DE2424690A1 - PYRAZOLES SUBSTITUTED WITH PERFLUORALKYL GROUPS AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

PATENT ADVOCATE DR. HANS-GUNTHER EGGERT ₁ DIPLOMA CHEMIST

5 COLOGNE 51, OBERLÄNDER UFER 90 ο / Ο / ΟΩΠ

-Köln, April 4, 1974 Eg / pz / 47

Produits Chlmlques Uglne Kuhlmann,

25, Boulevard de l'Amiral Bruix, Paris 16eme / France

Pyrazoles substituted with perfluoroalky groups and Process for their manufacture

The invention relates to pyrazoles substituted with perfluoroalkyl groups and a process for the preparation of these Links.

The substituted pyrazoles of the formula

N \
N

in which R and R ¹ denote aliphatic hydrocarbon groups or phenyl radicals are known. They are described, for example, by AR Katritzky and AS Boultone, Advances in Heterocyclic Chemistry, Vol. 6, p. 347.

The present invention provides with one or two perfluoroalkyl groups substituted pyrazoles available. The new pyrazoles according to the invention can by

409849/1111

general formula (I) are reproduced

(D

in which R ^, and R ^, can be identical or different and a perfluoroalkyl group C _n F _{3n + 1} , where η is an integer from 3 to 15, a phenyl radical, a phenyl radical substituted in the ortho, meta or para position or denote an alkyl group with up to 7 carbon atoms, at least one of the two groups EL ·, and Ri denote a perfluoroalkyl radical. It should be mentioned that in the cases in which R ^ ₁ and R ^ _{1 are} different, the pyrazoles according to the invention actually have the following tautomeric formulas:

and

N N

H H

The compounds according to the invention also include the pyrazoles of the formulas (I) or (II) in which the nitrogen atom seated hydrogen atom is replaced by an aliphatic or aromatic group X. These pyrazoles can are represented by the isomeric formulas (III) and (IV).

ORIGINAL INSPECTED

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Examples of X are alkyl groups with up to 7 carbon atoms, optionally substituted phenyl groups and perfluoroalkyl groups C _m ^F 2 _m -fi> where m is an integer from 2 to 7 inclusive.

The pyrazoles according to the invention were prepared by reacting hydrazine hydrate with a fluorinated β-diketone according to get the following equation:

H ₀ N-NH ₀ + R ₀ -C-CH ₀ -CR ₁ I solvent

A ZH ₁₁ Δ "t » »

O η reflux

where Rp and Kl have the meanings given.

Some of the fluorinated ß-diketones used are known (see, for example, R.A. Moore and R. Levine, J.Qrg.Chem., 29, 1964, p. 1439), others were synthesized for the first time by the applicant.

The reaction is carried out under reflux with hydrochloric acid as a catalyst in a solvent consisting of an aliphatic C, * alcohol or mixtures thereof, for a period of at least 1 hour. Preferably one works with stoichiometric amounts of fluorinated ß-diketone and of 98% hydrazine hydrate. After removing the solvent, an oily derivative of brown is usually obtained Colour. The oily phase is extracted in a known manner, for example by taking up with ether. One washes then the ether phase with water, dries and removes the ether. A perfluorinated pyrazole is obtained in In the form of a solid white powder which is recrystallized in a known manner, for example in petroleum ether.

A 0 9 8 U 9/1 1 1 1

The pyrazoles of the formulas (III) and (IV) have been prepared by the applicant by using hydrazine hydrate, which is produced by X was substituted, reacted with a fluorinated ß-diketone:

XHN-NH ₀ + Rp-C-CH-R ₀ -C Lösungsmi ttel /

O O

¹¹ · '· "' ι ίτ-t ο N. / Tl ₁ I ₁ + H ₀ O reflux \ / T 2

The procedure is completely the same as that used for presentation of the pyrazoles (I) and (II), but in the last stage instead of a Uinkrystallisierung one Distillation occurs because the pyrazoles of formulas (III) and (IV) are liquid.

The pyrazoles according to the invention have numerous possible uses, in particular as thermal liquids and as surface-active compounds in organic solution. The following examples illustrate the invention, without limiting it to this.

example 1

Dissolve o, oil mole (5.16 g) of phenyl-1-N-pentadecafluoroheptyl-1,3-propan-dione-1,3 in 20 ml of methanol. Hydrazine hydrate, dissolved in 20 ml of methanol, is then added dropwise then add 3 drops of concentrated HCl. The mixture is refluxed for 1 hour with constant stirring. The alcohol is steamed and receives a brown oil that is absorbed with ether. The ether phase is washed three times with 20 ml of water and then extracted the aqueous phase with ether. It is dried over sodium sulfate and the ether is absorbed Vacuum off. A white powder is obtained, which is

4 0 9 8 4 9/1111

ether recrystallized. 4.6 g of phenyl-3 (5) -N-pentadecafluoroheptyl-5 (3) -pyrazole, corresponding to a yield of 89%, with a melting point of 97 C. The characteristic data obtained by spectral analysis (IR,
NMR, mass spectrum, UV) of the product agree with the following structure:

analysis

% .C 5o 1 H 5 N 55 P. Calculated for
C F HN
16 15 7 2 37, 52 1 , 36 5 , 48 55 , 66 Found 37, , 33 , 49 , 61

Examples 2 to 7

Following a similar procedure to Example 1, the the following substituted pyrazoles:

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eipiel

X F. ° C b.p. ⁰ C yield

2 ^C 5 ^F 11 ^C 6 ^H 5 H 89 147 ° C-20 mm Hg
(Mixture of 2
not separated
ten isomers) 84 y 3 C ₃ F ₇ ^C 6 ^H 5 H 86 l65 ° C-20 mm Hg
(Mixture of 2
not separated
ten isomers) 86 4th ^C 7 ^F 15 tert-butyl H 62 92 5 ^C 7 ^F 15 ^C 7 ^F 15 H 116 93 6th ^C 3 7 ^C 6 ^H 5 CH ₃ 78 7th C ₃ F ₇ ^C 6 ^H 5 ^C 6 ^H 5 84

4 0 9 8 ü 9/11 1 1

Claims (4)

Patent claims 1. Substituted with one or two perfluoroalkyl groups Pyrazoles of the formula (I) or the isomeric formula (II) ⁷ w ^R - X
(D (II) in which R ^ and RA can be the same or different and a perfluoroalkyl group C ^F ₂ n + 1 ' ⁱⁿ ^ ^{er ne} ^ - ^ne ^ ^{Άτιζ &} number from 3 to 15, a phenyl group, a substituted phenyl group or an alkyl group with up to 7 Mean carbon atoms and at least one of the two groups R _{1 and R 1 is} a perf uoroalkyl group, and X fine is a hydrogen atom or an alkyl group with up to 7 carbon atoms, a phenyl group, a substituted phenyl group or a perfluoroalkyl group CF., Where m is an integer of 2 to 7 means. 2. A method for the preparation of pyrazoles according to claim 1, characterized in that hydrazine hydrate XHN - NH ₃ with a fluorinated ß-diketone Rp-C-CH ₀ -C-Ri ₁ , 0 0 where Rp, Rl and X have the meanings given, in the presence of a catalytic amount of concentrated Hydrochloric acid by refluxing for at least 1 hour in an aliphatic C., alcohol or a mixture this converts alcohols as solvents. A09849 / 1 1 1 1 3. Use of the pyrazoles according to claim 1 as thermal Plüssigkei th. 4. Use of the pyrazoles according to claim 1 as surface-active compounds in organic solution. 4098-49 / 1111