CS268590B1 - Method of 5-nitro-2-furan and 5-nitro-2-thiophene series' enamines preparation - Google Patents
Method of 5-nitro-2-furan and 5-nitro-2-thiophene series' enamines preparation Download PDFInfo
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- CS268590B1 CS268590B1 CS88219A CS21988A CS268590B1 CS 268590 B1 CS268590 B1 CS 268590B1 CS 88219 A CS88219 A CS 88219A CS 21988 A CS21988 A CS 21988A CS 268590 B1 CS268590 B1 CS 268590B1
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- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000002081 enamines Chemical class 0.000 title claims description 3
- 238000002955 isolation Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- -1 gasoline Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- AWNFREVPGMLRGV-UHFFFAOYSA-N C(=S)=S.C(C)C(=O)C Chemical compound C(=S)=S.C(C)C(=O)C AWNFREVPGMLRGV-UHFFFAOYSA-N 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- LWOWNIPZHGWKNR-UHFFFAOYSA-N 3-(5-nitrofuran-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=C([N+]([O-])=O)O1 LWOWNIPZHGWKNR-UHFFFAOYSA-N 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- IIJCRPJUZLOCIE-UHFFFAOYSA-N 3-(5-nitrothiophen-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=C([N+]([O-])=O)S1 IIJCRPJUZLOCIE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MWQLQWFDFNQTHI-UHFFFAOYSA-N 1-[2-(5-nitrofuran-2-yl)ethenyl]piperidine Chemical compound O1C([N+](=O)[O-])=CC=C1C=CN1CCCCC1 MWQLQWFDFNQTHI-UHFFFAOYSA-N 0.000 description 1
- MSCZZRXBIBUPKG-UHFFFAOYSA-N 2-(3-nitrophenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC=CC([N+]([O-])=O)=C1 MSCZZRXBIBUPKG-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Furan Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Rleil sa nový sposob pripravy enaalnov 5-nltro-2-furánového a 5-nltro-2-tlofénového radu obecného vzorce I vyznačený týa, ie 3-/5-n1tro-2-furyl/propénové alebo 3-/5-n1tro-2-tIenyl/propénová kyselina vzorca II aa nechá reagovat s broaoa za vzniku 2,3-dlbróa-3-/5-n]tro-2-furyl/- proplónovej, rejp. 2,3-d1broa-3-/5-nltro- -2-t1enyl/proplonovej kyseliny vzorca III, ktoré připadne po IzolécH sa nechajú reagovat s prlslušnya sekundérnya aalnoa alebo prlairnya aalnoa v prostředí organických rozpůčlad!et.A new way of preparing enaalnes was looted 5-nitro-2-furan and 5-nitro-2-thiophene of formula (I) t, 3- (5-nitro-2-furyl) propenoic acid; 3- (5-nitro-2-phenyl) propenoic acid formula IIa and reacts with broaoa to form 2,3-dibromo-3- (5-n-trichloro-2-furyl) - proplonic, rejp. 2,3-d1broa-3/5-nltro- -2-tertienyl / proplonic acid of formula III which are recovered after Isolation react with prlslušnya sekundérnya aalnoa or prlairnya aalnoa in organic environment rozpůčlad! et.
Description
Vynález aa týk» spoaobu přípravy enanínov 5-nítro-2~furánového a 5-nitro-2-tiofénového radu obecného vzorca I ' o2nThe invention relates to a process for the preparation of enanines of the 5-nitro-2-furan and 5-nitro-2-thiophene series of the general formula I 'o 2 n
H-CH-NR R 1 2 (I) kde Z je O elebo 8 a NR R_ je N(CH„) .H-CH-NR R 1 2 (I) wherein Z is O or 8 and NR R 2 is N (CH 2).
z * n<chch3)2 z * n <chch 3 ) 2
N ¢2/ NH'N ¢ 2 / NH '
CH NH, »5CH NH, »5
CHgCH^H, (CH^CHNH, CH3O-ς^>-ΝΗ,CH 2 CH 2 H, (CH 2 CHNH, CH 3 O-η 2> - ΝΗ,
Enaminy májá široké uplatněni» v organické) syntéze /Cook A.G., Enamines, Synthesis, Structures and Reactions, Dekker, New York-London 1969/. Enaniny 5-nitro-2-furinoviho a 5-nitro-2-tiofénového radu vykazujá výrazná antibakteriálnu aktivitu a *ά predmetom intenzivneho výskumu /Végh D., Šejnkman A.K., Nivorožkin L.E., Kováč J., Dandárová M., Ivančo L.: Coll. Czech. Chem. Commun., £5, 155 /1980/; Végh D., Šejnkman A.K., Kovií J., Kondratenko G.P., Geonja N.I.: ZSSR A0 671 254/. Ich přípravy vychádzajá z vysoko reaktivnych 5-nitro-2-furyl- resp. 5-nitro-2-tíenylvínylhalogenídov reakciou s amínmi, konkrétné sekundárnými /Végh 0., Kováč J., Dandárová K.: Tetrahedron letters Jj, 969 /1980/; Végh D., Kováč J., Dandárová K., Ivančo L. Coll. Czech. Chem. Commun. 155 /1980//.Enamins are widely used in organic synthesis (Cook A.G., Enamines, Synthesis, Structures and Reactions, Dekker, New York-London 1969). The enanins of the 5-nitro-2-furin and 5-nitro-2-thiophene series show significant antibacterial activity and are the subject of intensive research / Végh D., Šejnkman AK, Nivorožkin LE, Kováč J., Dandárová M., Ivančo L .: Coll. Czech. Chem. Commun., £ 5, 155 (1980); Végh D., Šejnkman A.K., Kovií J., Kondratenko G.P., Geonja N.I .: USSR A0 671 254 /. Their preparations are based on highly reactive 5-nitro-2-furyl- resp. 5-nitro-2-thienylvinyl halides by reaction with amines, in particular secondary ones (Végh 0., Kováč J., Dandárová K .: Tetrahedron letters Jj, 969 (1980)); Végh D., Kováč J., Dandárová K., Ivančo L. Coll. Czech. Chem. Commun. 155/1980 //.
Uvedené nevýhody v podstatné) miere odstraňuje sposob podía vynálezu, ktorého podstata spočívá v tom, že 3-/5-nitro—2-furyl/propénová alebo 3-/5-nitro-2-tienyl/propénová kyselina vzorca II .These disadvantages are substantially eliminated by the process according to the invention, which consists in that 3- (5-nitro-2-furyl) propenoic acid or 3- (5-nitro-2-thienyl) propenoic acid of the formula II.
0 N—2--CH-CH-COOH (11) __________ 2 'zJ ______ ______ ____ kde Z znamená to isté ako vo vzorci I, sa nechá reagovat s brómom za vzniku 2,3-dibróm3/5-nitro-2-furyl/propiónove) alebo Z,3-dibróm-3-/5-nitro-2-tienyl/.propiónovej kyseliny vzorca 111 rr~λ í t t i 1 0 N-___/ '\_-CHBr-CHBr~COOH 'Z ' kde Z Je hoře uvedené, ktorá popřípadě po ízolácií sa nechá reagoval io sekundárným amínom zvoleným zo skupiny zahrnujáce) zláčeniny vzorce · 0 N — 2 - CH-CH-COOH ( 11 ) __________ 2 'of J ______ ______ ____ where Z is the same as in formula I, is reacted with bromine to give 2,3-dibromo / 5-nitro-2 furyl / propionic acid), or Z, 3-dibromo-3- / 5-nitro-2-thienyl / .propiónovej of formula 111 rr ~ tti λ s 1 0 N -___ / '\ _- CHBr CHBr-COOH ~' Z wherein Z is indicated above, which optionally, after isolation, is reacted with a secondary amine selected from the group consisting of compounds of the formula
ΗΝ(0Η3)2,ΗΝ(0Η20Η3)2, Hn[cH(CH3)2]2» ' QnH * (2/41 '° O™ alebo s primárným amínom zvoleným zo skupiny zahrňujáce) zláčeniny vzorcaΗΝ (0Η 3) 2, ΗΝ (2 0Η 0Η 3) 2, H N [CH (CH3) 2] 2 » '* QNH (2/41" ™ ° H or a primary amine selected from the group zahrňujáce) zláčeniny formula
CH3NH2, CH3CH2NH2/ (CH3)2CHNH2, Q-NH2, CH30_-<^—’NH2' —'NH2# v prostředí organických rozpúJtadíel ako v kvapalných aromatických uhíovodíkoch ako....... v benzéne, toluéne, xyléne v éteroch ako v díetyléterí, tetrahydrofuráne, dfoxáne, 1,2-dímetoxyetáne, polyetylénglykole o strednej molekulové) hmotnosti 200 ai 600, ěalej v octane etylovom, acetonitrile, sirouhlíku, acetone a 2-butanóne alebo v ich zmesiach navzájem alebo s vodou pri teplotách 20 až 160 C.CH 3 NH 2 , CH 3 CH 2 NH 2 / (CH 3 ) 2 CHNH 2 , Q-NH 2 , CH 3 0 _- < ^ - ' NH 2' - ' NH 2 # in the environment of organic solvents as in liquid aromatic hydrocarbons as ....... in benzene, toluene, xylene in ethers as in diethyl ether, tetrahydrofuran, dfoxane, 1,2-dimethoxyethane, polyethylene glycol with an average molecular weight of 200 to 600, further in ethyl acetate, acetonitrile, carbon disulfide, acetone and 2-butanone or mixtures thereof with each other or with water at temperatures of 20 to 160 ° C.
CS 268 590 B1CS 268 590 B1
Reakcie prebiehajú podCa nasledujúcej schémy:The reactions proceed according to the following scheme:
H-CH-C00H + Br2 °2n —K /--CHBr-CHBr-COOH+HNR.R -4 'Z7 12H-CH-C00H + Br 2 ° 2 n —K /--CHBr-CHBr-COOH+HNR.R -4 'Z 7 12
O N—/^V-CH-CH-NR.R 1 2ON - N-CH-CH-NR.R 1 2
Látky podta vynálezu možno připravit aj posobenim málo bázických amtnov pK_ 6 ako BThe compounds of the invention can also be prepared by treating the low base amines pK_6 as B
Sú primárné aminy/ aromatické aminy.They are primary amines / aromatic amines.
Předmětný sposob využívá substituíno-fragmentaíné reakcie na rozdiel od doteraz používaných $NV reakcli. Nakotko substitúcie prebiehajú na nasýtenom uhlíku a predchádzajú fragmentaínú reakciu, májů širšie uplatneníe a představuji! nový typ reakcie.The present process utilizes substituent fragmentation reactions in contrast to the previously used $ N in the reaction. Since the substitutions take place on saturated carbon and precede the fragmentation reaction, they have a wider application and I present! new type of reaction.
Přiklad 1Example 1
19/3 g /0,1 mol/ 3-/5-nitro-2-furyl/propénovej kyseliny sa suspendovalo do 250 ml C$2 a pri teplote varu rozpúštadla v priebehu 3 h přidalo 16 g brómu. Po odfarbeni roztoku sa přidalo k intenzivně miešanému roztoku 30 g piperidínu a po 5 h miešania sa rozpúštadlo oddesti I ovalo za vákua. Získalo sa 17 g 1-/N-piperidyl/-2-/5-nitro-2-furyl/eténu ot.t. 77 až 79 °C.19/3 g (0.1 mol) of 3- (5-nitro-2-furyl) propenoic acid were suspended in 250 ml of C18 and 16 g of bromine were added at the boiling point of the solvent over a period of 3 hours. After decolorization of the solution, 30 g of piperidine were added to the vigorously stirred solution, and after stirring for 5 hours, the solvent was removed in vacuo. 17 g of 1- (N-piperidyl) -2- (5-nitro-2-furyl) ethene were obtained, m.p. 77-79 ° C.
Příklad 2Example 2
19/3 g /0,1 mol/ 3-/5-nitro-2-furylZpropénovej kyseliny v 300 ml dioxánu sa zmiešalo při teplote 40 C.s 216 g brómu a po 1 h zahrievania k varu rozpúštadla sa přidalo 30 g dímetylamínu naraz. Po 1 h miešania pri teplote laboratoria sa reakšná zmes zahrievala 2 h pri 100 až 110 °C. Po ochladení sa přefiltrovala cez 100 g sílíkagelu, eluent benzen-octan etylový. Získalo sa 17 g 1-N,N-d1metylamino-2-/5-nítro-2-furyl/etylénu o t.t. 65 až 67 °C.19/3 g (0.1 mol) of 3- (5-nitro-2-furyl) propenoic acid in 300 ml of dioxane were mixed at 40 DEG C. with 216 g of bromine and, after heating for 1 hour to the boiling point of the solvent, 30 g of dimethylamine were added all at once. After stirring at room temperature for 1 h, the reaction mixture was heated at 100-110 ° C for 2 h. After cooling, it was filtered through 100 g of silica gel, eluent benzene-ethyl acetate. 17 g of 1-N, N-dimethylamino-2- (5-nitro-2-furyl) ethylene of m.p. 65-67 ° C.
Přiklad 3Example 3
3,53 g 2,3-dibróm~3-/5~nitro-2-furyl/propiónovej kyseliny získanej halogenáciou 3-/5-nítro-2-furyl/propénovej kyseliny s bromom sa rozpustilo v 50 ml acetonitrilu a 50 ml acetonu a za intenzivneho miešania sa přidalo 4 g anizidínu. Po 3 h zahrievania na 60 až 70 °C sa zmes čistila filtráciou cez silikagel. Získalo sa 1,1 g 1-/4-aetoxyfenyl/am1no-2-/5-nitro-furyl/eténu o t.t. 123 až 127 °C.3.53 g of 2,3-dibromo-3- (5-nitro-2-furyl) propionic acid obtained by halogenation of 3- (5-nitro-2-furyl) propenoic acid with bromine were dissolved in 50 ml of acetonitrile and 50 ml of acetone and 4 g of anisidine were added with vigorous stirring. After heating at 60-70 ° C for 3 h, the mixture was purified by filtration through silica gel. 1.1 g of 1- (4-ethoxyphenyl) amino-2- (5-nitrofuryl) ethene of m.p. 123-127 ° C.
Přiklad 4Example 4
20,9 g /0,1 mot/ 3-/5-nitro-2-tienyl/propénovej kyseliny v 250 ml C$2 při teplote varu rozpúštadla sa zmiešalo s 16 g brómu. Po odfarbeni roztoku sa přidalo 14 g dimetylaminu a po 10 min miešania pri 20 °C sa zahrial do varu 1 h. Potom sa přidalo 50 ml polyetylénglykolu o strednej molekulové] hmotností 300 a sirouhlík sa oddest iloval. Teplota sa postupné zvýšila na 100 °C v priebehu 2 h. Po vyliati do vody sa získalo 11 g 1-N/N-dimetylamino-2-/5-nitro-2-tienyl/etánu o t.t. 126 až 127 °C.20.9 g / 0.1 mot / 3- / 5-nitro-2-thienyl / propenoic acid in 250 ml of C $ 2 at the boiling point of the solvent were mixed with 16 g of bromine. After decolorization of the solution, 14 g of dimethylamine were added and, after stirring for 10 minutes at 20 [deg.] C., the mixture was heated to reflux for 1 hour. Then 50 ml of polyethylene glycol with an average molecular weight of 300 were added and the carbon disulfide was distilled off. The temperature was gradually raised to 100 ° C over 2 h. After pouring into water, 11 g of 1-N (N-dimethylamino-2- (5-nitro-2-thienyl) ethane were obtained, m.p. 126-127 ° C.
Přiklad 5Example 5
20,9 g /0,1 mol/ 3-/5-nitro-2-tienyl/propénovej kyseliny a 16 g brómu sa zmiešalo v 100 ml 1,2-dimetoxyetánu a po 10 min miešania a zahrievania na 60 C sa přidalo naraz20.9 g (0.1 mol) of 3- (5-nitro-2-thienyl) propenoic acid and 16 g of bromine were mixed in 100 ml of 1,2-dimethoxyethane and, after stirring and heating at 60 DEG C. for 10 minutes, were added all at once.
CS 268 590 B1 g morfolinu v 200 ml acetonu. Po 3 h zahrievania do varu, vylůženA amóniovA so( sa odfiltrovala a filtrAt sa zahustil ku kryitali zAc i 1 . Získalo sa 12 g 1-N-morfol1no-2-/5-nitro-2-tienyl/etAnu o t.t. 167 až 168 °C.CS 268 590 B1 g of morpholine in 200 ml of acetone. After heating to reflux for 3 h, the ammonium salt was filtered off and the filter was concentrated to crystallize from Acc to give 12 g of 1-N-morpholino-2- (5-nitro-2-thienyl) ethane, mp 167-168. ° C.
Přiklad 6Example 6
35,3 g 2,3-d1bróm-3/5-nÍtro-2-fenyl/propionovej kyseliny ziskanej halogenAciou 3-/5-nitro-2-fenyl/propAnovej kyseliny s brómom sa rozpustilo v 500 ml benzAnu a za intenzivneho mieíania sa přidalo 0,22 mol aminu. Po 3 h zahrievania do varu finAlny produkt sa čistil filtrAciou cez silikagél. Získali sa anaminy vo výtažku 70 až 95 Xi35.3 g of 2,3-dibromo-3 (5-nitro-2-phenyl) propionic acid obtained by halogenation of 3- (5-nitro-2-phenyl) propanoic acid with bromine were dissolved in 500 ml of benzene and stirred vigorously with vigorous stirring. 0.22 mol of amine was added. After heating to reflux for 3 h, the final product was purified by filtration through silica gel. The anamines were obtained in a yield of 70 to 95 Xi
kovovofialový olej νμ2-°η 2°η3 nh2-ch(ch3)2 kovovoflalový olejmetal violet oil νμ 2 - ° η 2 ° η 3 nh 2 -ch (ch 3 ) 2 metal violet oil
, · A, · A
Látky podlá vynAlezu možno připravit sposobom uvedeným v přiklade 6 aj za použitia iných aromatických kvapalných uhtovodikov ako toluén, xylén resp. ich zmesi.The compounds according to the invention can also be prepared by the process described in Example 6 using aromatic liquid hydrocarbons other than toluene, xylene and mixtures thereof.
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CS88219A CS268590B1 (en) | 1988-01-13 | 1988-01-13 | Method of 5-nitro-2-furan and 5-nitro-2-thiophene series' enamines preparation |
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CS88219A CS268590B1 (en) | 1988-01-13 | 1988-01-13 | Method of 5-nitro-2-furan and 5-nitro-2-thiophene series' enamines preparation |
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CS21988A1 CS21988A1 (en) | 1989-08-14 |
CS268590B1 true CS268590B1 (en) | 1990-03-14 |
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