Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1995-01-24
1996-06-18
Killos, Paul J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
568 16, C07F 902
Patent
active
055279600
DESCRIPTION:
BRIEF SUMMARY
This invention relates to fluorinating reagents needed for producing compounds containing fluorine which are important as medicines and their intermediates and to the method of fluorination which uses the fluorinating reagent.
PRIOR ART
As reagents and methods of fluorinating an alcoholic hydroxyl group, following methods shown in (1) to (5) have been known so far.
(1) A method of fluorinating a hydroxyl group in secondary alcohol or tertiary alcohol by using HF or HF/pyridine solution (M. Hudlioky, "Chemistry of Organic Fluorine Compounds", 2nd ed., Ellis Hotwood Ltd. 1976, page 689: G. A. Olah et al., Synthesis, 1973, page 786).
(2) A method in which after a hydroxyl group in alcohol is converted to an ester of sulfonio acid, the ester is fluorinated by making it react with alkalimetal fluoride including KF (M. Hudlicky, "Chemistry of Organic Fluorine Compounds", 2nd ed., Ellis Horwood Ltd. 1976, page 689).
(3) A method of fluorinating a hydroxyl group by using fluoroalkylamine as a fluorinating reagent which is obtained from the reaction of secondary amine with ohlorotrifluoroethylene or hexafluoropropene (E. D. Bergmann et al., Isr. J. Chem., Vol. 8, page 925, 1970: Ishikawa et al., "Chemistry of Organic Synthesis", Vol. 37, No.7, page 607, 1979).
(4) A method of fluorinating a hydroxyl group by using diethylamino sulfur trifluoride (DAST) as a fluorinating reagent (W. J. Middleton et al., "Org. Synthesis", Vol. 57, page 50, 1977).
(5) A method of fluorinating a hydroxyl group by using as a fluorinating reagent difluorotriphenyl-phosphorane from the reaction of triphenylphosphine with sulfur tetrafluoride (Kobayashi et al., "Chem. Pharm. Bull." (Tokyo), Vol. 16, page 1009, 1968).
The inventor of this invention studied new fluorinating reagents, especially those containing phosphorus, in place of the above-mentioned well-known fluorinating reagents.
It is not easy to prepare the fluorinating reagent described in the above (5), because very poisonous and corrosive sulfur tetra-fluoride must be used as a raw material.
OBJECTS OF THE INVENTION
The object of this invention is to offer fluorinating reagents containing phosphorus which can be easily and safely synthesized.
Another object of this invention is to offer a method of efficiently fluorinating an alcoholic hydroxyl group by using the fluorinating reagent containing phosphorus.
THE CONSTITUTION OF THE INVENTION
As a result of eagerly repeating searches and studies of the above-mentioned fluorinating reagents which contain phosphorus and are easy to prepare, the inventor found that fluoro-(1-pentafluoro-1-propenyl)-tributyl phosphorane (hereinafter abbreviated FPTBP) obtained from the reaction of hexafluoropropene (hereinafter abbreviated HFP) with tributyl phosphine (hereinafter abbreviated TBP) could be used as a fluorinating reagent to fluorinate an alcoholic hydroxyl group, having reached the success of completing this invention.
That is, this invention relates to fluorinating reagents (e.g. FPTBP) expressed in a general formula; ##STR2##
(In the general formula, R is an alkyl group having 1 to 5 carbons or a dialkyl-amino group in which each alkyl group has 1 to 3 carbons.)
This invention also offers a fluorinating method that is characteristic of substituting fluorine for the above-mentioned alcoholic hydroxyl group by the reaction of the fluorinating reagent and an organic compound containing an alcoholic hydroxyl group.
A fluorinating reagent in this invention, FPTBP, for example, is easily produced by the reaction of TBP and HFP in such a solvent as methylene ohioride, diethyl ether, and diethylene glycol dimethyl ether (See D. J. Burton et al., "J. Fluorine Chem." Vol 44 page 167, 1989).
In this case, several ways can be taken, such as a way in which HFP is blown into TBP dissolved in a solvent to make them react, a reaction under normal pressure in which HFP is put into after being condensated by cooling and is made react with TBP, and a way that after putting a solvent and TBP into an autoclave HFP is introduced under pressure to
REFERENCES:
Chem Abst (CA) 93: 167763 1980.
CA 91: 123804 1979.
CA 111: 23589 1988.
CA 110: 192925 1988.
CA 105: 209036 1985.
CA 103: 105059 1985.
Daikin Industries Ltd.
Killos Paul J.
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