# US 2010/0168462 A1 · Process for the preparation of beta-gamma ene carbonyl derivatives

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- Number: US 2010/0168462 A1
- Document ID: US20100168462A1
- Status: Published application
- Kind: A1
- Application number: 12/278,938
- Filed: 2007-02-01
- Published: 2010-07-01
- Earliest claimed: 2006-02-23
- Assignees: Firmenich SA
- Inventors: Hubert Mimoun; Serge Bonnaudet
- Web page: https://patentgrep.com/patent/US20100168462A1

## CPC

- C07C 67/32: Decarboxylation
- C07C 2601/16: the ring being unsaturated
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention relates to a preparation of β-γ ene carboxylic or ketone derivatives, which may also have particular requirement on the configuration of the carbon-carbon double bond. The method requires a thermal treatment of α-β unsaturated malonate or acetylacetonate derivatives in the presents of at least one carboxylic acid and at least one alkaline, alkaline-earth or lanthanide halide or carboxylates.

## Claims

### Claim at position 1

-10. (canceled)

### Claim 11

A process for the preparation of a compound of formula (I)
wherein:
the dotted lines indicate that the compound is in the form of a mixture of the corresponding β-γ or α-β unsaturated derivatives, the molar ratio β-γ/α-β being at least 3;
Y represents a OR4 or R4 group, R4 representing a C1-C8 hydrocarbon group, optionally comprising 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen;
R1 represents a C1-C15 hydrocarbon group, optionally comprising 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen;
R2 represents a C1-C5 hydrocarbon group, optionally comprising 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen; and
R3 represents a hydrogen atom or a C1-C5 hydrocarbon group;
optionally wherein R1 and R2, or R1 and R3, taken together, form a C4-C12 hydrocarbon group optionally comprising 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen;
by a method which comprises:
reacting, at a temperature between 100° C. and 230° C., a compound of formula
wherein Y, R1, R2 and R3 are defined as in formula (I);
with at least one compound from the group i) and at least one compound from the group ii) to prepare the compound of formula I, wherein:
group i) includes a salts of formula MX2, M″X3 or M′X, wherein M is an alkali-earth cation and M′ an alkali cation or C0-C12 ammonium cation and M″ is a lanthanide cation, and X is a halide or an anion of an acid HX having a pKa comprised between 0 and 6; and
group ii) includes carboxylic acids of formula R5COOH, wherein R5 represents a C1-C18 hydrocarbon group optionally comprising one or two oxygen atoms; and
wherein the reaction is optionally conducted in the presence of a polar aprotic solvent having a boiling point of above 100° C.

### Claim 12 (depends on 11)

A process according to claim 11, wherein the compound of formula (I) is of formula
wherein:
the dotted lines indicate that the compound is in the form of a mixture of the corresponding β-γ or α-β unsaturated derivatives, the molar ratio β-γ/α-β being at least 3;
Y represents, independently of each other, a OR4 or R4 group, R4 representing a C1-C6 alkyl group or a C6-C10 phenyl or benzyl group optionally comprising 1 to 3 oxygen or nitrogen atoms;
R1 represents a C2-C12 hydrocarbon atom, optionally comprising 1 to 3 functional oxygen or nitrogen atoms; and
R2 represents a C1-C3 alkyl group;
with R1 and R2, taken together, optionally forming a C4-C11 hydrocarbon group optionally comprising 1 to 3 oxygen or nitrogen atoms.

### Claim 13 (depends on 11)

A process according to claim 11, wherein compound (I) is obtained in the form of a mixture of the corresponding β-γ or α-β unsaturated derivatives, wherein:
β-γ/α-β is at least 6; or
isomers E and Z of the β-γ unsaturated derivatives, ((E)-β-γ)/((Z)-β-γ), are present in a molar ration of above 3.

### Claim 14 (depends on 11)

A process according to claim 11, wherein the compound of formula (I) is a compound of formula V
wherein R6 represents a methyl or ethyl group or a OMe or OEt group; and
R7 represents:
a C10-12 hydrocarbon group;
a phenyl group optionally substituted with 1 or 2 C1-C3 alkoxy or amino groups; or
a C3-C6 alkyl or alkenyl group.

### Claim 15 (depends on 11)

A process according to claim 11, wherein the compound of formula (II) is reacted in the presence of at least one compound from group iii) and at least one compound from the group iv), wherein:
group iii) includes a salt of formula MX2, M″X3 or M′X, wherein M is an alkali-earth cation and M′ an alkali cation or C0-C12 ammonium cation and M″ is a lanthanide cation, and X is a halide or an anion of an acid HX having a pKa comprised between 0 and 6, in particular a MX2 or M″X3 salt; and
group iv) includes an acid R5COOH, wherein R5 represents a C1-C18 hydrocarbon group optionally including one or two oxygen atoms.

### Claim 16 (depends on 15)

A process according to claim 15, wherein the compound of group iii) is a salt of formula MX2 or M″X3.

### Claim 17 (depends on 15)

A process according to claim 15, wherein the compound of group iii) is a magnesium, calcium, cerium, lithium, sodium or potassium salt of chlorine, fluorine, iodine, or of a carboxylate of formula R9COO−, R9 representing a C1-C18 hydrocarbon group optionally including one or two oxygen atoms.

### Claim 18 (depends on 7, 17)

A process according to claim 17, wherein the group iii) salt is NaCl, NaF, NaI, Mg(R9COO)2, R9COONa, R9COOK, KF, CeCl3, Ce(R9COO)3, CaCl2 or CaF2, R9 being defined as in claim 7.

### Claim 19 (depends on 11)

A process according to claim 11, wherein the compound of group iv) is a carboxylic acid R9COOH, wherein R9 is a C2-C9 alkyl, alkenyl, phenyl or benzyl group.

### Claim 20 (depends on 19)

A process according to claim 19, wherein R9 represents a pent-2-yl, hept-3yl, propyl, isopropyl, isobutyl, tertbutyl, isopentyl, cyclohexyl, benzyl or (Me)2(CH2)3C(Me)=CH group.