Fluorination agent and preparation and use of same

Details Fluorination agent and preparation and use of same Fluorination agent and preparation and use of same

2000-10-13

2002-07-09

Shah, Mukund J. (Department: 1624)

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

Organic compounds

Nitrogen attached directly or indirectly to the purine ring...

C544S242000, C514S075000, C514S114000, C514S118000, C546S345000, C546S346000, C548S335100, C548S400000, C549S029000

Reexamination Certificate

active

06417361

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a novel hydrogen fluoride containing composition, application of the composition to a fluorination agent, and preparation process of a fluorine-containing compound by using the composition.
BACKGROUND ART
Many processes have so far been known on the halogenation reaction of an organic compound. Compounds which can be used for a halogenation agent include hydrogen halide, phosphorous halide, sulfur halide and halogen simple body. However, these compounds are very corrosive and toxic, and many of these compounds require special equipment and technique. Accordingly, the investigation for developing a halogenation agent has been still continued in view of handling, safety and reactivity.
The fluorination agents which have been conventionally used in fluorinating reactions include fluorine, anhydrous hydrogen fluoride and sulfur tetrafluoride. However, these conventional fluorination agents are difficult to handle because of toxicity, corrosivity and danger of explosion in reaction and thus special equipment and technique are required. It is also a problem that required selectivity of a fluorine bond in the reaction is poor. On the other hand, development of new products utilizing fluorine compounds has been carried out in various fields such as functional materials and physiologically active substances. Keeping pace with such trend, various fluorination agents are recently in a development stage.
Anhydrous hydrogen fluoride (HF) is widely used in a great amount as a basic fluorine source in the fluorine chemical industry. However, it is difficult to handle because of a low boiling point (b.p. 19.5° C.) and strong toxicity and corrosivity. When using hydrogen fluoride, the equipment must have acid proof property and pressure tight structure. Further, specific technique is required, and thus it is very difficult to use in industry.
In order to solve these problems, a complex of HF and Lewis base has been developed as a fluorination agent which is easy to handle and exhibits reaction mechanism similar to hydrogen fluoride (hereinafter referred to as HF-like fluorination agent). For example, pyridine-70 wt % (HF)n (Olah agent) has been reported in J. Org. Chem., 44, 3872 (1979) and triethylamine-3HF has been described in Aldrichimica Acta., 28, 31 (1995). However, these fluorination agents are difficult to control in the preparation step due to a considerably exothermic reaction. Further, it is difficult to use in industry in view of recovery and reuse.
HF is an important fluorine source in the fluorine chemical industry. Consequently, the development of an improved HF-like fluorination agent is very significant in the area of fluorine chemistry in order to overcome handling problems and to make the application simple in broad area.
The subject of the present invention is to provide hydrogen fluoride, which is a suitable fluorination agent for the preparation of a fluorine- containing compound, in the form of a fluorination agent which is easy to handle and can be conveniently used.
DISCLOSURE OF THE INVENTION
As a result of an intensive investigation in order to solve these subjects, the present inventors have found that a hydrogen fluoride containing composition obtained by adding hydrogen fluoride to a compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more, preferably to the compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more and pka of 12 or more at 25° C., the composition is easy to handle and useful as a novel fluorination agent having fluorinating effect similar to hydrogen fluoride, and further found that the fluorinating reaction can progress in high safety with ease without requiring special equipment and technique. Thus the present invention has been completed.
That is, the aspect of the present invention is a hydrogen fluoride containing composition obtained by adding hydrogen fluoride to a compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more, preferably to the compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more and pka of 12 or more at 25° C., use of said composition for fluorination agent and a preparation process of a fluorine containing compound by using said composition for a fluorination agent.
The invention will be more specifically illustrated in items (1) to (7) below.
(1) A hydrogen fluoride containing composition comprising hydrogen fluoride and a compound being liquid in the standard state (25° C., 1 atmosphere) and having a boiling point of 120° C. or more, and a fluorination agent comprising said composition.
(2) A hydrogen fluoride containing composition comprising hydrogen fluoride and a compound being liquid in the standard state (25° C., 1 atmosphere) and having a boiling point of 120° C. or more and pka of 12 or more at 25° C., and a fluorination agent comprising said composition.
(3) A hydrogen fluoride containing composition comprising 7 mol or more of hydrogen fluoride for 1 mol of a compound being liquid in the standard state (25° C., 1 atmosphere) and having a boiling point of 120° C. or more and pka of 12 or more at 25° C., and a fluorination agent comprise said composition.
(4) A hydrogen fluoride containing composition and a fluorination agent comprising said composition in items (1) to (3) wherein (I) the compound is represented by the formula (1):
wherein R
1
to R
4
are a substituted or unsubstituted alkyl or aryl group and can be the same or different, and R
1
and R
2
or R
3
and R
4
can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom, or R
1
and R
3
can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom, {circle around (2)} the compound is represented by the formula (6):
wherein R
7
and R
8
are a substituted or unsubstituted alkyl or aryl group, R
9
is a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, these groups can be the same or different, and R
7
and R
9
can bond to form cyclic amide, {circle around (3)} the compound is represented by the formula (10):
R
10
—O—R
11
  (10)
wherein R
10
and R
11
, are a substituted or unsubstituted alkyl or aryl group and can be the same or different, and R
10
and R
11
, can bond to form cyclic ether, {circle around (4)} the compound is represented by the formula (12):
wherein R
12
and R
13
are a substituted or unsubstituted alkyl or aryl group and can be the same or different, and R
12
and R
13
, can bond to form cyclic ester or {circle around (5)} the compound has the formula (14):
(5) A hydrogen fluoride containing composition and a fluorination agent comprising the composition wherein the compound represented by the formula (1) is: {circle around (6)} a compound represented by the formula (2):
{circle around (7)} a compound represented by the formula (3):
wherein a is an integer of 2 or 3, and R and R
6
are a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and can be the same or different, and the compound represented by the formula (3) is a compound having the formula (4):
or the formula (5):
and further {circle around (8)} the composition wherein the compound represented by the formula {circle around (6)} is a compound having the formula (7):
the formula (8):
or the formula (9):
{circle around (9)} the composition wherein the compound represented by the formula (10) is a compound having the formula (11):
(CH
3
OCH
2
CH
2
)
2
O  (11)
or {circle around (10)} the composition wherein the compound represented by the formula (12) is a compound having the formula (13):
As illustrated above, the invention is each composition above and the use of the composition for a fluorination agent.
(6) A preparation process comprising reacting the fluorination agent with a compound represented by the formula (15):
R
14
[C(X
1
)
3
]
m
  (15)
wherein R
14
is a

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