CS225513B1 - Alpha-substituted-4-pyridine salts of -3-/2-furyl/-acrylonitrile and their preparation - Google Patents

Description

The invention relates to α-substituted-5-pyridinium salts of 3- (2-furyl) -acrylonitrile of the general formula I

.......... \.-n -. Z /) ν '..

wherein X is a CN, CONH-COOCH ,,, i and QA / \ cioH, _J0 <- /. ')

1 / and the method of preparation thereof.

Substances and methods for their preparation according to the invention are not yet described in the literature.

The process according to the invention is characterized in that the pyridinium salts of the general formula II

II where Y ⁽ ' ⁾ is cf * ⁷ , Bi ^ ⁷ J) a

X is the same as in formula I,

225 513 are reacted with a β acid of formula MZ, where Z is as defined in formula I and M is Η, K, Na in an aqueous, hydroalcoholic or alcoholic medium having 1 to 3 carbon atoms in the temperature range of 0 to 35 ° C. The reaction proceeds according to the equation:

wherein X, Y, Z and M are as defined above.

An advantage of the process for the preparation of the pyridine salts according to the invention is that the syntheses are simple, unpretentious and the products obtained in high yields and purity. Compared to the halides of pyridinium salts, said substances are less soluble in water, better soluble in aprotic solvents than acetone, ether, dioxane, dimethylsulfoxide.

The invention is illustrated but not limited by the following examples. The compounds of the present invention may serve as intermediates in the preparation of 1,2 or 1,4 N-substituted dihydropyridines or 5-aminofuran derivatives.

Example 1 g (3.31 mole) of a compound of formula II wherein Y is Br and X is CN is dissolved in aqueous ethanol (1: 1) and 0.5 g of 70% perchloric acid is added to the solution thus prepared. . Yellow-brown crystals of the compound of formula I are excluded, wherein X is CN and Z = ⁷ is C104 ⁽ " ⁷ e Yield 0.9 g, i. E.

84.5

This compound can also be prepared in a similar manner from a compound of formula II wherein Y is Cl, J.

I «Β»

Example 2

225 513 g (3.88 mole) of a compound of formula II wherein Y is Cl and X is COOCH3 are dissolved in aqueous ethanol (1: 2) and 0.5 g of 70% HClO2 is added to the solution thus prepared. . Yellow-brown crystals of compound I, where X is COOCH2 and Z is C104, are separated _. The yield is 0.9 g, m.p. j _e 74

1H NMR spectrum measured on Tesla BS-487 C, hexadenteriodimethylsulfoxide, 25 ° C:

FROM'

6i.

8.32 ppm / s / 7.68 ppm / s / 7.78 ppm = 9.38 ppm / d / V

0¾ = 8.37 ppm / dd /% = 8.80 ppm / t /

W ^Γ Η-Ή

4

7> ° ^H

8.0 H _from 1.5 H ₃

4> ° ^H

Example 3 g (2.72 mole) of a compound of formula II wherein Y is J and X is COH ₂ is dissolved in ethanol and 0.5 g of 70% HClO ₄ is added. X is CONCEPT, and Z is C10 ₄ . Yield 0.85 g, i. 92%.

Example 4 g (3.31 mole) of a compound of formula II wherein Y is Br and X is CN is dissolved in ethanol and 0.5 g periodic acid is added. Exclude the yellow-brown crystals of compound I, wherein X is CR and Z is ₄ J0 '> Yield: 1.15 g t _{e 0} u 84%

Example 5 g (2.98 m small) of a compound of formula II wherein Y is Br and X is CO 2 CH 3 is dissolved in 1: 1 propanol: water and 0.6 g of periodic acid is added. A brownish pulverulent substance (I) where X is COOCH2 and Z is J4 () is obtained ₍ yield 1.1 g, i.e. 32.5%).

Example 6

225 513 g (3.63 mole) of substance II, wherein Y is Cl and X is CONEL, are dissolved in CH-OH and 0.5 g of periodic acid is added. A rye powder substance I, where X is CONH ₂ and Z is J _4, is separated _. The yield is 1.3 g, ie 84%.

1 H NMR spectrum of IHb / measured on a Tesla BS-4q7c instrument, eriodimethylsulfoxide hexadent, 25 ° C / ~ ^{7.89 PPm} - ⁹ ' ^{PP8 H} z <r _H. 3.39 ppm (aa) ^J J _HH = ₈ , oh _z

^{4/7 "PA 65"} / ^{S /} <= 3.80 ppm / t / V = H 3 4 watts \

Example 7

1.5 g (4.96 mole) of substance II, where Y is 3r, X is CN dissolved in water and 1.26 g (5.5 mole) of picric acid are added. A greenish-yellow substance I is excluded, wherein X is CN and Z is picrate. Yield 2.0 g. j ₀ «9.5

HNMR spectrum / measured on Tesla BS-48? C, eriodimethylsulfoxide hexadent, 25 ° C / ^H 4

H.

8.49 ppm / A / 9.40 ppm / D / 8.43 ppm / Dd / 7.53 ppm / 3 / P / 1 / 3.61 ppm 8.57 ppm / A /

The dubleium signals of the furan hydrogen H ^H ^ merged into one singlet. signal.

₃ _% v ⁼

3 _T ^h 3 ^h 4 ⁴ “Vr

T, 2 H _of 3.0 H _of

ABOUT

1.5 H _z

Example 8

S (3.44 moles) of substance II, wherein Y is Cl, X is COOCH3, is dissolved in methanol and 0.37 g (3.78 moles) of picric acid is added. A greenish-yellow substance (I), where X is COOCH2, Z is 5 times, in a yield of 1.5 g, m.p. j. 90.2

Example 9

225 513 g (2.72 mole) of substance (II) where Ϊ is J, X is CONH ₂ is dissolved in propanol and water in a ratio of 1: 1 and 0.75 &lt; 26 mole / picric acid is added. A yellowish brown compound (I), where CONH _{2 is present} and Z is a picrate, is obtained in a yield of 1.05 g, i. Similarly, said compound is also prepared from Compound II, wherein X is CONH ₂ and Y is Cl, Br.

Example 10

A g (3.31 mole) of substance II, wherein Y is Br, X is CN is dissolved in 25 ml of distilled water, the solution is filtered and 10 ml of a 10% aqueous 56% NaClO ₄ solution is added. Exclude the compound I, wherein X is CN, Z is a C 10 _4, in a yield of 0.83 g. T _e j · 77.9% ♦ A similar preparation is the compound II, wherein Z is C 10, and X ₄ is N, COOCH CONHgo

Example 11 δ / 3> 44 m mole / compound II, wherein X is Y is dissolved in 20 ml of distilled water and the resultant solution was added 13 mL of 10% aqueous solution of KJ0 ₄ · tan Exclude the compound I, where X is COOCHj and Z is J0 ₄ · Similarly, I is prepared, where CN, C0NH ₂ is X and Z is J0 ₄ ·

Example 12 g (2.72 mole) of substance II, where it is dissolved in 40 ml of HgO and then 20 ml of a 10% aqueous solution of sodium picric acid is added. A brownish-brown slat is obtained in a yield of 1 g, m.p. jo 84% ·

Physico-chemical properties of substances Come invention and elemental analyzes are shown in Table III No. 1 _e ·

-6 cm m Si S? ro r - - - - * * - r r r r r (((((((((((((((((((((((((

OH 00 00 cm cn mm cm cm ου ου

225 513

Compounds of formula I synthesized according to the invention

M

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Claims (2)

1'-substituted-5-pyridinium salt of 3- (2-furyl) acrylonitrile of formula I Ό where X is CN, CONHg, COOCH2 Z ⁽ l is O10), JO ₄ ^(-) YOU ·) A / ₍ ) A .A? Process for the preparation of the compounds of the formula I according to claim 1, characterized in that the pyridinium salts of the formula II r, II wherein Y ^(_) is Cl ^ '\ Br ^' ^, and X stands for the same as in formula I, react with an acid of formula MZ, wherein Z is as defined in formula I and M is Η, K, Na in aqueous , a hydroalcoholic or alcoholic medium having 1 to 3 carbon atoms in the range of 0 to 35 ° C.