Synthesis of vicinal difluoro aromatics and intermediates thereof

• US 6,894,200 B2
• Filed: 02/03/2003
• Issued: 05/17/2005
• Est. Priority Date: 01/23/2001
• Status: Expired due to Term

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Taege, Reiner, Lal, Gauri Sankar, Hayes, Kathryn Sue, Klauck-Jacobs, Axel, Casteel, William
• Primary Examiner(s): SHAMEEM, GOLAM M
• Application Number:
  US10/357,897
• Publication Number:
  US 20030149315A1
• Time in Patent Office: 834 Days
• Field of Search: 570/123, 570/143
• US Class Current: 570/143
• CPC Class Codes: C07B 39/00 Halogenation
• CPC Class Codes: C07C 17/18 of oxygen atoms of carbonyl groups
• CPC Class Codes: C07C 17/23 by dehalogenation
• CPC Class Codes: C07C 23/18 Polycyclic halogenated hydrocarbons
• CPC Class Codes: C07C 25/22 with condensed rings
• CPC Class Codes: C07C 45/512 the singly bound functional group being a free hydroxyl group
• CPC Class Codes: C07C 49/697 containing six-membered aromatic rings

Abstract

A method of preparing vicinal difluoro aromatic compounds in high yield from hydroxy aromatic compounds using various bases and a method of preparing intermediates thereof. A method for making a vicinal difluoro halogenated aromatic compound including providing a tetrafluoro derivative of a halogen substituted aromatic compound, wherein the tetrafluoro derivative has two fluorine atoms on each of two adjacent carbons and at least one additional halogen substituent; reacting the tetrafluoro derivative with a reducing agent in presence of a base for a reaction time sufficient to form the vicinal difluoro halogenated aromatic compound containing two vicinal fluorine substituents and the at least one additional halogen substituent, wherein the reducing agent is used in a reducing agent effective amount sufficient to retain the at least one additional halogen substituent.

Claims

1. A method for making an aromatic compound having two vicinal fluorine atoms, wherein said aromatic compound is selected from the group consisting of monocyclic aromatic ring, bicyclic separate aromatic rings, bicyclic fused aromatic rings tricyclic separate aromatic rings, tricyclic fused aromatic rings and mixtures thereof, comprising:

mixing a tetrafluoro derivative of an aromatic compound with a reducing agent in a presence of a base for a time needed to form an aromatic compound containing two vicinal fluorine atoms, said tetrafluoro aromatic compound having two fluorine atoms on each of two adjacent carbons on the ring.

2. The method of claim 1, wherein the tetrafluoro derivative of a halogen substituted aromatic compound is mixed with an organic solvent.

3. The method of claim 2, wherein said organic solvent is a member selected from the group consisting of tetrahydrofuran, methyl tert-butyl ether, acetonitrile, ethanol, and dimethylformamide.

4. The method of claim 1, wherein the base is ammonium hydroxide, hydroxylamine, hydrazine, or a substituted ammonium hydroxide.

5. The method of claim 4, wherein the substituted ammonium hydroxide is a member selected from the group consisting of tetramethylammonium hydroxide, ethyl ammonium hydroxide, and benzyltrimethyl ammonium hydroxide.

6. The method of claim 5, wherein the substituted ammonium hydroxide is tetramethylammonium hydroxide.

7. The method of claim 4, wherein the base is buffered to maintain a pH below 14.

8. The method of claim 1, wherein the reducing agent is present at −

25 to 90°

C.

9. The method of claim 1, wherein the aromatic compound having two vicinal fluorine atoms is a vicinal difluoro halogenated aromatic compound.

10. The method of claim 1, wherein a ring of the aromatic compound contains a heteroatom selected from the group consisting of oxygen, nitrogen, sulfur and mixtures thereof.

11. The method of claim 1, wherein a ring of the aromatic compound contains a substitution selected from the group consisting of halogen atom, a C₁ to C₂₀ alkyl, a C₅-C₁₀ cycloalkyl, a C₆ to C₁₂ aryl, an amino, a nitro, a C₁ to C₁₀ alkyl ether or thioether, a C₁ to C₁₀ alkyl ester, a CF₃, a R′

SO₂O,

where R′

is CF₃, a C₁ to C₂₀ alkyl, a substituted or unsubstituted C₅ to C₁₀ cycloalkyl, or a substituted or unsubstituted C₆ to C₁₂ aryl, in which the substitution on the cycloalkyl or aryl can be a C₁ to C₂₀ alkyl or a C₅ to C₈ cycloalkyl;

R″

is a C₁-C₁₀ saturated or unsaturated alkyl;

x is an integer from 0 to 10, and y is an integer from 0 to 10, and mixtures thereof.