CS226936B1 - 1-(5-nitro-2-furoyl)-1-phenylsulphonyl-2-(4-x-phenyl)ethylenes and method of preparing same - Google Patents

Description

(54) 1- (5-Nitro-2-furoyl) -1-phenylsulfonyl-2- (4-X-phenyl) ethylenes and a process for their preparation

The present invention relates to 1- (5-nitro-2-furoyl) -1-phenylsulfonyl-1- (4-X-phenylethylenes of formula I).

wherein ______________________ X is H, CH 3, CH 3 O, (CH 3) 2 N, F, Cl, NO 2, VN, and a method for preparing them.

1- (5-nitro o-2-fur oyl) -1-phenylsulphonyl-2- (4-phenyl Xf jets contain comonomers of this invention of ^one or heretofore prepared.

The process according to the invention consists in reacting phenyl 2- (5-nitro-2-furyl) -2-oxoethylsulfone of the formula II with aromatic aldehydes of the formula III.

where

X 1 = H, CH 3, CH 3 O, (CH 3 J 2 N, F, Cl, NO 2, CN in an environment of ethers, preferably dry ether, dibutyl ether, dioxane or a mixture thereof in the presence of titanium tetrachloride and pyridine at 0 ° C to the boiling point of solvents.

Advantages of the process for the preparation of the compounds according to the invention are that they are based on relatively available raw materials and are obtained in high yields and purity.

0 — vOTawneBi | JWíJrrmrera.

° 2 ^N jJ ~ ^C |

Example 1

0.1 mol (11 ml) of titanium tetrachloride in 25 ml of carbon tetrachloride was added dropwise at 0 [deg.] C. with stirring and exclusion of moisture to 200 ml of tetrahydrofuran. The resulting rye flocculent precipitate is stirred for a further 30 minutes and then successively at 282936 giving solutions of 0.05 mol of the corresponding aldehyde and 0.05 mol (14.7 g) of phenyl-2- (5-nitro-2-furyl) - Of 2-oxoethyl sulfone in 25 mL of tetrahydrofuran. After an additional 30 minutes, the suspension is allowed to proceed! a solution of 0.2 mol (16 ml) of pyridine in 30 ml of tetrahydrofuran is slowly added dropwise and stirring is continued for 6-10 hours at 0 ° C depending on the aldehyde reactivity. 50 ml of water and 50 ml of ether are added to the reaction mixture, the ether layer is separated and the aqueous is extracted three more times with 50 ml of ether. The combined ethereal solutions were shaken with 50 mL of saturated sodium chloride solution, water and dried over anhydrous MgSO 4. After removal of the solvent, the products are purified by crystallization from a suitable solvent, preferably ethanol or acetic acid, respectively, purified by chromatography. The yield of the reaction is 60-90%.

Example 2

As in Example 1, but as the dissolving agent, dtoxane or dibutyl ether is used and is operated at a temperature of 0 to 20 ° C. Reaction yields range from 50-80% of theory

Table 1 gives the physical constants and elemental analysis data and Table 2 gives the infrared spectra data of the compounds of the invention.

Table 1

1- (5-Nitro-2-fluoroyl) -1-phenylsulfonyl-2- (4-X-phenyl) ethylenes

Compound X Mol. formula (m. h) Mp ° C%) (yield, calculated / found % C % H % N % S la CisHisNOeS 130—131 ^a 59.52 3.42 3.65 8.36 H (383.3) (75) 59.21 3.38 3.61 8.31 lb CzoHisNOeS 190—192 ^b 60.46 3.81 3.52 8.07 CH3 (387.3) (67) 60.55 3.85 3.38 8j09 Ic C20H15NO7S 157—159 ^a 58.12 3.66 3.39 7.76 CHsO (413.3) (67) 57.88 3.52 3.36 7.66 Id C21H18N2O6S 192—194 ^a 59.15 4.25 6.57 7.52 (CH3) 2'N (426.4) (58) 58.73 4.19 6.50 7.28 Ie CwHizFNOeS 163—165 ^p 58.86 3.02 3.49 7.99 F (401.3) (89) 58.15 3.25 3.36 8.85 lf CwHuCINOeS 194—195 ^p 54.62 2.90 3.35 7.66 Cl (417.7) (87) 54.50 2.84 3.18 7.60 ig C19H12N2O8S 223—225 ^p 53.28 2.82 6.54 7.49 NO2 (428.3) (92) 53.21 2.84 6.29 7.39 Ih C20H12N2O6S 146—148 ^p 58.83 2.96 6.86 7.85 CN (408.3) (90) 58.47 2.87 6.80 7.74

crystallized from ethanol, ^b from acetic acid

Table 2

IR spectra of compounds Ia-Ih (cm ^-1 )

r Bile. 0 ií 0 γ C = C γ NO? as γ NO2 p γ SO ₂ as γ SO2 p yC C \ / O Ia 1678 1618 1554 1349 1324 1155 1023 at lb 1677 1610 1554 1349 1324 1154 1027 íc 1675 1612 1554 1349 1325 1153 1025 Id 1671 1618 1552 1349 1325 1155 1Ů27 Ie 1677 1610 1553 1348 1326 1155 1023 lf 1678 1614 1553 1349 1323 1154 1027 Ig 1678 1604 1553 1349 1325 1154 1024 Ih 1677 1621 1553 1349 1320 1155 1026

The compounds of the invention may serve as intermediates for the synthesis of other aminofuran derivatives.

Claims (2)

BEFORE ΜΕ Τ 1. 1- (5-Nitro-2-fluoroyl) -1-phenylsulfonyl-2- (4-X-phenyl) ethylenes of formula I OF THE INVENTION reacts with aromatic aldehydes of formula III (I) wherein X is H, CH 3, CH 3 O, (CH 3) 2 N, F, Cl, NO 2, CN. 2. A process for the preparation of 1- (5-nitro-2-furoyl) -1-phenylsulphonyl-2- (4-X-phenyl) ethylenes according to claim 1, characterized in that phenyl-2- (5- nitro-2-furyl-2-oxoethylsulfone of formula II XH®> -CH = O or where X = H, CH 3, CH 3 O, (CH 3) 2 N, F, Cl, NO 2, CN in an ether, preferably dry ether, dibutyl ether or a mixture thereof, tetrahydrofuran, dioxane in the presence of titanium tetrachloride and pyridine at 0 ° C to boiling point solvent.