# US 5,349,099 A · Process for preparing intermediates for the synthesis of antifungal agents

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 5,349,099 A
- Document ID: US5349099A
- Status: Granted
- Kind: A
- Application number: 08/166,332
- Filed: 1993-12-13
- Granted: 1994-09-20
- Earliest claimed: 1993-12-13
- Assignees: Schering Corporation
- Inventors: Shen-Chun Kuo; Donald Hou; Zheng-Yun Zhan
- Web page: https://patentgrep.com/patent/US5349099A

## CPC

- C07C 33/20: monocyclic
- C07C 17/14: in the side-chain of aromatic compounds
- C07C 17/35: by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C 25/24: Halogenated aromatic hydrocarbons with unsaturated side chains
- C07C 29/40: with compounds containing carbon-to-metal bonds
- C07C 29/64: by simultaneous introduction of -OH groups and halogens
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Disclosed is a process for preparing allylic halides of the formula I ##STR1## wherein X is Cl, Br or I, for use as intermediates in the synthesis of substituted tetrahydrofuran azole anti-fungal agents.

## Claims

### Claim 1

A process for preparing allylic halide compounds of the formula ##STR21## wherein X is Cl, Br or l, comprising dehydrating a tertiary alcohol of the formula ##STR22## by heating in the presence of an acid to form an olefin of the formula ##STR23## and treating the olefin with a halogenating agent to form the allylic halide.

### Claim 2 (depends on 1)

The process of claim 1 wherein the acid for dehydration of the tertiary alcohol is p-toluenesulfonic acid or H.sub.2 SO.sub.4.

### Claim 3 (depends on 2)

The process of claim 2 wherein the halogenating agent is selected from N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydantoin.

### Claim 4 (depends on 3)

The process of claim 3 wherein the halogenating agent is used in the presence of a catalyst.

### Claim 5 (depends on 4)

The process of claim 4 wherein the catalyst is azobisisobutyronitrile or an organic peroxide.

### Claim 6 (depends on 5)

The process of claim 5 wherein the organic peroxide is benzoyl peroxide.

### Claim 7 (depends on 2)

The process of claim 2 wherein the halogenating agent is used in the presence of water, to form a halohydrin of the formula ##STR24## wherein X is Br, Cl or l, and the halohydrin is dehydrated by heating in the presence of an acid to form the allylic halide.

### Claim 8 (depends on 7)

The process of claim 7 wherein the halogenating agent is selected from N-chlorosuccinimide, N-bromosuccinimide or l.sub.2.

### Claim 9 (depends on 8)

The process of claim 8 wherein the acid for dehydrating the halohydrin is p-toluenesulfonic acid.

### Claim 10 (depends on 1)

The process of claim 1 wherein the tertiary alcohol is prepared by reacting 2',4'-difluoroacetophenone with a methylating agent.

### Claim 11 (depends on 10)

The process of claim 10 wherein the methylating agent is CH.sub.3 MgBr, or methyllithium.