Process for the production of fluorinated organic compounds...

Details Process for the production of fluorinated organic compounds... Process for the production of fluorinated organic compounds...

2002-12-10

2004-08-31

Price, Elvis O. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Halogen containing

C570S161000, C570S123000, C570S140000, C570S141000, C570S142000, C570S143000, C570S144000, C570S145000, C570S146000, C570S147000, C570S148000, C570S149000, C570S153000, C570S154000, C570S159000, C570S162000, C570S164000, C570S165000, C570S166000

Reexamination Certificate

active

06784327

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process for fluorinating an organic compound having a hydrogen atom or hydrogen atoms using IF
5
.
BACKGROUND ART
The following are known as fluorinating agents for fluorinating organic compounds: HF, KF, IF, IF
5
, tetrabutylammonium fluoride, tris(dimethylamino)sulfur(trimethylsilyl)difluoride (TASF), SF
4
, diethylaminosulfurtrifluoride (DAST), fluorine gas, XeF
2
, CF
3
OF, CH
3
COOF, ClO
3
F, N-fluoropyridinium triflate, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), 1-hydroxy-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), N-fluorobenzenesulfonimide, etc. (Sheppard, W. A.; Sharts, C. M. Organic Fluorine Chemistry, 1969, W. A. Benjamin.: Chambers, R. D.; Fluorine in Organic Chemistry, 1973, Wiley-Interscience.: Hudlicky, M. Chemistry of Organic Fluorine Compounds, 1976, Ellis Horwood.: Hudlicky; M. and Pavlath, A. E., Chemistry of Organic Fluorine Compounds II, 1995, ACS Monograph 187.: N. Ishikawa and Y. Kobayashi, Fluorinated compounds-Chemistry and their application, 1979, Kodansha Ltd.: Outline of chemistry/New fluorine chemistry, 1980, Japan Scientific Societys Press: N. Ishikawa, T. Kitazume, and A. Takaoka, Journal of the Society of Synthetic Organic Chemistry, 1979, 37, 606.: T. Umemoto, Journal of the Society of Synthetic Organic Chemistry, 1992, 50, 338: S. D. Taylor, C. C. Kotoris, and G. Hum; Tetrahedron, 1999, 55, 12431: Japanese Unexamined Patent Publication No. 1997-227531, etc.)
Among those fluorinating agents, HF, KF, IF, tetrabutylammonium fluoride, and sulfoniumsilicate (TASF) have low reactivity, and therefore have limited uses. SF
4
is a toxic gas having a boiling point at −40.4° C., which is difficult to handle. Fluorine gas is so active that it is difficult to control its reaction. Furthermore, it is reported that CF
3
OF, CH
3
COOF, and ClO
3
F are explosive gases and should be handled with caution. Diethylaminosulfurtrifluoride (DAST), XeF
2
, N-fluoropyridinium triflate, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), 1-hydroxy-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), N-fluorobenzenesulfonimide, etc., are easy to handle and enable selective fluorination; however, they are expensive reagents and this causes a problem in using them for industrial purposes.
IF
5
is an industrially usable fluorinating agent that is a nonexplosive and easy-to-handle liquid having a boiling point at 100.5° C. and a melting point at 9.4° C. Fluorination using IF
5
is employed only in a process of adding IF to perfluoroolefin and substituting iodine of the perfluoroiodoolefin with fluorine (M. Sakai, Organic Fluorine Chemistry I, 1970, pp348-351, GIHODO SHUPPAN Co., Ltd.: A. A. Banks, H. J. Haszeldine, and V. Kerrigan, J. Chem. Soc., 1948, 2188.: R. D. Chambers, W. K. R. Musgrave, and J. Savory, J. Chem. Soc., 1961, 3779.). However, since it is difficult to control its high oxidizing property, using IF
5
for fluorinating organic compounds that have hydroxyl groups, carbonyl groups, etc., was hitherto not known.
DISCLOSURE OF THE INVENTION
The inventors of the present invention conducted extensive research on the above problems. Consequently, they found that various kinds of organic compounds having hydrogen atoms could be fluorinated by using IF
5
.
Specifically, the present invention relates to the following Items 1 to 12.
Item 1. A method for producing a fluorinated organic compound by fluorinating an organic compound having hydrogen atoms in the presence of IF
5
.
Item 2. The method for producing a fluorinated organic compound according to Item 1, wherein the organic compound having hydrogen atoms is fluorinated in the presence of IF
5
and HF.
Item 3. The production method according to Item 1, wherein the organic compound having hydrogen atoms is reacted in the presence of IF
5
, HF, and an organic base and/or a room temperature molten salt.
Item 4. The production method according to Item 1, wherein the organic compound having hydrogen atoms is reacted in the presence of IF
5
and a room temperature molten salt.
Item 5. The production method according to Item 1, wherein the fluorination reaction does not comprise substitution of bromine or iodine with fluorine, nor an addition reaction of iodine fluoride (IF) to a double bond or triple bond.
Item 6. The production method according to Item 5, wherein the fluorination reaction is conducted in the presence of IF
5
and at least one member selected from the group consisting of acids, salts, and additives.
Item 7. The production method according to Item 5, wherein the fluorination reaction is conducted in the presence of IF
5
and at least one member selected from the group consisting of bases, salts, and additives.
Item 8. A fluorinating agent for use in fluorinating an organic compound having hydrogen atoms, which comprises IF
5
, HF, and an organic base and/or a room temperature molten salt.
Item 9. A fluorinating agent for use in fluorinating an organic compound having hydrogen atoms, which comprises IF
5
and a room temperature molten salt.
Item 10. A fluorinating agent for use in fluorinating an organic compound having hydrogen atoms, which comprises IF
5
and at least one member selected from the group consisting of acids, salts, and additives.
Item 11. A fluorinating agent for use in fluorinating an organic compound having hydrogen atoms, which comprises IF
5
and at least one member selected from the group consisting of bases, salts, and additives.
Item 12. A fluorinating agent for use in fluorinating an organic compound having hydrogen atoms, which comprises IF
5
, HF, and triethylamine.
In the present invention, examples of a organic compound having hydrogen atoms include; compounds having an OH group; ketones (including diketone, &bgr;-ketocarboxylic acid, &bgr;-ketoester); aldehydes; Schiff base, hydrazone and like imines; esters; sulfides; olefins or epoxy; aromatic compounds (phenylhydrazine derivatives, phenol derivatives, 2-naphthol derivatives, aniline derivatives); and thiocarbonyl compounds, etc.
In fluorine substitution in a organic compound having hydrogen atoms, the following atom and groups are substituted with fluorine: hydrogen atom (CH→CF), carbonyl group (CO→CF
2
), hydrazino group (Ph—NHNH
2
→Ph—F; C═N—NH
2
→CF
2
), hydroxyl group (C—OH→C—F), epoxy group (C—O—→C—F), etc.
(1) Compounds having an OH Group
The following reactions are exemplified:
R
1
—OH→R
1
—F  (a)
R
1a
—CH═CH—CH
2
—OH→R
1a
—CH═CH—CH
2
—F+R
1a
—CHF—CH═CH
2
  (b)
[in the above formulas, R
1
represents an alkyl group that may have a substituent, an aralkyl group that may contain a substituent, an alkenyl group that may contain a substituent, an acyl group that may contain a substituent, a cycloalkyl group that may contain a substituent, a heterocycloalkyl group that may contain a substituent, or a mono-, di- or tri-saccharide that may contain a protecting group. R
1a
represents an alkyl group that may contain a substituent, an aryl group that may contain a substituent, an aralkyl group that may contain a substituent, an alkenyl group that may contain a substituent, an acyl group that may contain a substituent, a cycloalkyl group that may contain a substituent, a heterocycloalkyl group that may contain a substituent, or a mono-, di- or tri-saccharide that may contain a protecting group.]
In the present specification, “may contain a substituent” includes both cases where a substituent is contained and not contained. For example, an alkyl group that may contain a substituent includes alkyl groups and alkyl groups having a substituent.
Specific examples of compounds having an OH group include apliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, octanol, decanol, palmityl alcohol, stearyl alcohol, oleyl alcohol, etc., alicyclic alcohols, such as benzyl alcoh

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