Title of Invention	A PROCESS TO MAKE 2,3-DIHALOPROPANOL
Abstract	The present invention relates to a process to make 2,3-dihalopropanol co1llprising the step of reacting 2,3-dihalopropanal with molecular hydrogen in the presence of a transition metal-containing catalyst to form 2,3-dihalopropanol; said transition metal selected from any of Groups ill, lIB or lllA- VIllA on the periodic table of elements, as currently adopted by the International Union of Pure and Applied Chemistry (!UP AC); wherein the reaction is carried under a pressure of from 14 psia to 3000 psia and at a temperature of from about -10°C to 250°C such that 2,3- dihalopropanol is formed.

Title of Invention

A PROCESS TO MAKE 2,3-DIHALOPROPANOL

Abstract

The present invention relates to a process to make 2,3-dihalopropanol co1llprising the step of reacting 2,3-dihalopropanal with molecular hydrogen in the presence of a transition metal-containing catalyst to form 2,3-dihalopropanol; said transition metal selected from any of Groups ill, lIB or lllA- VIllA on the periodic table of elements, as currently adopted by the International Union of Pure and Applied Chemistry (!UP AC); wherein the reaction is carried under a pressure of from 14 psia to 3000 psia and at a temperature of from about -10°C to 250°C such that 2,3- dihalopropanol is formed.

Full Text	The present invention relates to a process to make 2,3-dihalopropanol. 2,3-dihalopropanols are usually represented by: Formula I wherein: each "X" is independently a halogen atom; and each "R" is independently a hydrogen atom or an organic group. 2,3- dichloropropanol is the most commonly used member of the class. 2,3-dihalopropanols are important intermediates in the manufacture of epihalohydrin. For instance, epichlorohydrin is usually made by a three-step process of: (1) reacting propylene and chlorine to make allyl chloride; (2) reacting allyl chloride with hypochlorous acid to make a mixture of dichloropropanols; and (3) reacting the dichloropropanols with a strong base to make epichlorohydrin. This process makes large quantities of halogen-containing waste. For each mole of epichlorohydrin which is produced, at least about two moles of molecular chlorine are required. Each molecule of epichlorohydrin contains WE CLAIM: 1. A process to make 2,3-dihalopropanol comprising the step of reacting 2,3-dihalopropanal with molecular hydrogen in the presence of a transition metal-containing catalyst to form 2,3-dihalopropanol; said transition metal selected from any of Groups IB, IIB or IIIA-VIIIA on the periodic table of elements, as currently adopted by the International Union of Pure and Applied Chemistry (IUPAC); wherein the reaction is carried under a pressure of from 14 psia to 3000 psia and at a temperature of from about -10°C to 250°C such that 2,3-dihalopropanol is formed. 2. The process as claimed in claim 1 wherein the 2,3-dihalopropanal is selected from 2,3-dichloropropanal; 2,3-dibromopropanal; 2,3-dichloro-2-methylpropanal and 2,3-dibromo-2-methylpropanal. 3. The process as claimed in claim 1 wherein the hydrogenating agent is a hydrogen source selected form molecular hydrogen and alcohols. 4. The process as claimed in claim 1 wherein the ratio of hydrogenating agent to dihalopropanal is at least 0.6:1. 5. The process as claimed in claim 1 wherein the catalyst is a homogeneous catalyst or a heterogeneous catalyst. 6. The process as claimed in claim 1 wherein the catalyst contains a Group VIIIA metal selected form iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof. 7. The process as claimed in claim 6 wherein the catalyst contains a ruthenium or iridium compound or complex. 8. The process as claimed in claim 1 wherein the catalyst contains a coordinating ligand selected from phosphines, l55-cyclooctadiene (COD), norbornadine (NBD), arsines, stibines, carbon monoxide, ethers, cyclopentadienyl, sulfoxides, and aromatic amines and mixtures thereof. 9. The process as claimed in claim 1 wherein the catalyst is a heterogeneous catalyst which contains a transition metal deposited upon a supporting material selected form carbon, silica, alumina, titania and combinations thereof. 10. The process as claimed in claim 1 wherein the catalyst is present in the reaction mixture at a ratio of 0.001 to 100 moles of catalyst metal for each mole of dihalopropanal. 11. The process as claimed in claim 1 wherein the catalyst is selected from RuCl2 (PPh3)3, RuH (CF3C02) (PPh3)3, RuH (CH3C02) (PPh3)3, RuHCl (PPh3)3, RuCl2 (PPh2-p-tol)3, RuHCl (CO) (PPh3)3, RuCl2 [P(C6H4-m-CH3)3]3, RuCl3/P(p-tol)3, RuCl3 /P(C6H4-p-Cl)3, {RuCl2 [P(C6H4-m-S03Na)3]2}2, RuHCl (PPh3)2 (NBD), RuH2 (PPh3)4, polystyrene supported RuCl2 (PPh3)3, RuHCl (dppe)2, RhCl (PPh3)3, (COD) Ir (PPh2Me)2+ PF6", Ru on carbon, Ru on alumina, Ru on silica, Ir on carbon, Ir on alumina, and Ir on silica, Rh on carbon, Rh on silica, Rh on alumina, Pt on carbon, Pt on silica, Pt on alumina, Pd on carbon, Pd on silica, Pd on alumina, and mixtures thereof. 12. The process as claimed in claim 1 which is carried out at a temperature of 0°C to 200°C. 13. The process as claimed in claim 1 which is carried out with a hydrogen partial pressure of at least 14 psia. 14. The process as claimed in claim 1 wherein the reaction mixture contains a protic solvent selected from water, carboxylic acids, phenolic compounds, aliphatic alcohols and mixtures thereof. 15. The process as claimed in claim 1 wherein the reaction mixture contains an aprotic solvent selected from aromatic hydrocarbons, aliphatic hydrocarbons, ethers, glymes, glycol ethers, and mixtures thereof. 16. The process as claimed in claims 14 or 15 wherein the protic or the aprotic solvent is present in the reaction mixture at a concentration of from 0 to 99.99 weight percent. 17. The process as claimed in claim 1 wherein the reaction mixture contains an acid scavenger selected from alkali metal carbonates, alkali metal bicarbonate, epoxides and mixtures thereof. 18. A process to make epihalohydrin comprising the steps of: (a) reducing 2,3-dihalopropanal as claimed in claim 1 to form 2,3- dihalopropanol; and (b) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is formed. 19. A process to make epihalohydrin comprising the steps of: (a) halogenating acrolein to make 2,3-dihalopropanal; (b) reducing 2,3-dihalopropanal as claimed in claim 1 to form 2,3- dihalopropanol; and (c) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is formed. 20. A process to make epihalohydrin comprising the steps of: (a) reacting a hydrocarbon which contains three carbon atoms with an oxidizing agent to form acrolein; (b) reacting acrolein with a molecular halogen to form 2,3-dihalopropanal; (c) reducing 2,3-dihalopropanal to form 2,3-dihalopropanol as claimed in claim 1 to form 2,3-dihalopropanol; and (c) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is formed.

Full Text

The present invention relates to a process to make 2,3-dihalopropanol. 2,3-dihalopropanols are usually represented by:
Formula I
wherein:
each "X" is independently a halogen atom; and
each "R" is independently a hydrogen atom or an organic group. 2,3-
dichloropropanol is the most commonly used member of the class.
2,3-dihalopropanols are important intermediates in the manufacture of epihalohydrin. For instance, epichlorohydrin is usually made by a three-step process of:
(1) reacting propylene and chlorine to make allyl chloride;
(2) reacting allyl chloride with hypochlorous acid to make a mixture of dichloropropanols; and
(3) reacting the dichloropropanols with a strong base to make epichlorohydrin.
This process makes large quantities of halogen-containing waste. For each mole of epichlorohydrin which is produced, at least about two moles of molecular chlorine are required. Each molecule of epichlorohydrin contains

WE CLAIM:
1. A process to make 2,3-dihalopropanol comprising the step of reacting 2,3-dihalopropanal with molecular hydrogen in the presence of a transition metal-containing catalyst to form 2,3-dihalopropanol; said transition metal selected from any of Groups IB, IIB or IIIA-VIIIA on the periodic table of elements, as currently adopted by the International Union of Pure and Applied Chemistry (IUPAC); wherein the reaction is carried under a pressure of from 14 psia to 3000 psia and at a temperature of from about -10°C to 250°C such that 2,3-dihalopropanol is formed.
2. The process as claimed in claim 1 wherein the 2,3-dihalopropanal is selected from 2,3-dichloropropanal; 2,3-dibromopropanal; 2,3-dichloro-2-methylpropanal and 2,3-dibromo-2-methylpropanal.
3. The process as claimed in claim 1 wherein the hydrogenating agent is a hydrogen source selected form molecular hydrogen and alcohols.
4. The process as claimed in claim 1 wherein the ratio of hydrogenating agent to dihalopropanal is at least 0.6:1.
5. The process as claimed in claim 1 wherein the catalyst is a homogeneous catalyst or a heterogeneous catalyst.
6. The process as claimed in claim 1 wherein the catalyst contains a Group VIIIA metal selected form iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof.

7. The process as claimed in claim 6 wherein the catalyst contains a ruthenium or iridium compound or complex.
8. The process as claimed in claim 1 wherein the catalyst contains a coordinating ligand selected from phosphines, l55-cyclooctadiene (COD), norbornadine (NBD), arsines, stibines, carbon monoxide, ethers, cyclopentadienyl, sulfoxides, and aromatic amines and mixtures thereof.
9. The process as claimed in claim 1 wherein the catalyst is a heterogeneous catalyst which contains a transition metal deposited upon a supporting material selected form carbon, silica, alumina, titania and combinations thereof.

10. The process as claimed in claim 1 wherein the catalyst is present in the reaction mixture at a ratio of 0.001 to 100 moles of catalyst metal for each mole of dihalopropanal.
11. The process as claimed in claim 1 wherein the catalyst is selected from RuCl2 (PPh3)3, RuH (CF3C02) (PPh3)3, RuH (CH3C02) (PPh3)3, RuHCl (PPh3)3, RuCl2 (PPh2-p-tol)3, RuHCl (CO) (PPh3)3, RuCl2 [P(C6H4-m-CH3)3]3, RuCl3/P(p-tol)3, RuCl3 /P(C6H4-p-Cl)3, {RuCl2 [P(C6H4-m-S03Na)3]2}2, RuHCl (PPh3)2 (NBD), RuH2 (PPh3)4, polystyrene supported RuCl2 (PPh3)3, RuHCl (dppe)2, RhCl (PPh3)3, (COD) Ir (PPh2Me)2+ PF6", Ru on carbon, Ru on alumina, Ru on silica, Ir on carbon, Ir on alumina, and Ir on silica, Rh on carbon, Rh on silica, Rh on alumina, Pt on carbon, Pt on silica, Pt on alumina, Pd on carbon, Pd on silica, Pd on alumina, and mixtures thereof.

12. The process as claimed in claim 1 which is carried out at a temperature of 0°C to 200°C.
13. The process as claimed in claim 1 which is carried out with a hydrogen partial pressure of at least 14 psia.
14. The process as claimed in claim 1 wherein the reaction mixture contains a protic solvent selected from water, carboxylic acids, phenolic compounds, aliphatic alcohols and mixtures thereof.
15. The process as claimed in claim 1 wherein the reaction mixture contains an aprotic solvent selected from aromatic hydrocarbons, aliphatic hydrocarbons, ethers, glymes, glycol ethers, and mixtures thereof.
16. The process as claimed in claims 14 or 15 wherein the protic or the aprotic solvent is present in the reaction mixture at a concentration of from 0 to 99.99 weight percent.
17. The process as claimed in claim 1 wherein the reaction mixture contains an acid scavenger selected from alkali metal carbonates, alkali metal bicarbonate, epoxides and mixtures thereof.
18. A process to make epihalohydrin comprising the steps of:
(a) reducing 2,3-dihalopropanal as claimed in claim 1 to form 2,3-
dihalopropanol; and
(b) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is
formed.

19. A process to make epihalohydrin comprising the steps of:
(a) halogenating acrolein to make 2,3-dihalopropanal;
(b) reducing 2,3-dihalopropanal as claimed in claim 1 to form 2,3-
dihalopropanol; and
(c) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is
formed.
20. A process to make epihalohydrin comprising the steps of:
(a) reacting a hydrocarbon which contains three carbon atoms with an oxidizing agent to form acrolein;
(b) reacting acrolein with a molecular halogen to form 2,3-dihalopropanal;
(c) reducing 2,3-dihalopropanal to form 2,3-dihalopropanol as claimed in claim
1 to form 2,3-dihalopropanol; and
(c) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is formed.

Documents:

1323-mas-1997- abstract.pdf

1323-mas-1997- assignment.pdf

1323-mas-1997- claims duplicate.pdf

1323-mas-1997- claims original.pdf

1323-mas-1997- correspondence others.pdf

1323-mas-1997- correspondence po.pdf

1323-mas-1997- description complete duplicate.pdf

1323-mas-1997- description complete original.pdf

1323-mas-1997- form 1.pdf

1323-mas-1997- form 26.pdf

1323-mas-1997- form 3.pdf

1323-mas-1997- form 4.pdf

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Patent Number

207656

Indian Patent Application Number

1323/MAS/1997

PG Journal Number

27/2007

Publication Date

06-Jul-2007

Grant Date

19-Jun-2007

Date of Filing

18-Jun-1997

Name of Patentee

M/S. DOW GLOBAL TECHNOLOGIES INC

Applicant Address

WASHINGTON STREET, 1790 BUILDING, MIDLAND, MICHIGAN 48674.

Inventors:

#	Inventor's Name	Inventor's Address
1	P.J.THOMAS	4310 ANDRE STREET, MIDLAND, MICHIGAN 48642.
2	R. GARTH PEWS	4403 ANDRE STREET, MIDLAND, MICHIGAN 48642.
3	PAUL C. VOSEJPKA	706 EAST CHIPPEWA RIVER ROAD, MIDLAND, MICHIGAN 48640.
4	GEORGE J. FRYCEK	3530 JANE DRIVE, MIDLAND, MICHIGAN 48642.

PCT International Classification Number

C07C31/36

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	00103429.7	1999-04-01	Argentina