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US 5,288,882 AGranted
Process for recovering an optically active epoxy alcohol
AssigneeArco Chemical Technology, L.P.
InventorsT. Thomas Shih, Wilfred P.-S. Shum
Life of this patent
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Abstract
A method of recovering optically active epoxy alcohols from asymmetric epoxidation reaction mixture is provided whereby the epoxy alcohol may be obtained in high yield with minimal degradation of optical purity. The process is also suitable for the synthesis of useful organic sulfonate derivatives of chiral epoxy alcohols.
Claims21
A process for recovering an optically active epoxy alcohol from an asymmetric epoxidation reaction mixture comprised of the optically active epoxy alcohol, an organic hydroperoxide, and a transition metal-chiral ligand complex epoxidation catalyst, said process comprising the steps of
- (a) contacting the asymmetric epoxidation reaction mixture with
- (i) a reducing agent selected from sulfur (II) compounds, sulfur (III) compounds and phosphorus (III) compounds, in an amount effective to reduce the organic hydroperoxide;
- (ii) a polyalcohol, in an amount effective to inhibit the epoxidation catalyst;
- or
- (iii) both said reducing agent and said polyalcohol;
- (b) conducting a distillation in the presence of an azeotropic agent forming a minimum boiling heterogeneous azeotrope with the epoxy alcohol selected from aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and aliphatic hydrocarbons to remove in vapor form from the asymmetric epoxidation reaction mixture an overhead product comprised of the optically active epoxy alcohol and the azeotropic agent;
- (c) condensing the overhead product in liquid form whereby the condensed overhead product phase-separates to form an epoxy alcohol-rich phase and an epoxy alcohol-lean phase;
- and
- (d) separating the epoxy alcohol-rich phase from the epoxy alcohol-lean phase.
6 more elements
A process for recovering optically active glycidol from an asymmetric epoxidation reaction mixture comprised of the optically active glycidol, cumene hydroperoxide, a titanium-chiral tartaric acid diester complex epoxidation catalyst, and allyl alcohol, said process comprising the steps of
- (a) contacting the asymmetric epoxidation reaction mixture with
- (i) an amount of a reducing agent selected from alkali metal bisulfites, alkali metal sulfites, and trialkyl phosphites at least equivalent on a molar basis to the amount of cumene hydroperoxide to reduce the cumene hydroperoxide;
- (ii) an amount of a 1,2-diol at least equivalent on a molar basis to the amount of titanium-chiral tartaric acid diester complex epoxidation catalyst to inhibit said epoxidation catalyst;
- or
- (iii) both said reducing agent and said 1,2-diol, each in an amount at least equivalent on a molar basis to the amount of cumene hydroperoxide and titanium-chiral tartaric acid diester complex epoxidation catalyst respectively to reduce the cumene hydroperoxide and inhibit the epoxidation catalyst;
- (b) conducting a distillation in the presence of an azeotropic agent forming a minimum boiling heterogeneous azeotrope with glycidol selected from cumene, hexyl chloride, tetrachloroethylene, n-octane, isooctane, ethyl cyclohexane, and n-heptane to sequentially remove in vapor form from the asymmetric epoxidation reaction mixture a first overhead product comprised of allyl alcohol and a second overhead product comprised of the optically active glycidol and the azeotropic agent;
- (c) condensing the second overhead product in liquid form at a temperature of from -20.degree. C. to 40.degree. C. whereby the condensed second overhead product phase-separates to form a glycidol-rich phase and a glycidol-lean phase;
- and
- (d) separating the glycidol-rich phase from the glycidol-lean phase.
6 more elements
A process for preparing an organic sulfonate derivative of an optically active epoxy alcohol from an asymmetric epoxidation reaction mixture comprised of the optically active epoxy alcohol, an organic hydroperoxide, and a transition metal-chiral ligand complex epoxidation catalyst, said process comprising the steps of
- (a) contacting the asymmetric epoxidation reaction mixture with
- (i) a reducing agent selected from sulfur (II) compounds, sulfur (III) compounds, and phosphorus (III) compounds, in an amount effective to reduce the organic hydroperoxide;
- (ii) a polyalcohol, in an amount effective to inhibit the epoxidation catalyst;
- or
- (iii) both said reducing agent and said polyalcohol;
- (b) conducting a distillation in the presence of an aromatic hydrocarbon azeotropic agent forming a minimum boiling homogeneous azeotrope with the epoxy alcohol to remove in vapor form from the asymmetric epoxidation reaction mixture an overhead product comprised of the optically active epoxy alcohol and the azeotropic agent;
- (c) condensing the overhead product in liquid form;
- (d) contacting the condensed overhead product with an organic sulfonyl halide for a time and at a temperature effective to form the organic sulfonate derivative of the epoxy alcohol.
5 more elements
A process for obtaining an aromatic sulfonate derivative of an optically active epoxy alcohol, said process comprising the steps of
- (a) contacting an asymmetric epoxidation reaction mixture comprised of the optically active epoxy alcohol, an organic hydroperoxide, and a transition metal-chiral ligand complex epoxidation catalyst, with
- (i) a reducing agent selected from sulfur (II) compounds, sulfur (III) compounds and phosphorus (III) compounds, in an amount effective to reduce the organic hydroperoxide;
- (ii) a polyalcohol, in an amount effective to inhibit the epoxidation catalyst;
- or
- (iii) both said reducing agent and said polyalcohol;
- (b) conducting a distillation in the presence of an azeotropic agent forming a minimum boiling heterogeneous azeotrope with the epoxy alcohol selected from aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and aliphatic hydrocarbons to remove in vapor form from the asymmetric epoxidation reaction mixture an overhead product comprised of the optically active epoxy alcohol and the azeotropic agent;
- (c) condensing the overhead product in liquid form whereby the condensed overhead product phase-separates to form an epoxy alcohol-rich phase and an epoxy alcohol-lean phase;
- and
- (d) contacting the condensed overhead product with an organic sulfonyl halide for a time and at a temperature effective to form the organic sulfonate derivative of the epoxy alcohol.
6 more elements
A process for obtaining an aromatic sulfonate derivative of an optically active glycidol said process comprising the steps of
- (a) contacting an asymmetric epoxidation reaction mixture comprised of the optically active glycidol, cumene hydroperoxide, a titanium-chiral tartaric acid diester complex epoxidation catalyst, and allyl alcohol, with
- (i) an amount of a reducing agent selected from alkali metal bisulfites, alkali metal sulfites, and trialkyl phosphites at least equivalent on a molar basis to the amount of cumene hydroperoxide to reduce the cumene hydroperoxide;
- (ii) an amount of a 1,2-diol at least equivalent on a molar basis to the amount of titanium-chiral tartaric acid diester complex epoxidation catalyst to inhibit said epoxidation catalyst;
- or
- (iii) both said reducing agent and said 1,2-diol, each in an amount at least equivalent on a molar basis to the amount of cumene hydroperoxide and titanium-chiral tartaric acid diester complex epoxidation catalyst respectively to reduce the cumene hydroperoxide and inhibit the epoxidation catalyst;
- (b) conducting a distillation in the presence of an azeotropic agent forming a minimum boiling heterogeneous azeotrope with glycidol selected from cumene, hexyl chloride, tetrachloroethylene, n-octane, isooctane, ethyl cyclohexane, and n-heptane to sequentially remove in vapor form from the asymmetric epoxidation reaction mixture a first overhead product comprised of allyl alcohol and a second overhead product comprised of the optically active glycidol and the azeotropic agent;
- (c) condensing the second overhead product in liquid form at a temperature of from -20.degree. C. to 40.degree. C. whereby the condensed second overhead product phase-separates to form a glycidol-rich phase and a glycidol-lead phase;
- and
- (d) contacting the condensed overhead product with an aromatic sulfonyl halide for a time and at a temperature effective to form the aromatic sulfonate derivative of the glycidol.
6 more elements
Dependencies are inferred from the claim text.