CS223434B1 - a-Substituované 5-pyridíniohalogenidy 3-(2-furyi) akrylonitrilu a sposob ich přípravy - Google Patents
a-Substituované 5-pyridíniohalogenidy 3-(2-furyi) akrylonitrilu a sposob ich přípravy Download PDFInfo
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- CS223434B1 CS223434B1 CS48282A CS48282A CS223434B1 CS 223434 B1 CS223434 B1 CS 223434B1 CS 48282 A CS48282 A CS 48282A CS 48282 A CS48282 A CS 48282A CS 223434 B1 CS223434 B1 CS 223434B1
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- Prior art keywords
- furyl
- substituted
- formula
- ppm
- acrylonitrile
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- 238000000034 method Methods 0.000 title claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- ZHKAQNFBQHPERX-HNQUOIGGSA-N (e)-3-(furan-2-yl)prop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CO1 ZHKAQNFBQHPERX-HNQUOIGGSA-N 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000008360 acrylonitriles Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 pyridinium halides Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 1
- DSPQMKOMBMQWDD-UHFFFAOYSA-N 3-(5-bromo-2-furanyl)-2-cyano-2-propenamide Chemical compound NC(=O)C(C#N)=CC1=CC=C(Br)O1 DSPQMKOMBMQWDD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- SZZYAOCSMNDGPI-UHFFFAOYSA-N methylsulfinylmethane;thiolane 1,1-dioxide Chemical compound CS(C)=O.O=S1(=O)CCCC1 SZZYAOCSMNDGPI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001622 two pulse phase modulation pulse sequence Methods 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Description
3 4 223134
Vynález sa týká a-substituovaných-5-pyri-díniových halogenidov 3-(2-furyl)akrylo-nitrilu všeobecného vzorca I
(I) kde X je CN, CONHz, COOCH3, Y znamená Cl, Br, J,a spósobu ich přípravy. Látky a spósob ich přípravy podlá vyná-lezu nie sú v literatuře doposial popísané.
Podstata sposobu přípravy látok podl'a vy-nálezu spočívá v tom, že a-substituovaná 3-(5-Y-2-furyl)akrylonitrily všeobecného vzor-ca IV
_ CN (IV) kde X je CN, CONHz, COOCH3, Y je Cl, Br, J, reagujú s pyridínom v prostředí organic-kých rozpúšťadiel zo skupiny aromatickýchkvapalných uhlovodíkov ako benzén, to-luén, xylén, éterov ako dietyléter, tetrahyd-rofurán, dioxán, dimetoxyetán, esterov ky-selin ako etylester kyseliny octovej, metyl-ester kyseliny octovej, ďalej v prostředí ace- 'tónu, sulfolanu, dimetylformamidu, dime-tylsulfoxidu v rozmedzí teplót —200 °C až+20 °C a tlaku 100 až 1000 kPa. *
Reakcia prebieha podl'a rovnice:
CHsC
CH=C
CN (-)
• Y kde X je CN, CONHz, COOCH3, Y znamená Cl, Br, ]. Výhoda spósobu přípravy pyridíniovýchhalogenidov podlá vynálezu spočívá v tom,že syntézy sú jednostupňové, pričom sa vy-chádza z poměrně dostupných surovin (fu-ral, chlór, bróm, pyridin).
Zlúčeniny predstavujú novů skupinu fu-ránových derivátov, kde pyridíniová skupi-na vnáša do molekuly cenné vlastnosti, kto-ré sa móžu využit v nukleofilných reakciáchso' širokým radom nukleofilných činidiel kys-líkatého, sírneho, dusíkatého i uhlíkatéhocharakteru. Výsledky elementárnej analýzy a fyzikál-no-chemické konstanty zlúčenín podlá vy-nálezu sú uvedené v tab. č. 1. Příklad 1 10 g (44,8 mmol) 5-brómfurfurylidénma-londinitrilu všeobecného vzorca IV (kdeX je CN a Y je Br) sa rozpustí v 300 ml ben-zenu a přidá sa 3,55 g (44,8 mmol) pyridinu.Zmes sa refluxuje 10 hodin. Získalo sa 11,7gramu, t. j. 88,5 % zelenej látky Ib.
Obdobné sa pripravujú i látky Ia z IV (kdeX je CN, Y je Cl) v octane etylovom a Icz IV (kde X je CN, Y a J) v dimetylformami-de při 120 °C. l· *H — NRM — spektrum Ib (merané na pří-stroji Tesla BS-467, TMS hexadeuteriodi-metylsulfoxid, 25 °C). S Hoi = 8.51 ppm (s),δ H3 = 7,80 ppm (d),δ H4 = 7,84 ppm (d), δ Ηα = 9,46 ppm (d),δ = 8,42 ppm (t),δ Hy = 8,87 ppm (t).3Jh3h4 = 4,0 Hz, !Jh«h„ = 7,0 Hz, SJh^h,, = 7,0 Hz, 3jHeHy = 1,5 Hz. Příklad 2 1 g (4,15 mmol) amidu kyseliny 2-kyano- -3- (5-bróm-2-furyl) akrylovéj všeobecnéhovzorca IV, kde X znamená CONHz a Y je Br,sa rozpustí v 40 ml dimetoxyetánu, přidá sa0,33 g pyridinu a zahrieva sa v zatavenejtrubici pri 150 °C až 200 °C pri tlaku 1000 kPa.Získalo sa 0,95 g zelenej látky IIb. Obdobnésa pripravujú i látky IIa z IV (kde X je CN,Y je Cl) v xyléne pri 180 až 220°C a látkyIIC z IV (kde X je CONH2, Y je J) v octaneetylovom pri 150 až 180 °C. XH — NMR — spektrum IIb (merané na pří-stroji Tesla BS-467, TMS, hexadeuteriodi-metylsulfoxid, 25 °C). 223434 3
S δ Hoi = 8,17 ppm (s),δ H3 = 7,67 ppm (d),δ H4 = 7,78 ppm (dj, δ Ha = 9,47 ppm, (d),δ Ηβ = 8,42 ppm (t),δ H,, = 8,06 ppm (t). 3Jh3h4 = 4,0 Hz, = 8,0 Hz,sJh^h,, = 8,0 Hz, = 1,5 Hz. Příklad 3 1,5 g (5,86 mmol) «-karbometoxy-3-(5--bróm-2-f uryl) akrylonitrilu všeobecného yzorca IV (kde X je COOMe a Y je Brj sarozpustí v 30 ml acetonu a přidá sa 3 mlpyridinu. Zmes sa nechá refluxovať 15 ho-din. Získalo- sa 1,53 g zelenej kryštalickejlátky IIIb.
Obdobné sa připravuje i látka IIIa z IV (kde X je COOCH3, Y je Cl v tetrahydrofurá-nej a látka IIIC z IV (kde X je COOCH3, Y jeJ) v dioxáne. lH-NMR spektrum IIIb (merané na přístrojiTesla BS-467, TMS, hexadeuteriodimetyl-sulfoxid, 25 °C). δ Hol = 8,37 ppm (s),δ H3 = 7,83 ppm (sj,δ H4 = 7,83 ppm (sj,δ OCH3 = 3,94 ppm (sj, δ Ηα = 9,47 ppm (d),δ Hs = 8,44 tppm (d, dj,δ Η? = 8,86 ppm (d, dj. 3Jh3h4 = 4,0 Hz, 3Jh«hí5 = 8,0 Hz, 3jH,Hy = 8,0 Hz, 4jf'K">. = 1,5 Hz. 223434 Λί o >im te ‘4-1'>>> E-t
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LQ in CO r-l CO 'tf O 1 1 1 1 f 1 I 1 CO CO 1 1 1 i CO CD ' 1 ' 1 co co cm cq CM CM CM CM
Zlúčeniny syntetizované podlá vynálezu,
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Claims (2)
- 223434 7 8 PREDMET 1. α-Substituované 5-pyridíniohalogenidy3-(2-furyl)akrylonitrilu všeobecného vzor-ca I VYNALEZU(t! kde X je CN, CONHz, COOCH3, Y je Cl, Br, J.
- 2. Spůsob přípravy látok všeobecného vzor-ca I podlá bodu 1 vyznačujúci sa tým, že«-substituované 3- (5-Y-2-f uryl) akrylonitrilyvšeobecného vzorca IV (IV) kde X a Y znamená to isté ako vo vzorci I,reagujú s pyridínom v prostředí organic-kých rozpúšťadiel zo skupiny aromatickýchkvapalných uhTovodíkov ako benzén, to-luén, xylén, éterov ako dietyléter, tetrahyd-rofurán, dioxán, dimetoxyetán, esterov ky-selin ako etylester kyseliny octovej, metyl-ester kyseliny octovej, ďalej v prostředí ace-tonu, sulfolanu, dimetylformamidu, dime-tylsulfoxidu v rozmedzí teplot —200 °C až+20 °C a tlaku 100 až 1000 kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS48282A CS223434B1 (cs) | 1982-01-25 | 1982-01-25 | a-Substituované 5-pyridíniohalogenidy 3-(2-furyi) akrylonitrilu a sposob ich přípravy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS48282A CS223434B1 (cs) | 1982-01-25 | 1982-01-25 | a-Substituované 5-pyridíniohalogenidy 3-(2-furyi) akrylonitrilu a sposob ich přípravy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS223434B1 true CS223434B1 (cs) | 1983-10-28 |
Family
ID=5336990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS48282A CS223434B1 (cs) | 1982-01-25 | 1982-01-25 | a-Substituované 5-pyridíniohalogenidy 3-(2-furyi) akrylonitrilu a sposob ich přípravy |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS223434B1 (cs) |
-
1982
- 1982-01-25 CS CS48282A patent/CS223434B1/cs unknown
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