PL157443B1 - Method for preparation of the new, n-phenylcarbamyle derivatives of difurylethane and difurylvinylchloride - Google Patents

Abstract

A method for producing new N-phenylcarbamoyl derivatives of difurylethane and difuryldichloroethane, by general formula 1 with R standing for an ethylidene or dichlorovinylidene group and X standing for an atom of hydrogen or chlorine, bromine, methyl, hydroxyl or methoxyl group in orto, metha or para arrangement of the benzene ring. The method is distinctive in that acid dichlorides by general formula 3 with R signifying as above, are condensed with aromatic amines by general formula 4, with X signifying as above, in the environment of an inert organic solvent and boiling temperature.<IMAGE>

Description

The subject of the invention is a process for the preparation of new N-phenylcarbamnium derivatives of difuΓylthane and difuryl dichlorethylate of the general formula I, in which R represents an ethylidene or dihalisilide group, and X represents a hydrogen atom or a chlorine, bromine atom, a methyl, hydroxyl or methoxy group in the ortho, meta or pair of benzene ring.

The new N-phenylcarbamnoyl derivatives obtained by the process according to the invention are used for the determination of difurylalphaatic dicarboxylic acids of the general formula 2, in which R represents a dtyliesne or dichlorinylidinyl group, and their dichlorides of the general formula 3, in which R is as defined above, used in the preparation of the corresponding diisocyanins of the furan series, which are intermediates for the synthesis of plastic materials.

According to the process of the invention, the new N-phenylbromylnum and difuryl dimethyl orthyl derivatives of the general formula I, in which R represents an ethylenne or dihrylowinyidesin group, and X represents a hydrogen atom or a chlorine, bromine, meeyl, hydroxy or hydroxyl group. methoxy in the ortho, meta or para position of the benzene ring, is obtained by knnding the acid dichlorides of the general formula III, in which R has the meaning given above, with aromatic amines of the general formula IV, in which X is as defined above, in an inert medium organic solvent at the reflux temperature of the reaction mixture. Acetone is preferably used as the inert organic solvent.

Difurylalyatic acid dichlorides, such as 1,1bbSs (5-HHO-olonormyl-fur-2-yl) atane and 1,1-bis (S-chloroformyl) -2-yl) -2,2-iichloroditylene, are obtained in a known manner by reaction of dicarboxylic acids: 1, lrbSs / - α-carboxyfur-2-yl) and l, lbbi8 / 5-carloxifur-2-yln / -2.2dCh0olOθdidine with thionyl chloride in benzene solution in the presence of pyridine.

Aromatic amines of the general formula 4, in which X is as defined above, are readily susceptible to clndθnsaayi with 1,1-bis / 5-chenrofnrmylofur-2-yOodβjsdmm and 1, ΐΜ> 1β / 5chinrnformylfui-2-yll / -2 in acetone. , 2idyhloroθtydneθm, forming rapidly crystallizing, homogeneous, stable products with sharp melting points. The chemical structure of the new N-pesylcarbamoyl derivatives obtained by the method according to the invention can be quickly and clearly confirmed by the IR and1H NMR spectra, making these combinations suitable for the identification of difurylalidatic dicarboxylic acids of the general formula 2 and their dichlorides of the general formula 3, in which R is as defined above. The use of acetone as a solvent in the process of condensation of aniline and its core derivatives with difurylaliphatic and acidic dichloromethics enables the products to crystallize directly from the reaction mixture, and the use of aromatic amines has a positive effect on the speed of the process and the yield of the reaction products.

The new N-phenylcarbamoyl derivatives obtained by the process according to the invention are also used as attractive raw materials in organic synthesis. In particular, due to the presence of chromophores and auxochromes in them, they find use as intermediates for the production of various types of dyes.

The simple technology is a significant advantage of the synthesis according to the invention. The condensation processes included in its composition do not require difficult-to-obtain romkeci conditions and I give products that are easy to separate in pure form.

The method according to the invention, without limiting its scope of protection, is explained in more detail in the following examples. · Melting points were determined with a Boetius apparatus · IR spectra were recorded on a Specord Μ-3Ο spectrophotometer, and NMR spectra were recorded on a BS 487C Tesla, 80 Mz spectrometer.

EXAMPLE 1 To a solution of 0.6 g / 0.00209 l, l-bas / 5-cltroroiiyl-fur-2-yl) ethane in 35 cm of anhydrous acetone, 0.5840 g (0.00627 oda) of aniline is added and after thorough mixing of _{) the} mixture is refluxed in a water bath for 2 hours. Then the reaction mixture is set aside and cooled to completely crystallize the product. The resulting precipitate was filtered off and then washed several times with small portions of cold acetone to give 1,1-bis (5-phenyio ^^^ οΠο fur-2-yl) et cs, mp 238-239 ° C.

IR analysis / ^sujrl, cm ¹ /: ^{3272, 3245,} 1596 / N-HA 31 ^ ^1273, 870 / C-HA 1647 / C "0 ^{/, 1520,} 1483 / C = C ^c r-rmagyczne ^/, 1322 / CN (j ¹ H NMR)? MSO-d 2 TMS J 4 1%: 1.70 (d, 3 H ^, -CH 6, 3 = 7 Hz), 4.50 (q, 1 H, CH, 3 = 7 Hz), 6.43 (d, 2H furan - 3.3 *, 3 = 4 Hz), 6.75 - 7.50 / m, 8H, 6H aromatics - 3.3 ', 4.4 *, 5.5 * and 2H furan - 4.4 '/, 7.78 (d, 4H aromatic - 2.2 *, 6.6 *, 3 = 8.5 Hz), 10.00 (broad band, 2H, 2 NH). For the formula C 8 H 2 N 6 O 4 (400.4-4) - the following was calculated:

7, C% Nj found: 7.1% N.

Example II. To a solution of 0.6 g (0.00209 l, l-bas / 5-troro-ylofu-23-yl) ethane in 35 cm of anhydrous acetone, 0.7999 g (0> 00627 of 2-chloroanSine) is added.

Further synthesis is as described in Example I to yield 1,1-bis £ 5 / 2chlorof ^Ur-2-yl J ethane, melting at 161 - ¹⁶ 2 ° C.

IR analysis (nujol, cm ^A ): 3384, 1593 / N-HA 31 ^ 1260, 855 / C-HA 1665 / C = 0A 1505 / C »C atroagic /, 1310 / CN /. For the formula ^ 24 ^H 18 ^ 12 ^N 2®4 / 459.33/ - Calculated: 6, C% Nj, found: 6.2% N.

Example III. To a solution of 0.6 g (0 C 0 209 oda / 1.1bbiβ) 5-hl0troroylofur-23yl / ethane in 35 ml of anhydrous acetone, 0.7999 g (00CO627 oda) 3-chlrraniline is added. Further synthesis is carried out analogously to Example uzyskujęc 1,1-bis £ 5 / ^f 3-chloro esylol ^<b ar amiillrfur- ² - ^yl / 'tanienia ethane at a temperature of 14 ² - ² 15.5 ° C.

IR analysis (nujol,? ^-1 ): 3279, 1594 (NH), 3175 ^, 311234, 869 (C-HA 1647 / C = 0.1534 ^, 1516 (C = C ctooagic), 1312 (CN). For the formula C24HjgCl (igO4 (469.33) - the following was calculated: 6, C% Nj, obtained: 6.1% N.

Example IV. To a solution of 0.6 g / 0 ^ 0209 οο ^ / l, l-bas / 5-clrorororoylofur “23 yl / ethane in anhydrous acetone, 0.7999 g / 0000627 ocTa / 4-chloroaniline are added. The further synthesis is carried out by is done analogously to Example 1 to give 1,1-bis-5- (4-chlorophenyto-bamoyl-fur-2-yl) ethane, mp 305.5-3O6.5 ° C.

Analysis: IR (nujol, co ¹ /: 3283 ^, 1594 (NH), 3181, 3118, 1243, 868 / C-HA 1647 / C = 0A 1525 ^, 1487 / C = 0 ctooagic /, 1320 / CN /. For the formula C24H ^ j ^ l ^ j ^^ N2O4 (469.33) - we calculated: 6, t% Nj, we got 5.9% N.

EXAMPLE 5 For a solution of 0.6 g / 3,000, 209 l. L-bas / 5-hlrr rororoyrf ur-2 ^y ln ^o / t ^ n ^{in 35 co3} congestion of acetone ^, 1 is added ^{, 0} 786 ^g / 0 ^ 0627 mole / 2-btooooa ⁿ foxes. Further synthesis is carried out analogously to Example otrzyoujęc 1,1-bis £ 5 / 2bromorβnyjokθrbamoilorfur-2-yl / 'ethane, m.p. 175.5 - 177 ^o C.

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Analyzes /: IR / nujol, cm ¹ /: 3373, 1593 / N-HA 3114, 1261, 854 / C-HA 1674 / C ^ A 1521 / C = C aromatic /, 1312, / CN /. For Formula C2 ₄ H ₁₈ B2 ^N 2 ° 4 (558.23), we calculated: 5.0¾ N; received: £ 4% N

Example 6 To a solution of 0.6 g (0.00209 mol) 1.1-bis / - chloroformyl fur-23 yl) atane in 35 cm3 of dry acetone, add 1.0786 g (0.00627 mol) of 3-bromooailin . A further synthesis is carried out analogously to Example 1, yielding 1,1-bis E 5- (3-bromorenyyokkabbamilorfur-2-yloyet) n with a melting point of 213-214.5 ° C.

Analysis: IR / nujol ^, cm ¹ /: 3280, 1590 / N-HA 3120 ^, 3066 ^, 1234 ^, 870 / C-HA 1650 / C = 0A 1535 ^, 1519 / C = C / aromatic, 1313 / CN /. For the formula C24 ^{H 18 Br} 2N2 ° 4/55 ⁸ "23 / - the following was calculated: 5 (% N; found: 5.1% N).

Example VII. To a solution of 0.6 g (0.0209 mol / l, l-bis (5-chrrorormyl-fur-23yl) ethane in 35 ml of anhydrous acetone, 1.0786 g (0.0627) of 4-bromooailin is added.

A further synthesis is carried out as described in Example I, to give 1,1-bis £ 5- / 4 ^b romo ^r βn ^and lokatba / Nilo / ^f Ur ² - ^yl / ethane at a temperature of 30, pressure ^p is ^7, 5 - ³⁰⁹ ° C.

Analysis: IR / nujc:!, Cm ¹ /; 3281, 1590 / NH /, 3115, 124), 866 (C-HA 1644 / C = 0 /, 1518, 1480 / C = C aromatic /, 1317 / CN /. For the formula ^C 24 ^{H and 8 Br} 2 N 2 ° 4 (558.23) - it was calculated: 5 ° C% Nj, found: 5.0% N.

Example VIII. To a solution of 0.6 g / 0 ^ 0209 (ηο ^ / 1,1-bis / - cbrorormylrfur-23 yl) atane in 35 cm3 of anhydrous acetone, 0.6719 g / 0 ^ 0627 mo ^ t 'o- toluidines / 2-methyla / nlins /. The further synthesis is carried out analogously as in Example 1, to give

1,1-bis E 5- (2-methylphenyl) rb (mm, chlorfur-2-yl) ethane, m.p. 157.5-159 ° C. Analysis ^: IR / nujol, cm ¹ /: 3425, 1584 / N-HA 3111, 1257 ^, 858 / C-HA 1668 / C = 0A 1519/0 = 0 aromatic A 1310 / CN /. Dl / of the formula θ26 ^Η 24 ^Ν 2 ° 4 / 428.49 / - calculated: 6.5% of Nj, we get:

6.6% N.

Example IX. To a solution of 0.6 g / O0OO2O9 mo2, / 1.1-bSs / 5-chrororormylfur-23yl / atane in 35 cm3 of anhydrous acetone, 0.6719 g / 0.0627 moo / m-toluidine / 3-methylor / is added. Iliny further synthesis is carried out analogously to example I, j-bis uzyskujęc £ ^5/3-y ney lofθn lock ^y / r ^b / ^f mnrlor Ur ² - ^yl / ethane at a temperature of 189-190 ° C topnieni./ . Analiz /: IR / nujol, cm ¹ /: 3242, 1610 / NH /, 3142, 1254 ^, 862 / C-HA 1645 / C = 0A 1542 ^, 1505 / C = C arrm8tycznβ /, 1326 / CN /. D1 (formula C26H24N2O4 (428.49) - Calculated: 6.1% Nj, found: 6.4% N.

Example X. To a solution of 0.6 g / 00 <03209 ύβ / 1,1-bis / S-cClorophorenyllrur-2-yl / 3 et / nu in 35 cm of anhydrous acetone, 0.6719 g / 0000627 mooa is added (p-toluidine A-methyl (nilines). Further synthesis is as described in Example I to yield 1,1-bis £ ⁵ - / 4-methyl ^{yy f} lo ^yl θn ^k / r ^{b r} lorfor amm ^ - ^ o / yr of ethane at a temperature than ^p / ² present ² 55- 56 ° C.

Analysis: IR / najo!., ¹ cm /: 3275, 1599 / N-HA ^ 31 ¹²⁴⁴ 868/1645 HA-C / C = 0 ^/, 1506 / C = C 1322 aromatyczneA / CN /. For the formula C 8 H 8 N 6 O 4 (428.49) - the following was calculated: 6.5% Nj, obtained:

6 ^ 4% N.

Example 11: To a solution of 0.6 g (0 ^ 0209 ιηο ^) 1,1-bis (5-chrorornyl-fur-2-yl) ethane in 35 cm3 anhydrous acetone, 0.6842 g (0 ^ 0627 ιηο ^ / 2-) is added / minophenol. The further synthesis is carried out analogously to example I, giving 1,1-bis £ 5- / 2 ^C y-hydroxyphenyl ¹ oxarbammyl / ^f u-2- ^{y 1} r. Yethane with a temperature of ^^ 1 ^ 1/256, ⁵ -2 ^{/ 8} ° ⁰ .

IR analyzes / nuijd, cm ¹ /: 3390, 1595 / N-HA 3127 ^, 1254 ^, 880 / CH /, 1648 / C = 0A 1552 ^, 1526 / C = C / aromatic A 1342 / CN /. D1 (formula C24H20N2B6 (432.43) - Calculated: 6.1% Nj, obtained: 6.5% N.

Example XII. To a solution of 0.6 g / 0000209 moo / l, l-bis (5-chroronnylfur-23-yl) athene in 35 cm of anhydrous acetone, 0.6842 g (0000209) (nda / 3- / 1 ^ 0 (^ 0 ^. further synthesis is carried out analogously to example uzyskujęc 1,1-bis £ 5/3-hydrrkβy ^f / ^b iylokar ammillr ^{f ur-2-yl} / e / an ^p yr a temperature of ni / iI / 1 ⁵⁶ - 1.57 ⁵ ° ^C.

Analyzes ^/: IR / nujol, cm ” ¹ /: 3329, 16C2 / NH /, 31 ^ 1243. 872 / CH /, 1646 / C = Q /, 1542, 1490 / OC arrm8 / icy / _l 1302 / CN /. Dl (formula C8HgNgOg (432.43) - Calculated: 6,%,, found: 6, (% N.

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Example XIII. For a solution of 0.6 g / 0.00209 nda / 1.1-bis55-chloroformyl3

Our-2-yl) ethane in 35 µl of anhydrous acetone, 0.6842 g (0.00627 n) of 4-arinoOenol are added. The further synthesis was carried out analogously to Example 1, obtaining 1,1-bis [5- (4-Cydroxyphenylcarbarn -HooOur-2-yl]) ethane, mp 172.5-174 ° C,

Anaaiz / a! IR / nujol ^, cm ¹ /: 3375 ^, 1615 / N-HA 31 ^ 1240. 877 / C-HA 1640 / C = 0A 1545 ^, 1502 / C = C aromatic /, 1333 / CN /. For the Formula C2 ₄ H ₂ QN ₂ Og (432.43) - we calculated: 6.1% N; found: 6, <% N ·

Example XIV. For a solution of 0.6 g / 0> 00209 nda / 0.1-bis / 5-c0loloroΓmylour3

2-yl (eaanu in 35 µl of anhydrous acetone, 0.7722 g (0.0627 g of moo (o-anisidine) (2-netoxyailine) is added. The further synthesis is carried out analogously to example 1, thus obtained

1.1- -is £ 5 = (2-methoxyO) methylcarbamrilorOuΓ-2-yl) ethane, mp 94.5-95 ° C. Analysis ^: IR / nujol, cr- ¹ /: 3413, 3398 ^, 1607 / N-HA 3122, 1251, 868 / C-HA 1667 / C = 0A 1540,

1527 / C = C arrmatic / _l 1339 / CN /. Formula C2gH24 ^N 20g / 460.49 / - calculated 6.1% Nj otrzynano 6 C% N

Example XV. For a solution of 0.6 g / 0 ^ 0 209 nda / 1,1-bis / 5-chOooorormylrOur3

2-yl (eaane in 35 µL of anhydrous acetone, 0.7722 g (0.00627 g of n-anisidine) (3-ratoxyanyl) is added. The further synthesis is carried out analogously to example 1, obtaining

1.1- bis £ 5 = (3-methoxyO) nylcarbamyilorfur-2-yl yetane, m.p. 189.5-191 ° C. Anaaiz ^a: IR / nuj ^o l, cr ¹ /: 3245, 1598 / N-HA 3132, 1255, 873 / CH /, 1649 / C = 0A 1543 ^, 1518 / C = C cannons ^ t ^^ r ^ e / , 1309 / CN /. For the formula C2gH24N2Og (460.49) it was calculated: 6.1% N; received:

6.2% N.

Example XVI. For a solution of 0.6 g /0.00209 Mo ^ a / 1,1-bS6 / 5-chOooorornylrOur =

2-yl (ethane in 35 µl of "anhydrous acetone), 0.7722 g (0.0627 ml) of p-anisidine (4retolsyaαilόny) is added. Further synthesis is carried out analogously to Example 1, thus obtained

1.1- ^- £ is 5- / 4-n / ^k sy tl ^o / nyllkarbamnilor ^on ur-2-yl ysaan melting point 245,5-247 ° C. AnaHz ^ IR '^ nujoL, cm ^-1 /: 3277 ^, 1600 / N-HA 31 ^ 1235 ^, 870 / C-HA 1639 / C-0A 153A 1500 / C = C αrryaticθA 1330 / CN /. For the formula c26H24 ^N 206 (460.49) - it was calculated: 6.1% of Nj, we found: 5.

Example XVII. For a solution of 0.8 g / 00 (03226 nda / 0.1-bis / 5-chloooroΓrylOur3

2-yOo (-2,2-dichloly) in 35 ml of anhydrous acetone, 0.6314 g (0000678 m) of aniline are added and, after thorough elution, it is heated under reflux in a water bath for 2 hours. . Thereafter, the reaction mixture is set aside and cooled to achieve complete crystallization of the product. The resulting precipitate was filtered off, and then quenched repeatedly with small portions of zirn / 6 l of acetone, 1,1-bis uzyskujęc / 5 / θnylokarbamriloror - 2ylor-2,2-dicCOoroetylen m.p. 257 - ² 58 ° C,

Ana ^a iza ^: IR / nujol, cr ^-1 /: 3348 ^, 3265 ^, 1600 / N-HA 31 ^ 1267.867 / C-HA 1646 / C = 0A 1538.

1497 / C = C arom and ^a-zcznae, 1328 / CN / j ^L H NMR TM3, CT ^pp 6 ^mA, 95 / d, 2H o ^{u u} ran - 3R,

3 = 4 Hz /, 7.03-7.45 (To, 6H aromatic - 3.3 *, 4.4 *, 5.5 * /, 7.50 / d, 2H Ouran - 4.4 *, 3 = 4 Hz /, 7.70 (d, 4H aroratic - 2.2 *, 6.6 *, 3 = 8.5 Hz /, 10.14 (broad band, 2H, 2 NH). For w: oru ^ 24 ^H 1E ^ 6 ^^^ 2 ^N 2 ° 4 / 467.31 / - calculated: 6, <% Nj, 5 ^ £% N was obtained.

Example XVIII. For a solution of 0.8 g / 0> 00226 nda / 0, = - iiβ / 5-c0lolororrylo0ur =

2-yl (-2.2-dichlolO-th) in 35 µl of anhydrous acetone, 0.8649 g (0> 00678 of 2-chloroaniline) is added. The further synthesis is carried out analogously to Example XVII, obtained

1.1- bis £ 5- / 2-chlorophenylcarbamnilor Our-2-yl y ^^ - dichloroethylene, melting point

195.5-197 ° C.

^A naai ^after: IR / ⁱ jejol ^, cm ^-1 /: 3368, 1593 / NH /, 3124 ^, 1256 ^, 863 / C-HA 1688 / C = 0A 1523 / C = C anmiitic /, 1312 / CN / «For the formula C 12 H 2 C 2 N 3 (536.20) - calc'd: 5.2% Nj found 5:% N

Example XIX. To a solution of 0.8 g / 0000226 rob / l, l-big / c0loloronryloOur 5-yl-23 / - ^2, 2-dichloroθty / θnu 35 cr of anhydrous acetone was added 0.8649 g / O0OO678 mooa / 3chllroaniliny. The further synthesis was carried out analogously to Example XVII, yielding 1,1-bis-(3-chloro / enylcar-αmrlloro-2-yl) 722, -dichlolO-ethylene, mp 256-257 ° C.

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Analysis: IR / nujol, cm ^-1 /: 3327, 3269, 1597 / N-HA 3123, 1268, 866 / C-HA 1648 / C = OA 1536 / C = C aromeaic /, 1313 / CN /. For the formula ^C 24 ^{H and} 4 ^Cl 4 N 2 ° 4 (536.20) - it was calculated: 5 → 2% Nj, 5.2% N was obtained.

Example XX. For a solution of 0.8 g (0.00226 mol / 1,1-bis) 5-chlorofommyl

Ur-2-yl / 22,2-dichloro-ethyl in 35 cm of anhydrous acetone, 0.8649 g (0.00678 g) of 4-chloroanthylline is added. Further synthesis is carried out analogously to Example XVII to yield 1,1-bis / of 5- / 4-chlorofenylok / rbamolll / fur-2-yl / 2,2-dicCloroetylenu and at a pressure ^p 316- ³ 17, ⁵ ° C.

IR analyzes / nujol, cm ^-1 /: 3340 ^, 3272 ^, 1599 / N-HA 3108 ^, 1270. 879 / C-HA 1646 / C = 0A 1535 ^, 1491 / C = C arlW / i ^ c; ^ r ^ e /, 1323 / CN /. For formula C ₂ C1 ₄ 4HJ ₄ N ₂ O ₄ / 536.20 / - Calculated: 5 _e 2% Nj obtained: 5;% N

Example XXI. For the solution 0.8 g / 0.00226 ιηο ^^, l-bis / 5-cCloroOormylof ur3

2-yl / -2,2-dicClorethylene in 35 cm3 of anhydrous acetone, 1.1663 g (0.00678 mol) of 2-bromooailin are added. The further synthesis is carried out analogously to Example 17, obtaining

1.1- bis £ 5- / 2b-bloro-enyl / rbamoyl / 0uι-2-yl / -2.2 -dichlolOθtyln with a melting point of 194-195 ° C.

Analysis ^: IR (nuj! ^ Cm ^-1 ): 3369 ^, 1588 / N-HA 3120 ^, 1252 ^, 860 (C-HA 1684 / C-0A 1514 / C "C aromatic", 1304 / CN /. For the formula C2 ₄ H1 _{4 5} r ₂ Cl ₂ N ₂ O ₄ (625.11) - the following was calculated: 4. £% Nj was 4.4% N.

Example XXII. For a solution of 0.8 g (0000226 l.1bbis) 5-Clloofomylofur

2-yl (-2,2-dicCloroethaneu) in 35 cm3 of anhydrous acetone, 1.1663 g (0 ^ 0678 mol) are added

3- bromoo / ilinl. The further synthesis is carried out analogously to example XVII, obtaining

1.1-bis (5- / 3b-blylphenylkaromlll) ur-2-yl) -2,2-dicClorletyl with a melting point of / 248.5-249 ° C.

IR analysis cm ^-1 /: 3339 ^, 329A 1590 / N-HA 314A 3103 ^, 1268. 863 / C-HA 1647 / C-0 /,

1523 / C = C / πμ (^^ ι:; ^ ^ γ θ /, 1306 / CN /. For the pattern C 4Hi _{2 4 2} 5r Cl ₂ N 2 O _4/525 ^ 11 / - Calculated: 4.5% N 4.6% of N.

Example XXHI. For a solution of 0.8 g / O0OO226 mdl / l, l-bis / 5-chlolofomy fur3

2-Ilyl (-2.2-Dichlol-Oyllene in 35 cm3 of anhydrous acetone, 1.1663 g (0000678 mol) are added

4- brlmoo / iliny. The further synthesis is carried out analogously to Example XVII, obtaining

1.1- bis / SA-biomofenylokarbammilo / fur -yl ^ _- / 22 ddichloloθtylen m.p.

318.5 - 320 ° C.

Analysis ^: IR (n [ ^mu] mol, cm ¹ /: 3335, 3266 ^, 1594 / N-HA 3108, 1264 ^, 873 (C-HA 1641 / C = A 1530 / C = C aromatic), 1319 / CN /. For the formula C ₂ 4Hi4B-2C12N ₂ ° 4/625 ^ 11 / - the following was calculated: 4.5% Nj and three mano: 4, f% N.

Example XXIV. For a solution of 0.8 g /0.(03226 mda / l, l-bis / 5-Chloiof omylofur

2-yl (-2,2-dichlol-Oylene) in 35 ml of anhydrous acetone, 0.7265 g (0.00678 mol) of o-toluidine (2-methylanniin) are added. Further synthesis is carried out in the same way as in Example 17, giving 1,1-bis £ 5- (2-methylpheyl) / rbamrllolfur-2-yliy-2-dic-chloroethylene with a melting point of 1.60.5 - 161.5 ° C .

Analyzes IR / ηφΐ, cm ¹ /: 3397. 33 ^ 1580 / N-HA 3158 ^, 3091 ^, 1263 ^, 866 / C-HA 1651 / C-0A 1505 / C = C / π ^ / υοζπθ /, 1307 / CN / . For the formula 6 ₂ θΗ ₂ θϋ12Ν20 ₄ / 495.36 / - it was calculated: 5.7% of Nj, we got: 5, i% N.

Example XXV. Di solution of 0.8 g / Ο0ΟΟ2Ϊ26 mol / 1.1-bsa / - Cdoiof omylofur3

2-yl (-2,2dichloelylene in 35 cm3 of anhydrous acetone, 0.7265 g (10000678 mol) m-toluidine (3-methylninia) is added. Ddszę synthesis is carried out analogously to Example XVII, uzyskujęc 1,1-bis £ 5/3-mθtlllfθnllok / rbammilo / fur-2-yl-2-J -dicCloroetylan melting at ²⁰² - ²⁰³ ° C.

Analyzes: IR / NUJ ^l l. ^-1 cy /: 3337. 3259 ^, 1604 / N-HA 3138 ^, 3100, 1264 ^, 879 / C-HA 1637 / C = 0 /, 1587, 1536 / C »C / aromatic /, 1311 / CN /. For the formula ^C 26 ^H 2 ^Cl 2 ^N 2 ° 4 (495.36) - the following was calculated:

5.7% of Nj. Found: 5, f% N.

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Example XXVI. To a solution of 0.8 g / 0.0 (03226 mol / 1.1-bls / 3-chloroformylOur-2-yl / 22.-diclrroethylene in 35 cm3 of anhydrous acetone, 0.7265 g (0.00678 rooa) is added. p-toluidine (4-retylaniniline). The further synthesis is carried out analogously to Example XVII, obtaining 1, i-bis 5 5 - (^^ - rethyl) oO iinyl oka ocobai roOur-2-yl -2, 2-DicCloroethylate, mp 270-271.5 ° C.

Analysis: IR / nujol, cr ¹ /: 3338 ^, 3253 ^, 1600 / Nh /, 3193 ^, 3105 ^, 1266 ^, 877 / C-HA 1643 / C = 0A

1532, 1503 / C = C aroratic /, 1323 / CN /. For the formula ^c gg ^H 20 ClgNgO ₄ (495.36) - the following was calculated:

5.1% of Nj, found: 5.3% of N.

Example XXVII. Oo of a solution of 0.8 g /0.00226 rcTa / 1,1-bis (5-chrororormyl)

0uo-2-yio (22, -diiclroroety) in 35 µl of anhydrous acetone, add 0.7399 g (0 ^ 0678 rcTa)

2-aminoOenol. The following synthesis is carried out analogously to example XVI!:, Giving

1.1- bis £ 5- / 2-hydroxyO / nylrkabamrilio Our-2-ylo y ^^ - dicClorethylene with a melting point of 320 - 321.5 ° C.

IR analysis / nujol, cr ^-1 /: 3384 ^, 1600 / N-HA 3139 "1280, 871 / C-HA 1638 / C» 0 / ^, 1586 ^, 1533 / C = C aorMt '/ cz ^ Γ ^ θ / ₁ 1335 / CN /. For the formula C ₂₄ H ^ 6 Cl ^^ ^N 20g / 499.31 / - we calculated: 5.6% Nj, we got: 5.4% N.

Example XXVIII. About a solution of 0.8 g / 0000226 rob / l, łbbis / 5-clrororormylure2 ^^ / - 2.2dichroroety / ene in 35 ml of anhydrous acetone, 0.7399 g (0 ^ 0678 nooa) is added

3-mninophenol. The further synthesis is carried out analogously to Example XVII, yielding 1,1-1 bis £ 5- (3-hydroxy O) nylrcarbamoyl ?ur-2-yl? -2,2-dicClorethylene, m.p.

263-264 ° C.

Analysis: IR / nujol, cr ¹ /: 3324, 3229 ^, 1599 (NH), 3134 ^, 3106, 1274 ^, 864 (C-HA 1640 / C = 0 / ^,

1561, 1538 / C = C aoMtyc ^ ne / ₁ 1340 / CN /. Ola pattern C 4HigC ₂ ¹ 2 ^N 2Og / 499.31 / - Calculated: 5 £% Nj was obtained: 5.5% N.

Example XXIX. Oo of a solution of 0.8 g / 0> 00226 role / l, lbbis / 5-chrrrorormylour-2o yl / -2,2-Ρ- ^ ο4 ^ οι ~ ο / ty / eisnu in 35 crn of anhydrous acetone, add 0, 7399 g / 0000678 different ¹ 4 f ^: enol u. The synthesis is analogous to that in Example XVII, thus obtaining

1.1- bis / 5- / 4-hydroxyO / nylrcarbamrilorOur-2-yl £ -2,2-dicClorrethylene with melting point

271.5 - 273 ° C.

^Analysis: IR / nujol, cr ¹ /: 3243 / N /, ^3130, 1269 / CH /, 1609/0 = 0 /, ^1558, 1497 / C = C ^Arora atyczns /, 1308 / CN /. Ola pattern C _l6 H ₂₄ Cl ₂ N ₂ 0 g / 499.31 / - Calculated: 5 <Nj% was obtained: 5.5% N.

Example XXX. About a solution of 0.8 g / 0> 00226 nda / 1.1-bSs / 5-chrororormylOur-23yl / -2,2-dicCloroethane in 35 µl of anhydrous acetone, 0.8350 g (0> 00678) is added 'o-anisidine / 2-retrksyatiiiny /. The further synthesis is carried out analogously to the example

XVII, to give 1,1-bis £ 5- / 2-retrksyOenylrkarbamorlorOur-2-yl -2,2-£ dicCloroetylan is at a temperature ^and a ^p nien 191.5 - 1 ⁹ 3 ° C.

Analysis: IR / Dujo ^ cr ^-1 / 3401, ¹⁶⁰⁷ / N-HA 3123, ^1258, 867/1678 HA-C / C = 0 ^/, 1585, 1527 / C = C aorfflatyczne /, 1335 / CN /. For the formula C26H20Cl2 ^N 2 ° 6 ( ⁵²⁷ → 96) - Calculated: 5;% Nj, found: 5.2% N.

Example XXXI. Oo of the solution 0.8 g / 0 »(03226 nda / 1.1-bi8 / 5-cCloooOormylof ur3

2-yl / -2,2-dicCloroethaneu in 35 ml of anhydrous acetone, 0.8350 g / 0.0678 moos / r-anisidine is added. The further synthesis is carried out analogously to the example

XVII, obtaining 1,1-bis £ 5- (3-retoxy-methylcarbamrilooOur-2-yl) -2, -dichroroethyl with a melting point of ²²² - ²²³ ° ^C ,

IR analysis / nujol, cr ¹ /: 3302 ^, 1597 / N-HA 3124, 1273, 863 / C-HA 1644 / C = 0A 1540 / C = C aoomatic A 1308 / CN /. Ola in? Oou CggHggCggNgOg (527.36) - calculated: 5.3% of Nj, obtained:

5.3% N.

Example W ^ XH. Oo of a solution of 0.8 g / 0t00226 ηο ^ / l, lbbis / 3-clrororormyl3

Ur-2-yro (-2.2 diclrrroθtyeene in 35 ml of anhydrous acetone, 0.8350 g (0.0678 of rooa) (p-anisidine (4-methoxyaniline) is added. The further synthesis is carried out analogously to the example

157 443

XVII, to give 1,1-white / · 5/4-metoksyfenylokarbamoilą / fur-2-yl-2,2-J dichloroetylan m.p. 243 - ² 44.5 ° C.

Analysis: IR / nujol, cm " ¹ /: 3344, 3251, 159Θ / NH /, 3162, 3108, 1229, 876 / CH /, 1640 / C = 0 /, 1537, 1503 / C» C aromatic, 1320 / CN /. For the formula ° 26 ^H 2cC ¹ 2 ^N 2 ° 6 /®27.36/ - it was calculated:

5.3% Nj. Found: 5:% N.

MODEL 1

HOOC

COOH

PATTERN 2

COCl

MODEL 3

NH

MODEL 4

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Claims (2)

Patent Claims A method for the preparation of new N-phenylcarbamoyl derivatives of difurylethane and difuryl dichloroethylene of the general formula I, in which R is an atyddene or dihalovinylddanone group and X is a hydrogen atom or a chlorine atom, bromine atom, a madyl group, hydroxyl or methoxy in the ortho, meta or para position of a benzene ring, characterized in that acid dichlorides of the general formula III, in which R is as defined above, are subjected to the disintegration of aromatic amines of the general formula IV, in which X has the above-mentioned meaning, in an inert organic solvent at the boiling point reaction mixture The method according to claim 1, characterized in that acetone is used as the inert organic solvent.