Process to make 2,3-dihalopropanols

• US 5,744,655 A
• Filed: 06/19/1996
• Issued: 04/28/1998
• Est. Priority Date: 06/19/1996
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Frycek, George J., Vosejpka, Paul C., Thomas, P. J., Pews, R. Garth
• Primary Examiner(s): Geist, Gary
• Assistant Examiner(s): Puttlitz, Jr., Karl J.
• Application Number:
  US08/667,526
• Time in Patent Office: 678 Days
• Field of Search: 568/840, 568/841, 568/842, 502/326
• US Class Current: 568/841
• CPC Class Codes: C07C 29/141 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/36 the halogen not being fluorine
• CPC Class Codes: C07C 45/35 in propene or isobutene
• CPC Class Codes: C07C 45/63 by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• CPC Class Codes: C07C 47/14 containing halogen
• CPC Class Codes: C07C 47/22 Acryaldehyde; Methacryaldehyde
• CPC Class Codes: C07D 301/26 Y being hydrogen
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

A 2,3-dihalopropanol is made by reacting 2,3-dihalopropanal with a hydrogenating agent in the presence of a transition metal-containing catalyst, under conditions such that 2,3-dihalopropanol is formed. The reaction is particularly useful as Step (3) in a process to make epihalohydrin by:

(1) reacting a 3-carbon hydrocarbon with an oxidizing agent to form acrolein;

(2) reacting acrolein with a molecular halogen to form 2,3-dihalopropanal;

(3) reducing 2,3-dihalopropanal to form 2,3-dihalopropanol; and

(4) cyclizing 2,3-dihalopropanol to make epihalohydrin.

The process produces epihalohydrin using only about one mole of halogen per mole of epihalohydrin. It also uses substantially less water than existing processes.

Claims

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, under conditions such that 2,3-dihalopropanol is formed.

2. The process as described in claim 1 wherein the catalyst contains a Group VIIIA metal.

3. The process as described in claim 2 wherein the catalyst contains ruthenium.

4. The process as described in claim 3 wherein the catalyst contains a ruthenium salt.

5. The process as described in claim 3 wherein the catalyst further contains a stabilizing ligand associated with the ruthenium compound.

6. The process of claim 5 wherein the ligand is a phosphine.

7. The process of claim 3 wherein the catalyst is a heterogeneous catalyst which contains ruthenium deposited upon a supporting material.

8. The process of claim 3 wherein the reaction mixture further contains water or a protic organic compound.

9. The process of claim 8 wherein the reaction mixture contains an alkanol which contains 1 to 12 carbon atoms.

10. The process of claim 8 wherein the reaction mixture contains water.

11. The process of claim 10 wherein the pH of the reaction mixture is at least about 5.

12. The process of claim 8 wherein the mixture further contains an additional aprotic solvent.

13. The process of claim 8 wherein the reaction mixture contains an acid scavenger.

14. The process of claim 13 wherein the acid scavenger is epichlorohydrin.

15. The process of claim 1 which is carried out at a temperature of about 0°

C. to 200°

C.

16. The process of claim 1 wherein the 2,3-dihalopropanal is unsubstituted 2,3-dichloropropanal.

17. A process of claim 1 comprising the step of contacting a 2,3-dihalopropanal with at least a stoichiometric quantity of molecular hydrogen in the presence of a ruthenium-containing catalyst and an alcohol, wherein the molar ratio of alcohol to dichloropropanal is no more than 5:

1 or wherein the mixture further contains an acid scavenger.

18. A process of claim 1 comprising the step of contacting a 2,3-dihalopropanal with at least a stoichiometric quantity of hydrogen in the presence of a ruthenium-containing catalyst and water.

19. A process to make epihalohydrin comprising the steps of:

(a) halogenating acrolein to make 2,3-dihalopropanal;

(b) reducing-the 2,3-dihalopropanal as described in claim 18 to form 2,3-dihalopropanol; and

(c) contacting the 2,3-dihalopropanol with a base, whereby an epihalohydrin is formed.