Process for preparing and recovering 4,4'-dihydroxy-alpha-alkylstilbene or 4,4'-dihydroxy-alpha, alpha'dialkylstilbene

• US 5,723,693 A
• Filed: 09/13/1996
• Issued: 03/03/1998
• Est. Priority Date: 09/13/1996
• Status: Expired due to Fees

• Current Assignee: Michigan Molecular Institute
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Hefner, Robert E. Jr., Carr, David A.
• Primary Examiner(s): Dees, Jose G.
• Assistant Examiner(s): BADIO, BARBARA P
• Application Number:
  US08/713,906
• Time in Patent Office: 536 Days
• Field of Search: 568/724, 568/729
• US Class Current: 568/729
• CPC Class Codes: C07C 37/002 by transformation of a functional group, e.g. oxo, carboxyl
• CPC Class Codes: C07C 37/20 using aldehydes or ketones
• CPC Class Codes: C07C 37/84 by crystallisation
• CPC Class Codes: C07C 39/215 containing , e.g. diethylstilbestrol
• CPC Class Codes: C07C 39/367 polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes

Abstract

A process for preparing a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene which includes the steps of (A) reacting at a temperature of from -20° C. to 20° C. a mixture of: (1) at least one alpha-haloketone; (2) at least one compound containing one phenolic hydroxyl group or aromatic alkoxy group per molecule such that the mole ratio of phenolic hydroxyl group-containing or aromatic alkoxy group-containing compound(s):alpha-haloketone(s) is at least 0.1:1; and (3) either (a) at least one strong protonic acid or (b) at least one Lewis acid, or (c) any combination thereof; thereby forming a reaction product containing at least one halogen-containing bisphenol compound which, upon being dehydrohalogenated, forms a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha, alpha'"'"'-dialkylstilbene; (B) reducing the acid content of the product resulting from step (A) to less than 10,000 ppm; (C) dehydrohalogenating the product obtained from step (B), thereby forming a dehydrohalogenated product containing 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene; (D) adding water to the product of step (C) in amounts sufficient to crystallize at least a portion of the, 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene and recovering the crystals and the remaining organic phase separately; (E) independently repeating steps (A), (B), and (C) to obtain a dehydrohalogenated product; (F) mixing at least a portion of organic phase obtained in step (D) with the product obtained in step (E); and (G) adding water to the mixture obtained in step (F) in amounts sufficient to crystallize at least a portion of the 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene and recovering the crystals.

Claims

1. A process for preparing a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene which comprises:

(A) reacting at a temperature of from -20°

C. to 20°

C. a mixture of;

(1) at least one alpha-haloketone;

(2) at least one compound containing one phenolic hydroxyl group or aromatic alkoxy group per molecule such that the mole ratio of phenolic hydroxyl group-containing or aromatic alkoxy group-containing compound(s);

alpha-haloketone(s) is at least 0.1;

1; and

(3) either (a) at least one strong protonic acid or (b) at least one Lewis acid, or (c) any combination thereof;

such that the mole ratio of phenolic hydroxyl group-containing or aromatic alkoxy group-containing compound(s);

alpha-haloketone(s);

strong protonic acid(s) or Lewis acid(s) or combination thereof is from 0.1;

1;

0.0026 to 20;

1;

8;

thereby forming a reaction product containing at least one halogen-containing bisphenol compound which, upon being dehydrohalogenated, forms a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

(B) reducing the acid content of the product resulting from step (A) to less than 10,000 ppm;

(C) dehydrohalogenating the product obtained from step (B), thereby forming a dehydrohalogenated product containing 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

(D) adding water to the product of step (C) in amounts sufficient to crystallize at least a portion of the 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene and recovering the crystals and the remaining organic phase separately;

(E) independently repeating steps (A), (B), and (C) to obtain a dehydrohalogenated product;

(F) mixing at least a portion of organic phase obtained in step (D) with the product obtained in step (E); and

(G) adding mater to the mixture obtained in step (F) in amounts sufficient to crystallize at least a portion of the 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene and recovering the crystals.

2. The process of claim 1 wherein step (A) comprises reacting a temperature of from -15°

C. to +10°

C. a mixture of;

(1) chloroacetone;

(2) phenol in amounts such that the mole ratio of phenol;

chloroacetone 2.1;

1 to 15;

1;

(3) sulfuric acid or methanesulfonic acid, such that the mole ratio of phenol;

chloroacetone;

sulfuric acid or methanesulfonic acid is in the range of from 2.1;

1;

1 to 15;

1;

4; and

(4) optionally, methylene chloride.

3. The process of claim 2 wherein step (A) is carried out at a temperature of from -13°

C. to 0°

C. and in the presence of methylene chloride.

4. The process of claim 1 wherein the organic phase used in (F) has been stripped by distillation to remove at least 20 percent by weight of the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

5. The process of claim 4 wherein the organic phase used in (F) has been stripped by distillation to remove at least 80 percent of the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

6. The process of claim 5 wherein the organic phase used in (F) has been stripped by distillation to remove the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

7. The process of claim 4 wherein the phenolic hydroxyl group-containing compound removed by distillation is used as a reactant in step (A)(2).

8. The process of claim 4 wherein a basic-acting compound is added to the organic phase prior to stripping via distillation.

9. The process of claim 8 wherein the basic-acting compound is sodium bicarbonate.

10. The process of claim 4 wherein said organic phase is additionally subjected to thermal, catalytic or thermocatalytic conditions which dedimerize all or a part of the dimeric coproducts contained in said organic phase prior to recycle.

11. A process for preparing a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene which comprises:

(A) reacting at a temperature of from -20°

C. to 20°

C. a mixture of;

(1) at least one alpha-haloketone;

(2) at least one compound containing one phenolic hydroxyl group or aromatic alkoxy group per molecule such that the mole ratio of phenolic hydroxyl group-containing or aromatic alkoxy group-containing compound(s);

alpha-haloketone(s) is at least 0.1;

1; and

(3) either (a) at least one strong protonic acid or (b) at least one Lewis acid, or (c) any combination thereof;

such that the mole ratio of phenolic hydroxyl group-containing or aromatic alkoxy group-containing compound(s);

alpha-haloketone(s);

strong protonic acid(s) or Lewis acid(s) or combination thereof is from 0.1;

1;

0.0026 to 20;

1;

8;

thereby forming a reaction product containing at least one halogen-containing bisphenol compound which, upon being dehydrohalogenated, forms a 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

(B) reducing the acid content of the product resulting from step (A) to less than 10,000 ppm;

(C) dehydrohalogenating the product obtained from step (B), thereby forming a dehydrohalogenated product containing 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

(D) adding water to the product of step (C) in amounts sufficient to crystallize at least a portion of the 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

(E) recovering the crystals and the remaining organic phase separately;

(F) independently repeating steps (A), (B), (C), and (D) to obtain an aqueous slurry containing crystallized 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene;

mixing at least a portion of the organic phase obtained in step (D) with the slurry obtained in step (F) under conditions sufficient to crystallize at least a portion of the 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene present in the organic phase obtained in step (D); and

recovering the crystals of 4,4'"'"'-dihydroxy-alpha-alkylstilbene or 4,4'"'"'-dihydroxy-alpha,alpha'"'"'-dialkylstilbene.

12. The process of claim 11 wherein step (A) comprises reacting a temperature of from -15°

C. to +10°

C. a mixture of;

(1) chloroacetone;

(2) phenol in amounts such that the mole ratio of phenol;

chloroacetone 2.1;

1 to 15;

1;

(3) sulfuric acid or methanesulfonic acid, such that the mole ratio of phenol;

chloroacetone;

sulfuric acid or methanesulfonic acid is in the range of from 2.1;

1;

1 to 15;

1;

4; and

(4) optionally, methylene chloride.

13. The process of claim 12 wherein step (A) is carried out at a temperature of from -13°

C. to 0°

C. and in the presence of methylene chloride.

14. The process of claim 11 wherein the organic phase used in (F) has been stripped by distillation to remove at least 20 percent by weight of the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

15. The process of claim 14 wherein the organic phase used in (F) has been stripped by distillation to remove at least 80 percent of the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

16. The process of claim 15 wherein the organic phase used in (F) has been stripped by distillation to remove the phenolic hydroxyl group-containing compound or aromatic alkoxy group-containing compound.

17. The process of claim 14 wherein the phenolic hydroxyl group-containing compound removed by distillation is used as a reactant in step (A)(2).

18. The process of claim 14 wherein a basic-acting compound is added to the organic phase prior to stripping via distillation.

19. The process of claim 18 wherein the basic-acting compound is sodium bicarbonate.

20. The process of claim 14 wherein said organic phase is additionally subjected to thermal, catalytic or thermocatalytic conditions which dedimerize all or a part of the dimeric coproducts contained in said organic phase prior to recycle.