CS196927B1 - Process for preparing 2-substituted 1-/5-nitro-2-furyl/ethylenes - Google Patents
Process for preparing 2-substituted 1-/5-nitro-2-furyl/ethylenes Download PDFInfo
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- CS196927B1 CS196927B1 CS578A CS578A CS196927B1 CS 196927 B1 CS196927 B1 CS 196927B1 CS 578 A CS578 A CS 578A CS 578 A CS578 A CS 578A CS 196927 B1 CS196927 B1 CS 196927B1
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- Prior art keywords
- nitro
- furyl
- ethylene
- substituted
- ethylenes
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- 238000004519 manufacturing process Methods 0.000 title claims 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 title 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- -1 2-substituted 1- (5-nitro-2-furyl) -ethylenes Chemical class 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- DWHDJUJHFAUWFM-UHFFFAOYSA-N 2-(2-bromoethenyl)-5-nitrofuran Chemical group [O-][N+](=O)C1=CC=C(C=CBr)O1 DWHDJUJHFAUWFM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LWOWNIPZHGWKNR-DUXPYHPUSA-N 3-(5-nitro-2-furyl)acrylic acid Chemical class OC(=O)\C=C\C1=CC=C([N+]([O-])=O)O1 LWOWNIPZHGWKNR-DUXPYHPUSA-N 0.000 description 2
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 description 2
- NUOVYYHNMGAOLS-UHFFFAOYSA-N C1=CC(=CC=C1C=CC2=CC=C(O2)[N+](=O)[O-])O Chemical group C1=CC(=CC=C1C=CC2=CC=C(O2)[N+](=O)[O-])O NUOVYYHNMGAOLS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LDDUFMLKAQVAAL-UHFFFAOYSA-N 2-ethenyl-5-nitrofuran Chemical group [O-][N+](=O)C1=CC=C(C=C)O1 LDDUFMLKAQVAAL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HXNCSUWRMWHFBO-UHFFFAOYSA-N C1=C(C=CC2=CC=CC=C12)C=CC=1OC(=CC=1)[N+](=O)[O-] Chemical group C1=C(C=CC2=CC=CC=C12)C=CC=1OC(=CC=1)[N+](=O)[O-] HXNCSUWRMWHFBO-UHFFFAOYSA-N 0.000 description 1
- RKZWSRMSZYLDSW-UHFFFAOYSA-N C1=CC(OC)=CC=C1C=CC1=CC=C([N+]([O-])=O)O1 Chemical group C1=CC(OC)=CC=C1C=CC1=CC=C([N+]([O-])=O)O1 RKZWSRMSZYLDSW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- OFPYJCBKSBUZBC-UHFFFAOYSA-N [N+](=O)([O-])C1=CC=C(O1)C(=C)Br Chemical group [N+](=O)([O-])C1=CC=C(O1)C(=C)Br OFPYJCBKSBUZBC-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Description
Vynález rieši spósob přípravy 2-substituovaných 1- (5-nitr o-2-f uryl) etylénov.The present invention provides a process for the preparation of 2-substituted 1- (5-nitro-2-furyl) ethylenes.
Příprava 2-substituovaných l-(5-nitro-2-furyljetylénových derivátov je doteraz riešená týmito píatimi spósobmi:The preparation of the 2-substituted 1- (5-nitro-2-furyl) ethylene derivatives has hitherto been addressed in the following five ways:
1. Kondenzáciou 5-nitro-2-furaldehydu, jeho acetátu resp. acetálu s alkylheterocyklami, ktorých alkylová skupina má kyslé vodíky (Ueno S., Shimogo E., Kawasaki T., Immaru D., Osaki Y.:.Jap, pat. výkl. spis 71 17 790 /1971/, Chem. Abstr. 74, 42 349 /1971/).1. Condensation of 5-nitro-2-furaldehyde, its acetate, resp. acetal with alkyl heterocycles whose alkyl group has acidic hydrogens (Ueno, S., Shimogo, E., Kawasaki, T., Immaru, D., Osaki, Y., Jap., U.S. Pat. No. 71,167,790 (1971), Chem. Abstr. 74, 424949 (1971)).
2. Kondenzáciou 5-nitro-2-furaldehydu s heteroaryloctovými alebo fenyloctovými kyselinami a nasledujúcou dekarboxláciou vzniknutého produktu (Hirao I., Kitamura Y., Furuno M.: Nippon Kagaku Zasshi 84, 940 /1984/, Chem. Abstr. 61, 14 617 /1964/).2. Condensation of 5-nitro-2-furaldehyde with heteroarylacetic or phenylacetic acids and subsequent decarboxlation of the resulting product (Hirao I., Kitamura Y., Furuno M .: Nippon Kagaku Zasshi 84, 940 (1984), Chem. Abstr. 61, 14) 617 (1964).
3. Priamou cyklizáciou reaktívnych derivátov kyseliny 3- (5-nitro-2-furyl)akrylovéj (Lanquist J. K.: Angl. patent 1028 152 /1966/, Chem. Abstr. 65, 2 273 /1966/).3. Direct cyclization of reactive 3- (5-nitro-2-furyl) acrylic acid derivatives (Lanquist J.K .: English patent 1028 152 (1966), Chem. Abstr. 65, 2 273 (1966)).
4. Kondenzáciou 2-furaldehydu v bázickom prostředí s alkalickými soíami alkylhomológov heterocyklov a následnou nitráciou vzniknutého produktu (Breuer H., NSR zverejnený spis 2135 171 /1972/, Chem. Abstr. 77, 5 485 /1972/).4. Condensation of 2-furaldehyde in a basic medium with alkali salts of alkyl heterocycles of heterocycles and subsequent nitration of the resulting product (Breuer, H., Germany 2135 171 (1972), Chem. Abstr. 77, 5 485 (1972)).
5. Wittigovou reakciou 5-nitro-2-fura.ldehydu s ylidmi heterocyklov (Tanaka A., Yoshina S.: Jap. pat. 69 13 505 /1969/, Chem. Abstr. 71, 124 210 /1969/), resp. reakciou 5-nitro-2-furfurylidénfosforanov (Saikachi H., Nakamura S.:5. Wittig reaction of 5-nitro-2-furyldehyde with heterocyclic ylides (Tanaka A., Yoshina S .: Jap. Pat. 69 13 505 (1969), Chem. Abstr. 71, 124 210 (1969)), respectively. . by the reaction of 5-nitro-2-furfurylidene phosphorans (Saikachi H., Nakamura S .:
Yakugaku Zasshi'88, 110 /1968/, Chem. Abstr. akciou 5-nitro-2-furfurylfosfátu (Jurášek A., Kováč J., Prousek J.: Chem. Zvěsti 29, 234 /1975/) s karbonylovými zlúčeninami heterocyklov.Yakugaku Zasshi88, 110 (1968), Chem. Abstr. by 5-nitro-2-furfuryl phosphate (Jurasek A., Kovac J., Prousek J .: Chem. Zvěsti 29, 234 (1975)) with carbonyl compounds of heterocycles.
Nevýhodou týchto metod přípravy sú nízké výtažky finálneho produktu. Niektoré spósoby přípravy sú náročné z dovodu syntézy medziproduktov, a tým zbýšeného počtu stupňov prípravy.A disadvantage of these methods of preparation is the low yields of the final product. Some methods of preparation are demanding because of the synthesis of intermediates and thus the increased number of preparation steps.
Tieto nedostatky v podstatné) miere odstraňuje spósob přípravy 2-substituovaných l-(5-nitro-2-furyl) etylénov obecného vzorca IThe process for the preparation of the 2-substituted 1- (5-nitro-2-furyl) ethylenes of formula I is substantially eliminated by these drawbacks.
OaM--^Qy-CH3CH-R [L) kde R je fenyl, 4-metylfenyl, 4-hydroxyfenyl, 4-metoxyfenyl, 2-tienyl, 2-naftyl, ktorého podstata spočívá v tom, že na 2-bróm-l-(5-nitro-2-furyljetylén sa pósobí aromatickými zlúčeninami, ktoré sú substituované elektro-donornými substituentami, ako benzen, toluen, fenol, anizol, tiofén, naftalén, za katalytického účinku chloridu hlinitého v prostředí organického rozpúšťadla, ako nitrobenzén, nitrometán, síroúhlík, 1,2-dichIóretán, dichlórmetán pri 0 °C až teplote varu rozpúšťadla.O and M - ( Q ) -CH 3 CH-R [L] wherein R is phenyl, 4-methylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 2-thienyl, 2-naphthyl, wherein: bromo-1- (5-nitro-2-furyl) ethylene is treated with aromatic compounds which are substituted with electron-donating substituents such as benzene, toluene, phenol, anisole, thiophene, naphthalene under the catalytic action of aluminum chloride in an organic solvent environment such as nitrobenzene , nitromethane, carbon disulfide, 1,2-dichloroethane, dichloromethane at 0 ° C to the boiling point of the solvent.
Výhodou spósobu přípravy 2-substituovaných-l-(5-nitro-2-furyl) etylénov podlá vynálezu sú vyššie výtažky ako u spósobov (1—4) a přibližné rovnaké ako u spósobu (5), ale ten je náročný na přípravu medziproduktov (Shigetaka Y., Akira T., Katsumi Y.: Yakugaku Zasshi 88, 65 (1968J, Chem. Abstr. 69, 27 134 (1968); Tanaka A., Yoshina S.: Jap. pat. 69 04, 975 (1969), Chem. Abstr. 70, 114 996 (1969); Hirao I., Kitamura Y.: Nippon Kagaku Zasshi 85, 506 (1964), Chem. Abstr. 62, 11 756 (1965); Krkoška P., Jurášek A.: Chem. Zvěsti 23, 143 (1969). Výhodou spósobu pripravy podlá vynálezu je jednoduchá příprava medziproduktu 2-bróm-l-(5-nitro-2-furylj etylénu, ktorý sa připravuje z 3-{5-nitro-2-furyl)akrylovej kyseliny /Vegh D., Kováč J., Hásová B.: Collect. Czech, Chem. Commun. 41, 614 (1976)/, ktorá je komerčně dostupná.An advantage of the process for the preparation of 2-substituted-1- (5-nitro-2-furyl) ethylenes according to the invention is higher yields than processes (1-4) and approximately the same as process (5), but it is difficult to prepare intermediates ( Shigetaka Y., Akira T., Katsumi Y .: Yakugaku Zasshi 88, 65 (1968J, Chem. Abstr. 69, 27 134 (1968); Tanaka A., Yoshina S .: Jap. Pat. 69 04, 975 (1969) , Chem., 70, 114, 996 (1969), Hirao I., Kitamura, Y .: Nippon Kagaku Zasshi 85, 506 (1964), Chem., 62, 11 756 (1965), Krkoška P., Jurášek A Advantages of the process according to the invention are the simple preparation of the intermediate 2-bromo-1- (5-nitro-2-furyl) ethylene, which is prepared from 3- {5-nitro-2- furyl) acrylic acid (Vegh D., Kovac J., Hasova B .: Collect. Czech, Chem. Commun. 41, 614 (1976)), which is commercially available.
V polohe 2 aromatickými alebo heteroaromatickými zlúčeninami substituované l-(5-nitro-2-furyl)etylény majú pře svoju vysokú antibakteriálnu účinnost a nízku toxicitu široké použitie v medicíně i v potravinárskom priemysle.Substituted 1- (5-nitro-2-furyl) ethylenes substituted in the 2-position by aromatic or heteroaromatic compounds have widespread use in medicine and the food industry for their high antibacterial activity and low toxicity.
Predmet vynálezu ilustrujú, ale neobmedzujú následujúce příklady.The invention is illustrated but not limited by the following examples.
Organická vrstva sa oddělí, premyje vodou, 5% roztokom uhličitanu draselného a suší bezvodým chloridom vápenatým. Rozpúšťadlo sa vákuovo odděluje a zvyšok sa stlpcovo chromatografuje na AI2O3. Výťažok 1,04g (45,5%) 2-(4-mety lf enyl )-l-(5-nitro-2-f uryl jety lénu (t. 1.120 až 121 °C, kryštalizovaný z n-heptánu).The organic layer was separated, washed with water, 5% potassium carbonate solution and dried with anhydrous calcium chloride. The solvent was removed in vacuo and the residue was chromatographed on Al 2 O 3. Yield 1.04g (45.5%) of 2- (4-methylphenyl) -1- (5-nitro-2-furyl) ethylene (m.p. 1.120-121 ° C, crystallized from n-heptane).
Příklad 3Example 3
Příprava 2- (4-hydroxyfenyl )-1-( 5-nitro-2-furyl) etylénuPreparation of 2- (4-hydroxyphenyl) -1- (5-nitro-2-furyl) ethylene
0tN0 t N
CH=CH— 1CH = CH-1
OHOH
K zmesi 2,18 g (0,01 molu) 2-bróm-l-(5-nitro-2-furyl) etylénu, 2 g (0,015 mólu) bezvodého chloridu hlinitého v 10 ml 1,2-dichlóretánu pri teplote 0°C sa za miešania přidá 4,7 g (0,05 mólu) fenolu v 10 ml 1,2-dichlóretánu. Reakčná zmes sa 0,5 h mieša pri teplote 20 °C, vyleje na zmes 20 g ladu a 20 ml konc. kyseliny chlorovodíkovej. Organická vrstva sa oddělí, premyje vodou, 5% roztokom uhličitanu draselného a suší bezvodým chloridom vápenatým. Rozpúšťadlo sa vákuovo oddestiluje a zvyšok sa stlpcovo chromatografuje na AI2O3. Výťažok 1,33 g (57,6%) 2-(4-hydroxyfenyl )-1-( 5-nitro-2-furyl)etylénu (t. t. 208—210 °C, kryštalizovaný z benzénu).To a mixture of 2.18 g (0.01 mol) of 2-bromo-1- (5-nitro-2-furyl) ethylene, 2 g (0.015 mol) of anhydrous aluminum chloride in 10 ml of 1,2-dichloroethane at 0 ° 4.7 g (0.05 mol) of phenol in 10 ml of 1,2-dichloroethane are added with stirring. The reaction mixture was stirred at 20 ° C for 0.5 h, poured onto a mixture of 20 g of ice and 20 mL of conc. hydrochloric acid. The organic layer was separated, washed with water, 5% potassium carbonate solution and dried with anhydrous calcium chloride. The solvent was distilled off in vacuo and the residue was chromatographed on Al 2 O 3. Yield 1.33 g (57.6%) of 2- (4-hydroxyphenyl) -1- (5-nitro-2-furyl) ethylene (m.p. 208-210 ° C, crystallized from benzene).
Příklad 1Example 1
Příprava 2-fenyl-l- (5-nitro-2-furyl) etylénuPreparation of 2-phenyl-1- (5-nitro-2-furyl) ethylene
K zinesi 2,18 g (0,01 molu) 2-bróm-l-(5-nítro-2-furyl)etylénu, 2g (0,015 molu) bezvodého chloridu hlinitého v 10 ml suchého 1,2-dichlóretánu pri teplote 0 °C sa za miešania přidá 3,9 g (0,05 molu) benzénu v 10 ml 1,2-dichlóretánu. Reakčná zmes sa 0,5 h zahrieva pri teplote varu rozpúštadla, potom sa vyleje na zmes 20 g ladu a 20 ml konc. kyseliny chlorovodíkovej. Organická vrstva sa oddělí, premyje vodou, 5% roztokom uhličitanu draselného a suší bezvodým chloridom vápenatým. Rozpúšťadlo sa vákuovo oddestiluje a zvyšok sa stlpcovo chromatografuje na AI2O3. Výťažok 0,9 g (42%) 2-fenyl-l-(5-nitro-2-furyl) etylénu (t. t. 110 až 111 °C, kryštalizovaný z n-heptánu).To yield 2.18 g (0.01 mol) of 2-bromo-1- (5-nitro-2-furyl) ethylene, 2g (0.015 mol) of anhydrous aluminum chloride in 10 ml of dry 1,2-dichloroethane at 0 ° 3.9 g (0.05 mol) of benzene in 10 ml of 1,2-dichloroethane are added with stirring. The reaction mixture is heated at the boiling point of the solvent for 0.5 h, then poured onto a mixture of 20 g of ice and 20 ml of conc. hydrochloric acid. The organic layer was separated, washed with water, 5% potassium carbonate solution and dried with anhydrous calcium chloride. The solvent was distilled off in vacuo and the residue was chromatographed on Al 2 O 3. Yield 0.9 g (42%) of 2-phenyl-1- (5-nitro-2-furyl) ethylene (m.p. 110-111 ° C, crystallized from n-heptane).
Příklad 4Example 4
Příprava 2- (4-metoxyfenyl )-1-( 5-nitro-2-fury] jety lénu w//Preparation of 2- (4-methoxyphenyl) -1- (5-nitro-2-furyl) ethylene w //
0,N0, N
CHsCHchsch
-OOCH«-OOCH «
Postupom ako v příklade 3 sa připraví z 2,18 g 2-bróm-l-(5-nitro-2-furyl) etylénu, 2 g (0,015 mólu) bezvodého chloridu hlinitého a 5,4 g (0,05 mólu) anizolu 2-(4-metoxyfenyl )-1-( 5-nitro-2-kuryl) etylén vo výťažku 1,43 g (58,2 proč.) (t. t. 144—145 °C, kryštalizovaný z n-heptánu).Using the procedure of Example 3, 2-bromo-1- (5-nitro-2-furyl) ethylene, 2 g (0.015 mol) of anhydrous aluminum chloride and 5.4 g (0.05 mol) of anisole are prepared. 2- (4-methoxyphenyl) -1- (5-nitro-2-kuryl) ethylene in a yield of 1.43 g (58.2 proc.) (Mp 144-145 ° C, crystallized from n-heptane).
Příklad 2Example 2
Příprava 2- (4-metylfenyl)-1-( 5-nitro-2-f ur yl) etylénuPreparation of 2- (4-methylphenyl) -1- (5-nitro-2-furyl) ethylene
Příklad 5Example 5
QaNQ and N
CH»CH—' “CHS CH »CH— '' CH S
Příprava 2- (2-naf tyl) -1- (5-nitro-2-f ur yl) etylénuPreparation of 2- (2-naphthyl) -1- (5-nitro-2-furyl) ethylene
K zmesi 2,18 g (0,01 molu) 2-bróm-l-(5-nitro-2furyl)etylénu 2g (0,015 molu) bezvodého chloridu hlinitého v 10 ml suchého 1,2-dichlóretánu pri teplote 0 °C sa za miešania přidá 4,6 g (0,05 molu) toluénu v 10 ml 1,2-dichlóretánu. Reakčná zmes sa 0,5 h zahrieva pri teplote varu rozpúštadla, potom sa vyleje na zmes 20 g řadu a 20 ml konc. ykseliny chlorovodíkovej.To a mixture of 2.18 g (0.01 mol) of 2-bromo-1- (5-nitro-2-furyl) ethylene 2g (0.015 mol) of anhydrous aluminum chloride in 10 ml of dry 1,2-dichloroethane at 0 ° C was added at 0 ° C. with stirring 4.6 g (0.05 mol) of toluene in 10 ml of 1,2-dichloroethane are added. The reaction mixture is heated at the boiling point of the solvent for 0.5 h, then poured onto a mixture of 20 g series and 20 ml conc. hydrochloric acid.
Postupom ako v příklade 3 sa připraví z 2,18 g (0,01 mólu) 2-bróm-l-(5mitro-2-furyl) etylénu, 2g (0,015 mólu) bezvodého chloridu hlinitého a 6,4 g (0,05 mólu) naftalénu 2-(2-naftyl)-l-(5-nitro-2-furyl)etylén vo výťažku 1,97 g (74,3%) (t. t. 102,5—104 °C, kryštalizovaný z n-heptánu).Following the procedure of Example 3, 2-bromo-1- (5-nitro-2-furyl) ethylene, 2g (0.015 mol) of anhydrous aluminum chloride and 6.4 g (0.05 g) were prepared from 2.18 g (0.01 mol). mole) of naphthalene 2- (2-naphthyl) -1- (5-nitro-2-furyl) ethylene in a yield of 1.97 g (74.3%) (mp 102.5-104 ° C, crystallized from n-heptane) ).
Příklad 6Example 6
Příprava 2- (2-tienyl )-1-( 5-nitro-2-furyl) etylénu CH aGH^S^Preparation of 2- (2-thienyl) -1- (5-nitro-2-furyl) ethylene AGH CH ^ S ^
Postupom ako v příklade 3 sa připraví z 2,18 g (0,01 molu) 2-bróm-l-(5-nitro-2-furyl) etylénu, 2 g (0,015 molu) bezvodého chloridu hlinitého a 4,2 g (0,05 molu) tiofénu 2-(2-tienyl)-l-(5-nitro-2-furyl)etylén vo výtažku 1,49 g (67,6 proč.) (t. t. 117,5—119 °C, krystalizovaný z n-heptánu).Following the procedure of Example 3, 2-bromo-1- (5-nitro-2-furyl) ethylene, 2 g (0.015 mol) of anhydrous aluminum chloride and 4.2 g of (2-bromo-1- (5-nitro-2-furyl)) are prepared. 0.05 mol of thiophene 2- (2-thienyl) -1- (5-nitro-2-furyl) ethylene in 1.49 g (67.6 proc.) Yield (mp 117.5-119 ° C, crystallized) from n-heptane).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS578A CS196927B1 (en) | 1978-01-02 | 1978-01-02 | Process for preparing 2-substituted 1-/5-nitro-2-furyl/ethylenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS578A CS196927B1 (en) | 1978-01-02 | 1978-01-02 | Process for preparing 2-substituted 1-/5-nitro-2-furyl/ethylenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196927B1 true CS196927B1 (en) | 1980-04-30 |
Family
ID=5331435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS578A CS196927B1 (en) | 1978-01-02 | 1978-01-02 | Process for preparing 2-substituted 1-/5-nitro-2-furyl/ethylenes |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196927B1 (en) |
-
1978
- 1978-01-02 CS CS578A patent/CS196927B1/en unknown
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