Przedmiotem wynalazku jest sposób otrzymywania nowych podstawionych w pierscieniu fenylowym pochodnych 2,6-difenylo-2,3,6,7-tetrahydro -1 H,5H-1,4-ditiino-[2,3-c:5,6-c'] dipirolo- 1,3,5,7-tetraonu o ogólnym wzorze 1, w którym R oznacza grupe metylowa lub metoksylowa albo atom halogenu. Nowe zwiazki otrzymywane sposobem wedlug wynalazku stanowia zielone pig¬ menty organiczne do przyrzadzania farb i lakierów oraz do barwienia mas plastycznych.Sposobem wedlug wynalazku na podstawiona w pierscieniu fenylowym pochodna 3,4- dichloro-l-fenylo-lH-pirolo-2,5-dionu o ogólnym wzorze 2, w którym R ma wyzej podane znacze¬ nie, dziala sie tiomocznikiem w obecnosci dimetyloformamidu. Otrzymuje sie z wydajnoscia przekraczajaca przewaznie 90% zielone pigmenty o róznych odcieniach, charakteryzujace sie trwaloscia na rozpuszczalniki 5 ewentualnie 4,5 w skali pieciostopniowej.Sposób wedlug wynalazku ilustruja nastepujace przyklady, w których procenty oznaczaja procenty wagowe, a stopnie temperatury podano w stopniach Celsjusza: Przyklad I. Do roztworu 13,83g (0,05 mola) 3,4-dichloro-l- /4-chlorofenylo/-lH-pirolo- 2,5-dionu w 100 cm3 dimetyloformamidu dodano 7,61 g (0,1 mola) tiomocznika i mieszanine wstrzasano do momentu rozpuszczenia sie osadu tiomocznika. Po 20 godzinach odsaczono wytwo¬ rzone krysztaly, przemyto trzykrotnie porcjami po 50 cm3 metanolu, wody, etanolu i acetonu, a nastepnie wysuszono. Otrzymano 11,24 g 2,6-bis /4-chlorofenylo/-2,3,6,7-tetrahydro -1H,5H-1,4- ditiino [2,3-c:5,6-c'] dipirolo-1,3,5,7-tetraonu w postaci zóltozielonych blyszczacych plytek o tem¬ peraturze topnienia powyzej 300°. Wydajnosc wyniosla 95%. Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.IR /KBR/: 1695, 1710, 1780 /C=C-N-C=0/; 1575 cm'1 /C=C/ MS: 478 [M + 4]+- /22,2%/, 476 [M + 2]+/80,3%/, 474 M+- /100%/, 442[M - 32]*- /1,1%/, 432 [M + 2-44f-/8,9%/, 430 [M-44]-/13,1%/.Przykladu. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 13,83 g (0,05 mola) 3,4-dichloro-l-/3-chlorofenylo/-lH-pirolo-2,5-dionu. Otrzymano 11,0 g 2,6-bis/3-chloro- fenylo/ -2,3,6,7-tetrahydro-lH, 5H-l,4-ditiino [2,3-c:5,6-c*] dipirolo-1,3,5,7-tetraonu w postaci zielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 92%.Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.2 143 804 IR/KBr/: 1695, 1710, 1775 /0=C-N-C=0/; 1575 cm"1 /C=C/ MS: 478 [M + 4]+- /21,4%/, 476 [M + 2]+- /76,1%/, 474M+- /100%/, 444 [M + 2-32]*- /6,0%/, 442 [M-32]+• /8,6%/, 432 [M + 2-44]+- /4,5%/, 430 [M-44]+- /6,5%/.Przyklad III. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 13,60 g /0,05 mola/ 3,4-dichloro-l-/4-metoksyfenylo/ -lH-pirolo-2,5-dionu. Otrzymano ll,22g 2,6-bis /4- metoksyfenylo/-2,3,6,7-tetrahydro-lH, 5H-l,4-ditiino- [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zóltozielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 96%. Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.IR/KBr/: 1695, 1715, 1780 /0=C-N-C=CV; 1757 cm"1 /C=C/ MS: 468 [M + 2]+- /16,4%/, 466 M+- /100%/, 434 [M-32]+- /2,8%/, 422 [M-]+- /12,7%/.Przyklad IV. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 13,6g /0,05 mola/ 3,4-dichloro-l-/3-metoksyfenylo/-lH-pirolo-2,5-dionu. Otrzymano 8,81 g 2,6-bis/3-meto- ksyfenylo/-2,3,6,7-tetrahydro-lH,5H, l,4-ditiino[2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 76%.Pigment odznacza sie trwaloscia na rozpuszczalniki 4-5 w skali pieciostopniowej.IR/KBr/: 1705, 1715, 1775/0=C-N-C=0/; 1575cm"1 /C=C/ MS: 468 [M + 2]+- /14,2%/, 466 M+- /100%/, 434 [M- 32]+- /l 1,9%/, 422 [M- 44]+- /2,4%/.Przyklad V. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 12,8g /0,05 mola/ 3,4-dichloro-l-/4-metylofenylo/ -lH-pirolo-2,5-dionu. Otrzymano 10,25 g 2,6-bis/4- metylofenylo/-2,3,6,7-tetrahydro-lH, 5H-l,4-ditiino [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zóltozielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 94%. Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.IR/KBr/: 1695, 1710, 1780 /0=C-N-C=0/; 1575 cm"1 /C=C/ MS: 436 [M + 2f • /15,2%/, 434M+- /100%/, 402 [M-32]+- /0,8%/, 390 [M-44]+- /24,1%/ Przyklad VI. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 12,8g /0,05 mola/ 3,4kiichloro-l-/3-metylofenylo/ -lH-pirolo-2,5-dionu. Otrzymano 9,81 g 2,6-bis /3-metylo- fenylo/-2,3,6,7-tetrahydro -IH, 5H-l,4-ditiino [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 90%.Pigment odznacza sie trwaloscia na rozpuszczalniki 4-5 w skali pieciostopniowej.IR/KBr/: 1705, 1715, 1780 /0=C-N-C=0/: 1575 cm"1 /C=C/ MS: 436 [+2]*- /14,1%/, 434M+- /100%/, 402 [M-32]+- /1,2%/, 390 [M-44]+- /4,6%/.Przyklad VII. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 16,05 g /0,05 mola/ l-/4-bromofenylo/-3,4-dichloro -lH-pirolo-2,5-dionu. Otrzymano 13,38 g 2,6-bis /4- bromofenylo/ -2,3,6,7-tetrahydro-lH, 5H-l,4-ditiino [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zóltozielonych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 95% Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.IR/KBr/: 1685, 1700, 1710, 1780 /0=C-N-C=0/; 1575cm"1 /C=C/.MS: 566 [M + 4]+- /56,9%/, 564 [M + 2]+- /100%/, 562 M+- /49,3%/, 534 [M + 4-32]+- /5,2%/, 532 [M + 2-32]+- /6,6%/, 530 [M-32f- /3,4%/, 522 [M + 4-44]+- /7%/, 520 [m + 2 - 44]+- /9,9%/, 518 [M-44]+- /6,5%/.Przyklad VIII. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 16,05 g /0,05 mola/ l-/3-bromofenylo/-3,4-dichloro-lH-pirolo-2,5-dionu. Otrzymano 13,08 g 2,6-bis /3-bro- mofenylo/-2,3,6,7-tetrahydro-lH,5H-l,4-ditiino [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zielonego drobnokrystalicznego zwiazku o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 93%. Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.IR/KBr/: 1710, 1775 /0=C-N-C=0/, 1565, 1575cm"1 /C=C/ MS: 566 [M + 4]+• /60,0%/, 564 [M + 2]+- /100%/, 562 M+- /49,2%/, 534 [M + 4- 32]+- /6,7%/ 532 [M + 2- 32]+- /6,7%/ 530 [M- 32]+- /4,7%/, 522 [M + 4 - 44]+- /3,6%/,520[M + 2-44]+-/7,8%/, 518[M-44f-/2,9%/.Przyklad IX. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 13,0g /0,05 mola/ 3,4-dichloro-l-/4-fluorofenylo/ -lH-pirolo-2,5-dionu. Otrzymano 10,6 g 2,6-bis /4-fluoro- fenylo/-2,3,6,7-tetrahydro -IH, 5H-l,4-ditiino [2,3-c: 5,6-c'] dipirolo-l,3,5,7-tetraonu w postaci zóltozielonych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 96%. Pigment odznacza sie trwaloscia na rozpuszczalniki 5 w skali pieciostopniowej.143804 * IR /KBr/: 1685,1695,1710,1780 /0=C-N-C=0/; 1575 cm"1 /C=C/ MS: 444 [M + 2]4- /12,2%/, 442 M*- /100%/. 410 [M-32]*- /l,2%/, 398 [M-44]*- /l 1,3%/ Przyklad X. Postepowano sposobem opisanym w przykladzie I, przy uzyciu 13,0g /0,05 mola/ 3,4-dichloro-l-/ 3-fluorofenylo/-lH-pirolo -2,5-dionu. Otrzymano 10,5 g 2,6-bis /3- fluorofenylo/-2,3,6,7-tetrahydro-lH, 5H-l,4-ditiino [2,3-c:5,6-c*] dipirolo-l,3,5,7-tetraonu w postaci zóltozielonych blyszczacych plytek o temperaturze topnienia powyzej 300°. Wydajnosc wyniosla 95%. Pigment odznacza sie trwaloscia na rozpuszczalniki 4-5 w skali pieciostopniowej.IR /KBr/: 1680, 1695, 1710. 1775 /0=C-N-C=0/, 1575 cm"1 /C=C/ MS: 444[M +2f• /14,3%/. 442M*- /100%/, 410 [M-32]*• /1,3%/, 398 [M-44]*• /5,8%/.Zastrzezenie patentowe Sposób otrzymywania nowych podstawionych w pierscieniu fenylowym pochodnych 2,6- difenylo-2,3,6,7-tetrahydro -IH, 5H-l,4-ditiino [2,3-c:5,6-c'] dipirolo-l,3,5,7-tetraonu o ogólnym wzorze 1, w którym R oznacza grupe metylowa lub metoksylowa albo atom halogenu, znamienny tym, ze na podstawiona w pierscieniu fenylowym pochodna 3,4-dichloro-l-fenylo-lH-pirolo-2,5- dionu o ogólnym wzorze 2, w którym R ma wyzej podane znaczenie, dziala sie tiomocznikiem w obecnosci dimetyloformamidu.143804 o WZOR 2 Pracownia Poligraficzna UP PRL. Naklad 100 egz Cena 220 zl PLThe subject of the invention is a method for the preparation of new 2,6-diphenyl-2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino- [2,3-c: 5,6-c '] dipyrrole-1,3,5,7-tetraone of the general formula I, in which R is a methyl or methoxy group or a halogen atom. The new compounds obtained by the method according to the invention are green organic pigments for the preparation of paints and varnishes and for coloring plastic masses. According to the invention, the 3,4-dichloro-1-phenyl-1H-pyrrole-2,5-derivative substituted in the phenyl ring is based on the method of the invention. of the dione of general formula II, in which R is as defined above, is treated with thiourea in the presence of dimethylformamide. Green pigments of various shades are obtained with a yield generally exceeding 90%, and they have a solvent stability of 5 or 4.5 on a five-point scale. The method according to the invention is illustrated by the following examples, in which the percentages are percentages by weight and the temperature degrees are given in degrees Celsius: Example 1 To a solution of 13.83 g (0.05 mol) of 3,4-dichloro-1- (4-chlorophenyl) -1H-pyrrole-2,5-dione in 100 cm 3 of dimethylformamide was added 7.61 g (0.1 mol) of thiourea and the mixture was shaken until the precipitate of thiourea was dissolved. After 20 hours, the crystals formed are filtered off, washed three times with 50 cm 3 of methanol, water, ethanol and acetone, and then dried. 11.24 g of 2,6-bis (4-chlorophenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c '] dipyrrolo were obtained. -1,3,5,7-tetraon in the form of glossy yellow-green plates with a melting point above 300 °. The yield was 95%. The pigment has a stability to solvents on a five-point scale. IR (KBR): 1695, 1710, 1780 (C = C-N-C = 0); 1575 cm -1 (C = C / MS: 478 [M + 4] + - (22.2%), 476 [M + 2] + (80.3%), 474 M + - (100%), 442 [ M - 32] * - (1.1%), 432 [M + 2-44f - (8.9%), 430 [M-44] - (13.1%). The method described in Example 1 is followed, using 13.83 g (0.05 mol) of 3,4-dichloro-1- (3-chlorophenyl) -1H-pyrrole-2,5-dione. 11.0 g of 2,6-bis (3-chlorophenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c * ] dipyrrole-1,3,5,7-tetraone in the form of glossy green plates with a melting point above 300 °. The yield was 92%. The pigment has a 5-point solvent stability. 2 143 804 IR (KBr): 1695, 1710, 1775 (0 = C-N-C = 0); 1575 cm < 1 > (C = C / MS: 478 [M + 4] + - (21.4%), 476 [M + 2] + - (76.1%), 474M + - (100%), 444 [ M + 2-32] * - / 6.0% /, 442 [M-32] + • / 8.6% /, 432 [M + 2-44] + - / 4.5% /, 430 [M -44] + - (6.5%). Example III The procedure of example I is followed, using 13.60 g (0.05 mol) 3,4-dichloro-1- (4-methoxyphenyl) -1H- pyrrole-2,5-dione Obtained 11.22 g 2,6-bis (4-methoxyphenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino- [2,3-c: 5,6-c '] dipyrrole-1,3,5,7-tetraon in the form of glossy yellow-green plates with a melting point above 300 ° C. The yield was 96%. The pigment has a solvent stability of 5 on a five-point scale. IR/KBr/ : 1695, 1715, 1780/0 = CNC = CV; 1757 cm "1 / C = C / MS: 468 [M + 2] + - / 16.4% /, 466 M + - / 100% /, 434 [M -32] + - (2.8%), 422 [M -] + - (12.7%). Example IV. The method described in Example 1 is followed, using 13.6 g (0.05 mol) 3,4-dichloro-1- (3-methoxyphenyl) -1H-pyrrole-2,5-dione. There was obtained 8.81 g of 2,6-bis (3-methoxyphenyl) -2,3,6,7-tetrahydro-1H, 5H, 1,4-dithiino [2,3-c: 5,6-c ' ] dipyrrole-1,3,5,7-tetraon in the form of glossy green plates with a melting point above 300 °. The yield was 76%. The pigment has a stability to solvents 4-5 on a five-point scale. IR/KBr/: 1705, 1715, 1775/0 = C-N-C = 0 /; 1575cm "1 (C = C / MS: 468 [M + 2] + - (14.2%), 466 M + - (100%), 434 [M- 32] + - / l 1.9% /, 422 [M- 44] + - (2.4%). Example 5 The procedure described in Example 1 is followed, using 12.8 g (0.05 mol) 3,4-dichloro-1- (4-methylphenyl) -1H -pyrrole-2,5-dione There was obtained 10.25 g 2,6-bis (4-methylphenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c : 5,6-c '] dipyrrole-1,3,5,7-tetraon in the form of glossy yellow-green plates with a melting point above 300 ° C. The yield was 94%. The pigment has a solvent stability of 5 on a five-point scale.IR/KBr /: 1695, 1710, 1780/0 = CNC = 0 /; 1575 cm "1 / C = C / MS: 436 [M + 2f • / 15.2% /, 434M + - / 100% /, 402 [M- 32] + - (0.8%), 390 [M-44] + - (24.1%). Example VI. The method described in Example 1 was followed using 12.8 g (0.05 mol) of 3,4-chloro-1- (3-methylphenyl) -1H-pyrrole-2,5-dione. There were obtained 9.81 g of 2,6-bis (3-methylphenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c ' ] dipyrrole-1,3,5,7-tetraon in the form of glossy green plates with a melting point above 300 °. The yield was 90%. The pigment is resistant to solvents 4-5 on a five-point scale. IR/KBr/: 1705, 1715, 1780/0 = CNC = 0 /: 1575 cm "1 / C = C / MS: 436 [+ 2] * - / 14.1% /, 434M + - / 100% /, 402 [M-32] + - / 1.2% /, 390 [M-44] + - /4.6%/. Example VII The method described in Example 1 was followed with 16.05 g (0.05 mol) of 1- (4-bromophenyl) -3,4-dichloro-1H-pyrrole-2,5-dione. 13.38 g of 2 were obtained. , 6-bis (4-bromophenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c '] dipyrrole-1,3,5 , 7-tetraon in the form of yellow-green plates with a melting point above 300 ° C. Efficiency 95% The pigment has a 5-point stability to solvents.IR/KBr/: 1685, 1700, 1710, 1780/0 = CNC = 0 /; 1575cm "1 /C=C/.MS: 566 [M + 4] + - / 56.9% /, 564 [M + 2] + - / 100% /, 562 M + - / 49.3% /, 534 [M + 4-32] + - / 5.2% /, 532 [M + 2-32] + - / 6.6% /, 530 [M-32f- / 3.4% /, 522 [M + 4-44] + - (7%), 520 [m + 2 - 44] + - (9.9%), 518 [M-44] + - (6.5%). Example VIII. The method described in Example 1 is followed using 16.05 g (0.05 mol) 1- (3-bromophenyl) -3,4-dichloro-1H-pyrrole-2,5-dione. There was obtained 13.08 g of 2,6-bis (3-bromophenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c ' ] dipyrrole-1,3,5,7-tetraon as a green, fine crystalline compound with a melting point greater than 300 °. The yield was 93%. The pigment has a resistance to solvents on a 5-point scale. IR/KBr/: 1710, 1775/0 = CNC = 0 /, 1565, 1575cm "1 / C = C / MS: 566 [M + 4] + • / 60, 0% /, 564 [M + 2] + - / 100% /, 562 M + - / 49.2% /, 534 [M + 4- 32] + - / 6.7% / 532 [M + 2- 32 ] + - / 6.7% / 530 [M- 32] + - / 4.7% /, 522 [M + 4 - 44] + - / 3.6% /, 520 [M + 2-44] + - (7.8%), 518 [M-44f- (2.9%). EXAMPLE IX The method described in Example 1 is followed, but with 13.0 g (0.05 mol) 3,4-dichloro-1- (4-fluorophenyl) -1H-pyrrole-2,5-dione There was obtained 10.6 g of 2,6-bis (4-fluorophenyl) -2,3,6,7-tetrahydro-1H, 5H-1, 4-dithiino [2,3-c: 5,6-c '] dipyrrole-1,3,5,7-tetraon in the form of yellow-green plates with a melting point above 300 ° C. The yield was 96%. The pigment is stable to solvents 5 on a five-point scale. 143804 * IR / KBr /: 1685,1695,1710.1780 / 0 = CNC = 0 /; 1575 cm "1 / C = C / MS: 444 [M + 2] 4- / 12.2 % /, 442 M * - (100%). 410 [M-32] * - / 1.2% /. 398 [M-44] * - / 1.3% / Example X. The procedure described in example I was followed, using 13.0 g / 0.05 mol (3,4-dichloro-1- (3-fluorophenyl) -1H-pyrrole -2,5-dione. 10.5 g of 2,6-bis (3-fluorophenyl) -2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c *] dipyrrolo were obtained. -1,3,5,7-tetraon in the form of shiny yellow-green plates with a melting point above 300 °. The yield was 95%. The pigment is resistant to solvents 4-5 on a five-point scale. IR / KBr /: 1680, 1695, 1710.1775 / 0 = CNC = 0 /, 1575 cm "1 / C = C / MS: 444 [M + 2f • / 14.3% /. 442M * - / 100% /, 410 [M-32] * • / 1.3% /, 398 [M-44] * • /5.8%/. Patent disclaimer Method for obtaining new 2,6-diphenyl-2,3,6,7-tetrahydro-1H, 5H-1,4-dithiino [2,3-c: 5,6-c '] dipyrrole-1,3, substituted in the phenyl ring, 5,7-tetraone of the general formula I, in which R is a methyl or methoxy group or a halogen atom, characterized in that the 3,4-dichloro-1-phenyl-1H-pyrrole-2,5- derivative substituted in the phenyl ring is of the dione of the general formula 2, in which R has the meaning given above, acts with thiourea in the presence of dimethylformamide.143804 o PATTERN 2 Printing Workshop of the Polish People's Republic of Poland. Mintage 100 copies Price PLN 220 PL