CS219181B1 - Picoline salts 5-nitro-2-vinylfurane and method of preparation the same - Google Patents

Description

The process for the preparation of a salt of formula I wherein X is Br is characterized in that cis (Z) 5-nitro-2-furylvinyl bromide of formula IV is reacted with picolines, namely 2-methylpyridine of formula V,

3-methylpyridine VI or 4-methylpyridine VII, in organic solvents such as aromatic hydrocarbons such as benzene, toluene, xylenes, ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, acid esters such as ethyl acetate, acetic acid methyl ester, formic acid ethyl ester, acetic acid butyl ester, further alcohols having 1 to 5 carbons, thiophene, carbon disulfide, acetonitrile, dimethylsulfoxide or dimethylformamide or mixtures thereof, as well as their mixtures; mixtures with water in the temperature range of 25 to 100 ° C.

The reaction proceeds as follows:

II in position 3

III in the 4 and nature of the process for preparing salts of the formula I, where X a J, C1O ₄ or the picrate of the present invention is also characterized that the thread-5-furyl-2-vinylpikolíniumbromidy of formulas I-III are reacted with alkali;

iodides such as NaJ, KJ, LiJ, with perchloric acid or picric acid in an organic solvent medium of their mixture or mixture, with water as described in the preparation of 5-nitro-2-iuryl-vinyl picolinium bromides in the temperature range of 0 to 70 C.

The reaction proceeds as follows:

ΓΛ © Μ-χ

0, N- (1-CH-CH-n ', 1'-Br- ² ', 2'-1'-1-H-X)

CHt ®r ~ W ©

02N-V CH = CH-N ' ^x > X

CH-3

M, Na, K, 11

X - J, cio ₄ . - ° - \ O NO 2

An advantage of the processes for preparing the picolinium salts of 5-nitro-2-vinylfuran according to the invention is that the syntheses are one-stage starting from relatively available raw materials. The products are obtained in high yields and purity. The compounds represent a novel group when X is Br, water-soluble respectively. partially soluble if X is J,

5-nitro-2-vinylfuran antibacterial preparation.

. Antibacterial effect was monitored on selected bacterial, yeast and fungal strains using the diffusion method:

The following examples illustrate the invention.

EXAMPLE

2.18 g (0.01 mol) of cis (Z) 5-nitro-2-furylvinyl bromide was dissolved in 30 ml of acetonitrile and 10 ml of 2-methylpyridine was added at 60 ° C. After 100 hodinách hours of stirring and heating, the solvent was evaporated in vacuo. The residue was purified with ethyl alcohol ether. 2 g (64%) of a light brown crystalline compound of 1.1 were obtained. 227-222 ° C. *

Elemental analysis was for the silver ₂ O ₃ (310.9) found calculated 9.00% N, 25.05% Br, 9.10% Found: N, 23.90% Br. UV spectrum (measured on UV VIS - Zeiss Jena) in methanol: k _max = 224 nm log ε = 3.27, λ _raax = 268 nm log ε - 2.92, k _rnax = 333 nm log ε = 3.06 . IR spectrum (measured by a UR-20 KBr): 1515, 1347, 1629, 1246, _and 1040 cm ^'first

_t 1 H-NMR (measured on a Tesla BS-467,

BS-487C, TMS) in DMSO-d _6):

HH ₃ = 7.11 ppm, δΗ ₄ = 7.67 ppm, J _{3 4} = 4 Hz δΐί _Α = 7.36 ppm, δΗ _Β = 7.64 ppm, J _AB = 9 Hz δH _{CH 3} = 2.50 ppm .

Example 2

2.18 g (0.01 mol) of trans (E) 5-nitro-2-furylvinyl bromide and 2 ml of 2-diethylpyridine were mixed with 10 ml of nitrobenzene and heated at 50-70 ° C for 30 hours. The precipitate was filtered off with suction and washed several times with ether and crystallized from methanol-ether. 0.4 g (13%) of a yellow crystalline substance of m.p. t. Mp 248-250 ° C with decomposition.

1 H NMR analysis revealed to be E isomer (I). 1 H-NMR spectrum obtained on the unit Tesla BS-467, BS-487 C to T> MSO-d _about δΗ ₃ = 7.30 ppm, 7.83 δΗ = _4, J _{3, 4} = 4 Hz _δΗ Α = 7, 95 ppm, _δΗ Β = 8.47, J _AB = 15? H = 2.45 ppm _CHi.

Example 3

21.8 g (0.1 mol) of cis (Z) 5-nitro-2-furylvinyl bromide were dissolved in 100 ml of 3-methylpyridine. The mixture was heated in a boiling water bath for 10 hours. Recrystallization from ethanol-ether gave 21 g (61%) of a light green crystalline compound rt. t. Mp 197-199 ° C.

Elemental analysis for C ₁₂ H _N BrNO ₃ (310.9), it was found: calculated 9.00% N, 25.05% Br, 8.91% Found: N, 25.80% Br. IR spectrum (measured on a _row unit UR-20 KBr): 1035, 1Í245, 1349, 1528,

1633 cm ¹ .

UV spectrum (measured on UV VIS - Zeiss Jena in methyl alcohol):

= 2? 3 nm log ε = 3.25, λ _max = 268 log ε = 3.00,

Λ _max = 334 nm log ε - 3.05

1 H NMR spectrum (measured on Tesla i BS-467-4870, TMS in DMSO-d ₆ ):

, δΗ ₃ = 7.20 ppm, δΗ ₄ = 7.68 ppm, J _{3 4} = 4 Hz δΗ _Α = 7.37 ppm, δΗ _Β = 7.77 ppm, J _AB = 9.2 Hz i SH _C h ₃ = 2.47 ppm.

Example 4,

2.18 g (0.01 mol) of trans (E) 5-nitro-2-furylvinyl bromide was dissolved in 50 ml of benzene and 30 ml of 3-methylpyridine was added. The mixture was heated at the boiling point of the solvent for 5 hours. 2.56 g (80%) of trans (E) 5-nitro-2-furylvinylpicolinium bromide of m.p. -254 ° -256 ° C. A light brown crystalline solid was obtained, crystallized as an ethanol-ether mixture.

@ 1 H NMR spectrum (measured on Tesla

BS-467, BS-487 C, TMS in DMSO-d ₆ ): δΗ ₃ = 7.26 ppm, δΗ ₄ = 7.84 ppm, J ₃₄ = 4 Hz δΗ _Α = 8.01 ppm, δΗ _Β = 8 41 ppm, J _AB = 14 H to 6 H _ch , = 2.50 ppm.

Example 5. 1 ·

2.18 g (0.01 mol) of cis (Z) 5-nitro-2-furylvinyl bromide and 5 ml of 4-methylpyridine were dissolved in 30 ml of acetonitrile and 10 ml of ethyl acetate and heated at the reflux temperature of the solvent for 10 hours. 1 g (32% yield) of a light brown crystalline compound of mp 205-207 ° C was obtained. Elemental analysis found for C ₁₂ H _for BrN ₂ O ₃ (310.9): calculated 9.00% N, 25, 0.5% Br, found 8.92% N, 25.10% Br. UV spectrum (measured on UV VIS - Zeiss Jena in methyl alcohol):

Λ _max = 223 nm log ε = 3.25, λ _max = 263 nm log ε = 2.93,

Λ _max = 351 nm log ε = 3.04;

IR (measured on a UR-20, KBr technique): 1040, 1245, 1349, 1528, 1633 cm ^{@ -1} ; 1 H NMR spectrum (measured by the unit Tesla BS-467, BS-487C, TMS in DMSO-d 6): δΗ3 = 7.18 ppm, 7.68 ppm = δΗ4, J 3 = ⁴ 4 Hz δΗΑ ~ 7.35 ppm, δΗ _Δ = 7.80 ppm, J _AB = 9.2 Hz. _C 6 H h ₃ = 2.45 ppm.

Example 6

1.7 g (0.0055 mol) of trans (E) 5-nitro-2-furylvinyl bromide and 10 ml of 4-methylpyridine were mixed in 50 ml of acetomitrile and 50 ml of butyl acetate and the solution was heated at the reflux temperature of the solvent for 5 hours. 0.6 g (25% yield) of a yellow-brown crystalline compound (III) with a trans (E) configuration of 1.1 was obtained. 224-225 ° C with decomposition.

1 H NMR spectrum (measured on Tesla BS-467, BS-487C, TMS in DMSO-d ₆ ): δΗ ₃ = 7.28 ppm, δΗ ₄ = 7.80 ppm, J ₃₄ = 4 Hz OH _A = 7, 95 ppm, OH _B = 8.46 ppm, J _AB = 15.0 Hz 6H _{CH 1} = 2.46 ppm.

Example 7

0.62 g of cis (Z) 5-nitro-2-furylvinyl-2-methylpyridinium bromide was dissolved in 50 ml of ethyl alcohol and 3 g of sodium iodide soluble in 5 ml of water was added. 0.5 g (70% yield) of a dark brown crystalline solid of m.p. t. 227 DEG -230 DEG C. with decomposition of 5-nitro-2-furylvinylpicolinium iodide.

UV spectrum (measured on a UV VIS - Zeiss Jena in methanol):

^ max “nm log ε = 3.61, X _max = 270 nm log ε = 3.13,

Λ _max = 336 nm log ε = 3.16.

Example 8

0.62 g of the substance as in Example 7 was dissolved in 40 ml of ethyl alcohol and 2 g of picric acid dissolved in 50 ml of ethyl alcohol was added. 0.85 g of picolinium 5-nitro-2-vinylfuran picrate, m.p. t. 166-170 ° C as a yellow-orange, crystal. material.

UV spectrum (measured on a UV VIS - Zeiss Jena in methanol):

\ nax = 225 nm log ε = 3.27, λ _max = 261 nm log ε = 3.01,

Λ _max = 268 nm log ε = 3.00, λ _max = 351 nm log ε = 3.52.

Example 9

0.62 g of the cis (Z) compound as in Example 7 was dissolved in 10 ml of water and 5 ml of 70% perchloric acid was added. The precipitated light brown crystalline material was filtered off. 0.62 g (90% yield) of 5-nitro-2-vinylfuran-2-methylpyridinium perchlorate of m.p. t. Mp 117-119 ° C.

UV spectrum (measured on a UV VIS - Zeiss Jena in methanol):

Λ _max = 225 nm log ε = 3.25, λ _max = 269 nm log ε = 2.99,

Λ _max = 338 nm log έ = 3.06.

Example 10

1.25 g of 5-nitro-2-furylvinyl-3-methylpyridinium bromide was dissolved in a solution of 3 g of sodium iodide in 50 ml of ethanol to obtain 1 g of dark red 5-nitro-2-furylvinyl-3-methylpyridinium iodide of m.p. t. 200-201 ° C.

5-nitro-2-furylvinyl-3-methylpyridinium monohydrate was obtained by t. t. 189-191 ° C, as described in Example 8. Perchlorate was obtained as described in Example 9, m.p. Mp 131-133 ° C.

Claims (3)

3 acetic acid and heated at the boiling point of the solvent for 10 hours. 1 g (32% yield) of a light-colored crystalline compound of m.p. 205-207 ° C was obtained. Analysis found for C 12 H 11 BrN 2 O 3 (310.9): calculated 9.00% N, 25.5% Br Found: 8.92% N, 25.10% Br. UV spectrum (measured on a UV VIS instrument - Zeiss Jenav methylakohole): Xmax = 223 nm log ε = 3.25, Xmax = 263 nm logε = 2.93, λmax = 351 nm log ε = 3.04, IR spectrum (measured on instrument UR-20, KBrtechnikou: 1040, 1245, 1349, 1528, 1633 cm -1; 1 H NMR spectrum (measured on a TeslaBS-467, BS-487C, TMS in DMSO-d6): δΗ3 = 7.18 ppm , δΗ4 = 7.68 ppm, J3 4 = 4 HzδΗΑ ~ 7.35 ppm, δΗΒ = 7.80 ppm, JA B = 9.2 Hz.6HCl3 = 2.45 ppm Example 6 1.7 g (0, 0055 mol) of trans (E) 5-nitro-2-furylvinylbromide and 10 ml of 4-methylpyridine mixed with 50 ml of acetomitrile and 50 ml of butyl acetate and heated at the boiling point of the solvent for 5 hours. The yield of the yellow-brown crystalline compound (III) with the trans (E) configuration at 1.14-225 ° C with decomposition: 1 H NMR spectrum (measured on a TeslaBS-467, BS-487C, TMS in DMSO-d 6): δΗ3 = 7.28 ppm, δΗ4 = 7.80 ppm, J34 = 4 HzδΗΑ = 7.95 ppm, δHB = 8.46 ppm, JA B = 15.0 Hz6HCHi = 2.46 EXAMPLE 7 0.62 g of cis (Z) 5-nitro-2-furylvinyl-2-methylpyridium bromide was dissolved in 50 ml of ethyl alcohol and 3 g of 5 ml of sodium iodide was added. 0.5 g (70% yield) of a dark brown crystalline solid, m.p. 227-230 ° C, was obtained as a 5-nitro-2-furylvinylpicionium iodide. UV spectrum (measured on a UV VIS apparatus - Zeiss Jena in methanol): 219181 ^ max 'nm log ε = 3.61, Xmax = 270 nm logε = 3.13, 7max = 336 nm log ε = 3.16. EXAMPLE 8 0.62 g of the compound of Example 7 was dissolved in 40 ml of ethyl alcohol and 2 g of picric acid dissolved in 50 ml of ethyl alcohol were added. 0.85 g of picolinium 5-nitro-2-vinylfuran, p. 166-170 ° C, were obtained as yellow-orange crystals. substance. UV spectrum (measured on UV VIS - Zeiss Jena in methanol): x = 225 nm log ε = 3.27, Xmax = 261 nm logε = 3.01, Xmax = 268 nm log ε = 3.00, Xmax = 351 nm logε = 3.52. Example 9 0.62 g of the cis (Z) substance as in Example 7 was dissolved in 10 ml of water and 5 ml of 70% perchloric acid was added. The precipitated light brown crystalline material was filtered off. 0.62 g (90% yield) of 5-nitro-2-vinylfuran-2-methylpyridinium perchlorate (m.p. 117-119 ° C) was obtained. UV spectrum (measured on a UV VIS-Zeiss Jena instrument in methanol): λ max = 225 nm log ε = 3.25, λ max = 269 nm logε = 2.99, λ max = 338 nm log ε = 3.06. EXAMPLE 10 1.25 g of 5-nitro-2-furylvinyl-3-methylpyridinium bromide was dissolved in a solution of 3 g of sodium iodide in 50 ml of ethyl alcohol to give 1 g of dark-colored 5-nitro-2-furylvinyl-3-methylpyridinium y-didu with tt 200-201 ° C. 5-nitro-2-furylvinyl-3-methylpyridine was obtained in the manner described in Example 8 by m.p. 189 DEG -191 DEG C. The perchlorate was obtained as described in Example 9 above. 131-133 ° C. OBJECT 1. Picolinium salts of 5-nitro-2-vinylfuran of the general formula I Z ' wherein CH 3 is in the 2, 3 or 4 position and wherein X is Br, J, C 104, NO 0 and cis (Z) and trans (E) configurations FILLED 2. A process for the preparation of picolinium salts of 5-nitro-2-vinylfuran according to claim 1, wherein X is Br characterized by the fact that trans (E) and (b) are respectively. cis (Z) 5-nitro-2-furyl-; nyl bromide reacts with picojins, namely 2-methylpyridine, 3-methylpyridine or 4-methylpyridine in an organic solvent environment such as aromatic hydrocarbons such as benzene, toluene, xylenes, ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethene, further esters of acids such as ethyl acetate, methyl acetate, 1 to 5 carbons, thiophene, carbon disulfide, acetonitrile, dimethylsulfoxide or dimethylformamide, or mixtures thereof, as well as mixtures thereof with water in a temperature range of 25 to 100 ° C. 4 3. A process for the preparation of picolinium salts of 5-nitro-2-vinylfuran according to claim 1, wherein X is J, C1O4 but is not characterized in that the 5-nitro-2-furyl-vinyl picolinium bromides mentioned in point 2 are reacted with 219181 with alkaline iodides such as for example, NaJ, RJ, Li, with perchloric acid and picric acid in an environment of organic solvents as described in point 2, in a temperature range of 0 to 70 ° C. Printed by Moravian Printing Works, Price: 2,40 Kčs operation 12, Leninova 21, Olomouc