# US 5,705,713 A · Preparation of fluoro compounds

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- Number: US 5,705,713 A
- Document ID: US5705713A
- Status: Granted
- Kind: A
- Application number: 08/545,844
- Filed: 1995-12-12
- Granted: 1998-01-06
- Earliest claimed: 1993-05-12
- Assignees: Rhone-Poulenc Chemicals Limited
- Inventors: Owen Ross Chambers; Patrick Charles Youmans
- Web page: https://patentgrep.com/patent/US5705713A

## CPC

- C07H 13/08: having the esterifying carboxyl radicals directly attached to carbocyclic rings
- C07H: SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS (derivatives of aldonic or saccharic acids C07C, C07D; aldonic acids, saccharic acids C07C59/105, C07C59/285; cyanohydrins C07C255/16; glycals C07D; compounds of unknown constitution C07G; polysaccharides, derivatives thereof C08B; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; sugar industry C13)

## Abstract

Fluoro compounds are made by reaction of an activated oxy-acid ester or cyclic ether starting material with hydrogen fluoride in the presence of an organometallic compound.

## Claims

### Claim 1

Process for the preparation of a fiuoro-compound by reaction of a reactive oxy-acid ester or a reactive cyclic ether other than an anhydrouridine with hydrogen fluoride wherein the reaction is carried out under anhydrous conditions in the presence of an organometallic compound of formula:
MY.sub.m Z.sub.n (I)
where M is a 4-, 6-, or 8-coordinated metal wherein said metal is iron, Y is a monodentate ligand, Z is a bidentate ligand or a cyclopentadienyl ligand, and m and n are each zero or positive integers such that (m +2 n)=4, 6 or 8.

### Claim 2 (depends on 1)

Process according to claim 1 in which a reactive oxy-acid ester of formula:
R.sub.1 R.sub.2 CHOX (II)
is converted into a fluoride of formula:
R.sub.2 R.sub.2 CHF (III)
wherein X is a sulphonic acid residue and R.sub.1 and R.sub.2 are each hydrogen or alkyl of 1 to 6 carbon atoms, said alkyl radicals being optionally linked to form a 4 to 7 membered ring and being unsubstituted or substituted by phenyl, halogen, hydroxy, or alkoxy of 1 to 6 carbon atoms.

### Claim 3 (depends on 2)

Process according to claim 2 in which --OX is a tosylate, mesylate, triflate, or imidazole-sulfonate residue.

### Claim 4 (depends on 1)

Process according to claim 1 in which an epoxide compound of formula: ##STR12## is converted into a .beta.-hydroxy-fluoro-compound of formula: ##STR13## where R.sub.5, R.sub.6, R.sub.7, R.sub.8 may be the same or different, and each represents hydrogen or alkyl of 1 to 12 carbon atoms, optionally linked to form a 4- to 7- membered ring and unsubstituted or substituted by alkyl, aryl or aralkyl substitutents.

### Claim 5 (depends on 1)

Process according to claim 1 wherein for said organometallic compound, Y is halogen, alkoxy of 1 to 4 carbon atoms which may be halogenated, or phenoxy optionally substituted by alkyl of 1 to 4 carbon atoms, halogen, or nitro, and Z is a carboxylato radical derived from an alkanoic acid of up to 12 carbon atoms which may be halogenated or from benzoic acid optionally substituted by alkyl or 1 to 4 carbon atoms, halogen or nitro, a radical derived from an alkanesulphonic acid of 1 to 12 carbon atoms, or a .beta.-diketo residue of a compound of formula: R'--COCH.sub.2 CO--R", where R' is alkyl or haloalkyl of 1 to 4 carbon atoms and R" is hydrogen, hydroxy, alkoxy of 1 to 4 carbon atoms, or alkyl or haloalkyl of 1 to 4 carbon atoms, or a cyclopentadienyl ligand.

### Claim 6 (depends on 5)

Process according to claim 5 in which m is O, n is 3 and Z is a said .beta.-diketo residue.

### Claim 7 (depends on 6)

Process according to claim 6 in which Z is acetylacetonato.

### Claim 8 (depends on 1)

Process according to claim 1 wherein the reaction is carried out in the presence of an inert organic solvent.

### Claim 9 (depends on 8)

Process according to claim 8 in which said solvent is 1,4-dioxane, tetrahydrofuran, 1,2-dimethoxyethane, or bis(2-methoxyethyl)ether.

### Claim 10 (depends on 1)

Process according to claim 1 wherein 2 to 20 moles of hydrogen fluoride are used per mole of starting material.

### Claim 11 (depends on 1)

Process according to claim 1 wherein 0.5 to 2.0 moles of said organometallic compound are used per mole of starting material.

### Claim 12 (depends on 1)

Process according to claim 1 wherein the reaction is operated at 50.degree. to 150.degree. under autogenous pressure.

### Claim 13 (depends on 1)

Fluoro-compounds prepared by the process as claimed in claim 1.

### Claim 14 (depends on 2)

Fluoro-compounds prepared by the process as claimed in claim 2.

### Claim 15 (depends on 4)

Fluoro-compounds prepared by the process as claimed in claim 4.

### Claim 16 (depends on 5)

Fluoro-compounds prepared by the process as claimed in claim 5.