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US 6,686,498 B2Granted
Process for the preparation of Michael-adducts
AssigneeFirmenich SA
InventorDenis Jacoby
Life of this patent
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Abstract
The present invention relates to the field of organic synthesis and more specifically to a process for the preparation of Michael-adducts, as defined below, by reacting a β,β- or a α,β-disubstituted, or a α,β,β-trisubstituted, α,β-unsaturated ketone (I) with a β-ketoester or a β-diketone (II) in presence of a suitable catalyst of formula M(X)n, according to scheme 1:
Claims15
A compound selected from the group consisting of methyl 2-acetyal-3,3-dimethyl-5-oxo-hexanoate, 3-acetyl-4,4-dimethyl-2,6-heptanedione and methyl 2-acetyl-3,4-dimethyl-5-oxo-hexanoate.
A process for the preparation of a compound of formula (III):
- wherein
- Q is selected from the group consisting of R′ and OR′ group;
- R1, R′, and R″ are selected, independently from each other, from the group consisting of a linear C1-C5 alkyl group, linear C1-C5 alkenyl group, a C1-C4 alkyl group, a C1-C4 alkenyl group, a C1-C4 alkoxy group, a C5-C6 cycloalkyl group, and a cycloalkenyl group;
- R′″ is selected from the group consisting of a hydrogen atom, and a linear or branched C1-C3 alkyl group;
- and
- R2, R3, and R4 are selected, independently from each other, from the group consisting of a hydrogen atom, a linear C1-C5 alkyl group, a linear C1-C5 alkenyl group, a C1-C4 alkyl group, a C1-C4 alkenyl group, a C1-C4 alkoxy group, a C5-C6 cycloalkyl group, and a C5-C6 cycloalkenyl group;
- wherein at least two of said R2, R3 and R4 groups do not represent simultaneously an hydrogen atom;
- which comprises reacting a β,β- or a α,β-disubstituted, or a α,β,β-trisubstituted, α,β-unsaturated ketone (I)
- wherein R1, R2, R3 and R4 have the same meaning as in formula (III), with a β-ketoester or a β-diketone (II)
- wherein Q, R″ and R′″ have the same meaning as in formula (III),
- in the presence of a catalyst of formula M(X)n, wherein
- M is selected from the group consisting of a 3d transition metal, a lanthanide, a trimethylsilane group, a vanadyl group, an alkaline metal, Sc, Y, Sn, Pb, Al and Bi;
- n is an integer from 1 to 3;
- and
- X is selected from the group consisting of CF3SO3−, RSO3−, SbF6−, PF6−, ClO4−, [BF3(RCOCRCOR)]−, [BF3(RCOCRCO2R)]−, [BF3(RCOO)]−, [BF3(RO)]−, and BF4−, with R selected from the group consisting of an C1-C10 aromatic, alkylaromatic or alkyl group, halides atoms, and C1-C6 alkyl or alkoxy groups.
12 more elements
Dependencies are inferred from the claim text.