16. The process according to any one of claims 1 to 14, characterized in that the base is in form of an aqueous solution or the base is provided in an organic solvent, preferably the organic solvent is selected from the group comprising methanol, ethanol, n-propanol, tert.-butanol, dichloromethane,

tetrachloroethylene, tetrahydrofuran, ethyl acetate, acetone, N,N- dimethylformamide, dimethylsulfoxide, dioxane, such as 1 ,3-dioxane or 1 ,4- dioxane, 1 ,2-dimethoxyethane, diethyleneglycol dimethyl ether, triethyleneglycol dimethyl ether and mixtures thereof.

17. The process according to any one of claims 1 to 16, characterized in that the process is carried out at a temperature of at least 30 °C, preferably in the range from 30 to 120 °C, more preferably in the range from 40 to 100 °C, and most preferably in the range from 40 to 90 °C.

18. The process according to any one of claims 1 to 17, characterized in that the process is carried out in an organic solvent, preferably the organic solvent is selected from the group comprising methanol, ethanol, n-propanol, tert.-butanol, dichloromethane, tetrachloroethylene, tetrahydrofuran, ethyl acetate, acetone, Ν,Ν-dimethylformamide, dimethylsulfoxide, dioxane, such as 1 ,3-dioxane or 1 ,4- dioxane, 1 ,2-dimethoxyethane, diethyleneglycol dimethyl ether, triethyleneglycol dimethyl ether and mixtures thereof.

19. The process according to any one of claims 1 to 18, characterized in that the process is carried out in the presence of a phase-transfer catalyst, preferably the phase-transfer catalyst is selected from a quaternary ammonium salt,

tetraalkylphosphonium chloride, tetraalkylphosphonium bromide and mixtures thereof, preferably the phase-transfer catalyst is a tetraalkylammonium salt or a trialkylarylammonium salt, more preferably the phase-transfer catalyst is selected from the group comprising benzyltrimethylammonium hydroxide,

benzyltriethylammonium chloride, tetrabutylammonium chloride,

tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate,

tetrabutylammonium hydroxide, methyltrioctylammonium chloride, cetyl pyridinium and mixtures thereof.

20. The process according to any one of claims 1 to 19, characterized in that the a- functionalized ketone is obtained in an one-pot reaction.

21 .The process according to any one of claims 1 to 20, characterized in that the process further comprises a step of

i) separating the obtained organic and aqueous phases, and/or

ii) extracting the obtained aqueous phase with the organic solvent used in the process and combining the obtained organic phases, and/or iii) acidifying the obtained organic phase to a pH of 3 to 6.5.

22. An a-functionalized ketone obtained by a process according to any one of claims 1 to 21 .

23. An a-functionalized ketone as defined in any one of claims 1 to 13, with the

proviso that at least one of R3, R4, R5, R6 and R7 is linear or branched C2-C8- alkenyl, preferably C2-C6-alkenyl and most preferably C2-C3-alkenyl, C2-C8- alkenyloxy, preferably C2-C6-alkenyloxy and most preferably C3-Cs-alkenyloxy, and C9-Ci5-alkenylarylalkoxy, preferably C9-Ci2-alkenylarylalkoxy and most preferably Cg-Cio-alkenylarylalkoxy.

24. A photopolymerizable composition comprising the a-functionalized ketone according to claims 22 or 23 and at least one photopolymerizable unsaturated compound.

25. A method of preparing an article, the method comprising the steps of:

a) preparing a coating and/or ink composition comprising the a-functionalized ketone of claim 22 or 23 or the photopolymerizable composition comprising an α-functionalized ketone of claim 24,

b) applying the coating and/or ink composition at least partially on at least one surface of an article, and

c) curing the coating and/or ink composition by means of ultra-violet radiation.

26. An article obtained by a method of preparing an article according to claim 25.

27. The article according to claim 26, wherein the article is a packaging article, more preferably a food or beverage packaging article, an article of flooring or an article of furniture.

28. Use of the α-functionalized ketone according to claim 22 or 23 or the

photopolymerizable composition according to claim 24 as photoinitiator.

29. The use according to claim 28 in a method of preparing an article or in an article, preferably a packaging article, more preferably a food or beverage packaging article, an article of flooring or an article of furniture.