US 7,002,049 B2Granted

Process for α,β-dihydroxyalkenes and derivatives

AssigneeEastman Chemical Company

InventorsRobert Thomas Hembre, Jonathan Michael Penney

Life of this patent

Estimating the term…

Loading patent…

Abstract

Disclosed is a process wherein a first olefin selected from certain α,β-dihydroxyalkenes and 4-(alkenyl)ethylenecarbonates is reacted with a second olefin reactant to produce an olefin metathesis product. When the first olefin reactant is an optically enriched or enantiomerically pure α,β-dihydroxyalkene, cross metathesis reactions produce products possessing the same optical purity. The α,β-dihydroxyalkenes and the 4-(alkenyl)ethylene carbonates may be converted to hydrogenated products, and the 4-(alkenyl)ethylenecarbonates may be decarboxylated to provide the corresponding epoxides. The products of the disclosure may be used as monomers for the preparation of specialty polyesters and as intermediates in the manufacture pharmaceuticals and other chemicals.

Claims22

Dependent claims

Process for the preparation of a compound having the formula:

which comprises contacting a first olefin selected from α,β-dihydroxyalkenes having the formula:
and at least one olefin having the formula H2C═CHR2 (V) or R2HC═CHR2 (VI) or a cycloalkene (VII) in the presence of an olefin metathesis catalyst under olefin metathesis conditions of pressure and temperature wherein
R1 is hydrogen, a C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
a C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
a C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
a C6 to C10, substituted or unsubstituted aryl radical;
or a C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
R2 each is C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
C6 to C10, substituted or unsubstituted aryl radical;
or C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
and
cycloalkene (VII) is selected from the group consisting of substituted or unsubstituted cyclobutenes, cyclopentenes, cyclopentadienes, cyclohexenes, cycloheptenes, and cyclooctenes.

11 more elements

Process for the preparation of an enantiomerically enriched compound having the formula:

which comprises contacting an enantiomerically enriched α,β-dihydroxyalkene having the formula:
and at least one olefin selected from olefins having the formula H2C═CHR2 (V) or R2HC═CHR2 (VI) or a cycloalkene (VII) in the presence of an olefin metathesis catalyst under olefin metathesis conditions of pressure and temperature wherein
R1 is hydrogen, a C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
a C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
a C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
a C6 to C10, substituted or unsubstituted aryl radical;
or a C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
R2 each is C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
C6 to C10, substituted or unsubstituted aryl radical;
or C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
and
cycloalkene (VII) is selected from the group consisting of substituted or unsubstituted cyclobutenes, cyclopentenes, cyclopentadienes, cyclohexenes, cycloheptenes, and cyclooctenes.

11 more elements

Process for the preparation of a compound having the formula:

which comprises the steps of:
(1) contacting an α,β-dihydroxyalkene having the formula:
with at least one olefin having the formula H2C═CHR2 (V) or R2HC═CHR2 (VI) or a cycloalkene (VII) in the presence of an olefin metathesis catalyst under olefin metathesis conditions of pressure and temperature to produce a compound having the formula:
and
(2) hydrogenating compound (I) produced in step (1) to obtain a compound having the formula of VIII wherein
R1 is hydrogen, a C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
a C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
a C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
a C6 to C10, substituted or unsubstituted aryl radical;
or a C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
R2 each is C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
C6 to C10, substituted or unsubstituted aryl radical;
or C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
and
cycloalkene (VII) is selected from the group consisting of substituted or unsubstituted cyclobutenes, cyclopentenes, cyclopentadienes, cyclohexenes, cycloheptenes, and cyclooctenes.

14 more elements

Process for the preparation of an enantiomerically enriched diol compound having the formula:

which comprises the steps of:
(1) contacting an enatiomerically enriched α,β-dihydroxyalkene having the formula:
with at least one olefin having the formula H2C═CHR2 (V) or R2HC═CHR2 (VI) or a cycloalkene (VII) in the presence of an olefin metathesis catalyst under olefin metathesis conditions of pressure and temperature to produce a compound having the formula:
and
(2) hydrogenating compound I-A or I-B produced in step (1) to obtain a compound having the formula VIII-A or VIII-B wherein
R1 is hydrogen, a C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
a C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
a C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
a C6 to C10, substituted or unsubstituted aryl radical;
or a C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
R2 each is C1 to C10, substituted or unsubstituted, straight or branched chain alkyl radical;
C2 to C10, substituted or unsubstituted, straight or branched chain alkenyl radical;
C3 to C10, substituted or unsubstituted cycloalkyl or cycloalkenyl radical;
C6 to C10, substituted or unsubstituted aryl radical;
or C4 to C10, substituted or unsubstituted heterocylic radical containing from 1 to 3 heteroatoms selected from oxygen and sulfur;
and
cycloalkene (VII) is selected from the group consisting of substituted or unsubstituted cyclobutenes, cyclopentenes, cyclopentadienes, cyclohexenes, cycloheptenes, and cyclooctenes.

14 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/453,705Filed 3 Jun 2003 · us provisional application
Priority: 19 Aug 2002
Published: US 2004/0044229 A14 Mar 2004
Granted: 21 Feb 2006
Term ends: Not estimatedThe source records don’t support an estimate.

Classification8 codes

C07D 301/14
By oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds: with organic peracids, or salts, anhydrides or…
C07C 29/172
By hydrogenation of carbon-to-carbon double or triple bonds: with the obtention of a fully saturated alcohol
C07C 29/44
Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring: increasing the…
C07B 2200/07
Indexing scheme relating to specific properties of organic compounds: optical isomers