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1.
The title compound ( 14 ), a representative of a novel ring system, was prepared from 9H-carbazole-1-carboxylic acid 1-methylhydrazide ( 7 ) and triethyl orthoformate. Attempted cyclization of 7 with triethyl orthoacetate led only to 9H-carbazole-l-carboxylic acid 2-(l-ethoxyethylidene)-l-methylhydrazide ( 16 ). Treatment of 16 with trifluoroacetic acid gave 9H-carbazole- 1 -carboxylic acid ( 12 ). A postulated mechanism for this transformation was supported by studies with model compounds. A new synthesis of 1 -benzoyl-2-methylhydrazine ( 24 ), using 1-acetyl-1-methylhydrazine ( 22 ) as a synthon, is described. 相似文献
2.
A simple synthesis of furo[2,3-c]pyridine and its 2- and 3-methyl derivatives from ethyl 3-hydroxyisonicotinate ( 2 ) is described. The hydroxy ester 2 was O-alkylated with ethyl bromoacetate or ethyl 2-bromopropionate to give the diester 3a or 3b . Cyclization of compound 3a afforded ethyl 3-hydroxyfuro [2,3-c]pyridine-2-carboxylate ( 4 ) which was hydrolyzed and decarboxylated to give furo[2,3-c]pyridin-3(2H)-one ( 5a ). Cyclization of 3b gave the 2-methyl derivative 5b . Reduction of 5a and 5b with sodium borohydride yielded the corresponding hydroxy derivative 6a and 6b , respectively, which were dehydrated with phosphoric acid to give furo[2,3-c]pyridine ( 7a ) and its 2-methyl derivative 7b . 4-Acetylpyridin-3-ol ( 8 ) was O-alkylated with ethyl bromoacetate to give ethyl 2-(4-acetyl-3-pyridyloxy) acetate ( 9 ). Saponification of compound 9 , and the subsequent intramolecular Perkin reaction gave 3-methylfuro[2,3-c]pyridine ( 10 ). Cyclization of 9 with sodium ethoxide gave 3-methylfuro[2,3-c]pyridine-2-carboxylic acid, which in turn was decarboxylated to give compound 10 . 相似文献
3.
The tricyclic dimethylene hydrocarbons 5 , 6 , 7 , 8 and d2- 5 , (Scheme 2), which are prepared by Wittig-reaction from the corresponding ketones, are rearranged, by heating, to 4-aryl-but-1-yne derivatives via the unstable 6-allenyl-1-methylene-cyclohexa-2, 4-diene intermediates (e.g. Scheme 14). Using the deuterium-labelled compound d2- 5 , it was shown that the allenyl moiety, formed by a retro-Diels-Alder reaction (cycloreversion) of the tricyclic dimethylene compound, migrates with complete inversion in the final o-semibenzene-benzene rearrangement (Schemes 11 and 14). Reaction of 6-propargyl-cyclohexa-2, 4-dien-1-ones with triphenylphosphonium methylide gives 6-propargyl-1-methylene-cyclohexa-2 4-dienes, which immediately undergo a [3s, 3s]-rearrangement to form 4-aryl-buta-1, 2-dienes (Scheme 9). In contrast, the rearrangement of the corresponding 4-propargyl-1-methylene-cyclohexa-2, 5- dienes proceeds by a radical mechanism (Schemes 10 and 13). 相似文献
4.
The synthesis of the title compound 9 is described. Benz[a]anthracene 8,9-oxide (6) was reacted with sodium azide in aqueous acetone and the trans-9-azido-8,9-dihydrobenz[a]anthr-8-ol (7), so formed, was cyclized by tri-n-butylphosphine. Attempts to dehydrogenate 10,11-dihydrobenz[a]anthracene 8,9-imine (4) with DDQ or by allylic bromination followed by base assisted dehydrobromination was unsuccessful. The N-tosyl derivative of 4, prepared from the free imine, N,O-bis(trimethylsilyl)acetamide and tosyl chloride underwent rapid aziridine-ring cleavage by the silylating agent to give trans-8,9,10,11-tetrahydro-8-(4-methyl)benzensulfon-amido-9- [(trimethyl)oxy]benz[a]anthracene (10). 相似文献
5.
A Further Approach to 2,6-Dioxatricyclo[3.3.2.03,7]decane A further synthesis of 2,6-dioxatricyclo[3.3.2.03,7]decane ( 10 ) is described by bridging the 9-oxabicyclo[4.2.1]non-7-en-3endo-ol ( 9 ). The latter compound was prepared by ring expansion starting from the known 8-oxabicyclo[3.2.1]oct-6-en-3-on ( 1 ). 相似文献
6.
A convenient synthesis of furo[3,2-b]pyridine and its 2- and 3-methyl derivatives from ethyl 3-hydroxypiconate ( 1 ) is described. The hydroxy ester 1 was O-alkylated with ethyl bromoacetate or ethyl 2-bromopropionate to give the diester 2a or 2b . Cyclization of compound 2a afforded ethyl 3-hydroxyfuro[3,2-b]pyridine-2-carboxylate ( 3 ) which in turn was hydrolyzed and decarboxylated to give furo[3,2-b]pyridin-3-(2H)-one ( 4a ). Cyclization of 2b gave the 2-methyl derivative 4b . Reduction of 4a and 4b with sodium borohydride yielded the corresponding hydroxy derivative 5a and 5b respectively, which were dehydrated with phosphoric acid to give furo[3,2-b]pyridine ( 6a ) and its 2-methyl derivative ( 6b ). 2-Acetylpyridin-3-ol ( 8 ) was converted to the ethoxycarbonylmethyl ether ( 9 ) by O-alkylation with ethyl bromoacetate, which was cyclized to give 3-methylfuro[3,2-b]pyridine-2-carboxylic acid ( 10 ). Decarboxylation of 10 afforded 3-methylfuro[3,2-b]pyridine ( 11 ). 相似文献
7.
Giorgio Stefancich Romano Silvestri Marino Artico 《Journal of heterocyclic chemistry》1993,30(2):529-532
Reaction of 2-nitrobenzyl iodide with 1H-imidazole, in the presence of potassium tert-butoxide and 18-crown-6, gave 1-(2-nitrobenzyl)-1H-imidazole. Trichloroacetylation of this compound furnished trichloroacet-ylimidazole 8 , which on treatment with sodium ethoxide was transformed into the corresponding ethoxycarbonyl derivative 9 . Catalytic reduction of the nitro group to the amino group yielded 10 , which was then cyclized to 10,11-dihydro-11-oxo-5H-imidazo[2,1-c][1,4]benzodiazepine 11. Treatment of this lactam with di-4-morpholinylphosphinic chloride followed by reaction of the intermediate 12 with formylhydrazine gave the title compound or its 1-derivatives when acetylhydrazine or isonicotinoylhydrazine were used instead of formylhydrazine. 相似文献
8.
S. C. Mojumdar P. Šimon A. Krutošíková 《Journal of Thermal Analysis and Calorimetry》2009,96(1):103-109
(E)-3-(1-Benzofuran-2-yl)propenoic acid (1) was prepared from 1-benzofuran-2-carbaldehyde under the Doebner’s conditions. The obtained acid was converted to the corresponding
azide 2, which was cyclized by heating in diphenyl ether to [1]benzofuro[3,2-c]pyridine-1(2H)-one (3). This compound was aromatized with phosphorus oxychloride to chloroderivative 4 which was reduced with zinc and acetic acid to the title compound 5. [1]Benzofuro[3,2-c]pyridine-2-oxide (6) was synthesized by reaction of 5 with 3-chloroperoxybenzoic acid in dichloromethane. Treatment of 6 with benzoyl chloride and potassium cyanide (Reissert-Henze reaction) was shown to produce the corresponding [1]benzofuro[3,2-c]pyridine-1-carbonitrile (7). The title compound was used for preparation of complexes Cu2(ac)4(bfp)2 (8) and CoCl2(bfp)2 (9), where ac=CH3CO2− and bfp=[1]benzofuro[3,2-c]pyridine. Both oxygen atom of carboxylate ions is used in the coordination to Cu(II). Thermal
properties of the complexes 8 and 9 have been studied by TG and DTA and both complexes exhibited high thermal stability while complex 9 are thermally more stable than complex 8. 相似文献
9.
A. Monge Vega I. Aldana M. M. Rabbani E. Fernandez-Alvarez 《Journal of heterocyclic chemistry》1980,17(1):77-80
This paper describes the synthesis of the previously unknown 11H-1,2,4-triazolo[4,3-b]pyridazino[4,5-b]indoles (2) and 11H-tetrazolo[4,5-b]pyridazino[4,5-b]indoles (3) from 4-hydrazino-5H-pyridazino[4,5-b]indoles (1) , as well as the synthesis of 1,2,4-triazolo[3,4-f]-1,2,4-triazino-[4,5-a]indoles (10) from 2-indolecarbohydrazide (4) . Compounds 2 were obtained by acylation of compounds 1 , followed of thermal cyclization and compounds 3 by treating compounds 1 with nitrous acid. The reactions of compound 4 with formic acid or ethyl orthoformiate gave 1,2-dihydro-1-oxo-1,2,4-triazino[4,5-a]indole (6) . Treating this last compound with phosphorus oxychloride or phosphorus pentasulfide, followed by hydrazine, gave 1-hydrazino-1,2,4-triazino-[4,5-a]indole (9) . Acylation of this last compound, followed of cyclization gave compounds 10 . All the compounds were characterized by elemental analysis and ir and 1H-nmr spectra. 相似文献
10.
Mnika Szab Jzsef Kksi Lszl
rfi Attila Kovcs Istvn Hermecz 《Journal of heterocyclic chemistry》1997,34(1):21-25
3H,7H-[1,4]Diazepino[3,4-b]quinazolone-3,7-diones 9, 11 were synthesized starting from 2-(1-bromo-ethyl)quinazolin-4(3H)-ones 3 and 17 via 2-[1-(4-methoxyphenylamino)ethyl]quinazolin-4(3H)-ones 4 and 18. Cyclization of 3-[2-(1-bromoethyl)-4-oxo-3,4-dihydroquinazolin-3-yl)propionic acid 14 by the action of triethylamine provided the first representative of the tricyclic 7H-[1,4]oxazepino[3,4-b]quinazoline-3,7-dione system, compound 15. The new tricyclic derivatives 9, 11 and 15 are characterized by uv, ir and 1H nmr spectroscopy. 相似文献
11.
Seiji Yamaguchi Kunihiro Tsuzuki Minoru Kinoshita Yutaka Oh-Hira Yoshiyuki Kawase 《Journal of heterocyclic chemistry》1989,26(2):281-284
Some 8- or 9-halobenzofuro[2,3-b]quinolines ( 1a , 8-F, 8-C1, 9-F, 9-Cl) and 9-halobenzofuro[2,3-b]quinoline-11-carboxylic acid ( 1b , F, Cl) were synthesized from 6- or 7-halo-3-(2-methoxyphenyl)-2-oxo-1,2-dihydroquino-line-4-carboxylic acids ( 3 ). And, some 9-halo-11(6H)-benzofuro[2,3-b]quinolinone ( 8 , F, Cl, Br) and 2-halo-6(5H)-benzofuro[3,2-c]quinolinone ( 9 , F, Cl, Br) were synthesized from 6-halo-4-hydroxy-3-(2-methoxyphenyl)-2(1H)-quinolinone ( 7 ), and they were converted to the corresponding chlorohalobenzofuroquinolines ( 1c , 9-F, 9-C1, 9-Br, and 2 , F, Cl, Br). 相似文献
12.
The hydrazones derived from coumarin-6-ylhydrazine and ethyl 6-hydrazinochromone-2-carboxylate undergo facile indolization to give 3H,7H-pyrano[3,2-e]indol-7-ones (IIIb-IIIg) and ethyl 9-oxo-3H,9H-pyrano[3,2-e]indole-7-carboxylates (IVb-IVd), respectively, in good yields. Compounds IVb-IVd are derivatives of a new ring system. 相似文献
13.
Patrik Kolar Andrej Petri
Miha Tiler Fulvia Felluga 《Journal of heterocyclic chemistry》1991,28(7):1715-1720
From the corresponding heterocyclic amino acids 2 and 9a the heterocyclic systems imidazo[1,5-a]pyridine ( 3 ) and imidazo[1,5-a]quinoline ( 10 ) are easily accessible. From compound 7 the tricyclic system 11 was prepared and from compound 17a a pyridyl-1,2,4-triazinone ( 18 ) could be obtained. 相似文献
14.
Francesco Savelli Alessandro Boido Gianluca Damonte 《Journal of heterocyclic chemistry》1996,33(6):1737-1742
With a continuing interest on heteropolycyclic structures which may show biological activities, we synthesized new tricyclic derivatives in which the pyridopyrazine skeleton is fused with pyrazine 7 and 8, B , n = 1. However, the initial design of obtaining also the cyclohomologous structure B (n = 2) produced instead a pyranopyridopyrazine derivative 11 . Thus during the attempt to prepare a pyridodiazepine intermediate, beside a very small amount of the desired product 10 , the pyridopyrazine 9 was obtained. The latter compound reacted with chloroacetyl chloride/chloroketene to give 4-carbethoxy-10-(chloroacetyl)-5,10-dihydro-5-methyl-2H-pyrano[2,3-b]pyrido[2,3-e]pyrazin-2-one ( 11 ). In studying the behavior of this derivative, compounds 12–14 were obtained. Compounds 4b,c, 5a,b, 7, 8, 9 and 14 have been submitted to preliminary pharmacological screening as CNS depressant agents. 相似文献
15.
The acid catalysed dienol-benzene rearrangement of methyl substituted o- and p-propargylcyclohexadienols ( 18–22 , 34 and 35 ) was investigated. In the first step water is eliminated to yield the corresponding methyl propargyl benzonium ions (cf. scheme 6, a ), which undergo [1s, 2s] sigmatropic rearrangements to give propargylbenzenes ( 28 , 29 , 30 , 38 ) and [3s, 4s] sigmatropic rearrangements to give allenylbenzenes ( 24–27 , 40) (cf. schemes 2, 3, 5, 6). [3s, 3s] sigmatropic rearrangements occur only to a small extend. In the rearrangement of 2-propargyl-2,4,6-trimethylcyclohexa-3,5-dien-1-ol ( 18 ) a [1s, 2s] sigmatropic methyl shift is observed (4%). 相似文献
16.
The preparation, isolation, structure determination, and some reactions of the two stereoisomers of 2-iodo-9-oxabicyclo[4.2.1]nonane ( 9 and 10 ) and of 2-iodo-9-oxabicyclo[3.3.1]-nonane ( 11 and 12 ), respectively, are described. Iodine cleavage of the [4.2.1]-iodomercuri compound 3 yielded the iodides 9, 10 , and 11 , and iododemercuration of the [3.3.1]-iodomercuri compound 6 afforded the iodo compounds 9, 11 , and 12 , respectively. Direct treatment of 4-cycloocten-1-ol ( 1 ) with iodine in chloroform resulted in the exclusive formation of the two endo-iodides 9 and 11 . Raney nickel treatment as well as lithium aluminium hydride reduction of each índividual iodo compound 9, 10, 11 , and 12 gave the corresponding unsubstituted 9-oxabicyclononane ( 4 or 8 , respectively) with the unaltered skeleton. No rearrangement products could be observed. An oxonium ion is involved as an intermediate in the reaction of the endo-iodides 9 and 11 with silver acetate leading to an identical mixture of the two acetates 15 and 16 as well as in the isomerization of 9 to 11 . 相似文献
17.
M. Luisa Quijano M. Nogueras A. Snchez M. Melgarejo R. Lpez M. Luisa Jimeno J. N. Low R. A. Howie G. Ferguson 《Journal of heterocyclic chemistry》1994,31(6):1583-1588
The nmr and X-ray diffraction data of the novel ring system furo[3,2-e]imidazo[1,2-c]pyrimidine are reported in this paper. The crystal and molecular structure of this compound (C9H7N3O2·1/2H2O) has been solved at room temperature. Crystals are monoclinic in a space group of P2/n with cell constants a = 9.982(8), b = 13.526(9) and c = 13.981(9) Å, β = 107.44(5)°, V = 1800.9 Å3, Z = 8, Dx = 1.462 Mg·m?3. The structure was solved by full matrix least square refinement giving a final R = 0.054 (Rw = 0.069) for 1263 reflections (I>3.0σ(I)). The compound is essentially planar, existing in two slightly structural different forms, A and B. These are held in pairs with symmetry related molecules by hydrogen bonds formed with two water molecules. Then the dimeric units are stacked parallel to the c axis to form the tridimensional packing. 相似文献
18.
Treating 2-mercaptobenzohydrazide ( 1a ) with cyanogen bromide gave 3-amino-2-imino-3,4-dihydro-2.H-1,3-benzothiazin-4-one ( 2a ). This compound underwent further cyclocondensation with a second molecule of cyanogen bromide or S-methylisothiourea sulfate to afford the biologically interesting 2-amino-1,2,4-triazolo-[5,1-b][1,3]benzothiazin-9-one ( 3c ). Compound 3c could also be prepared directly from 1a by treating with excess amount of cyanogen bromide in more satisfactory yield. 相似文献
19.
Rudolph A. Abramovitch Muthiah N. Inbasekaran Adrian L. Miller James M. Hanna 《Journal of heterocyclic chemistry》1982,19(3):509-512
2-(2-Mercaptophenyl)pyridines are prepared from the corresponding phenols and oxidized with N-chloro-succinimide and silver tetrafluoroborate to benzisothiazolo[2,3-a]pyridine salts ( 4 ). The latter do not rearrange thermally or photochemically to benzothiopheno[3,2-b)pyridines ( 19 ) and are attacked by nucleophiles at sulfur rather than in the pyridine ring, to give the original 2-(2-mercaptophenyl)pyridine back in a reaction involving a dismutation. 19 is prepared by rearranging O-[2-(3-bromo-2-pyridyl)-4-nitrophenyl]dimethylthio-carbamate to the S-aryl compound and heating the latter with strong base. 相似文献
20.
John Anthony Armen M. Boldi Corinne Boudon Jean-Paul Gisselbrecht Maurice Gross Paul Seiler Carolyn B. Knobler Franois Diederich 《Helvetica chimica acta》1995,78(4):797-817
Tetraethynylethene (3,4-diethynylhex-3-ene-1,5-diyne) molecular scaffolding provided access to novel macrocyclic nanometer-sized C-rich molecules with unusual structural and electronic properties. Starting from cis-bis-deprotected cis-bis(trialkylsilyl)protected tetraethynylethenes, the per(silylethynyl)ated octadehydro[12]annulenes 1 and 2 and the corresponding dodecadehydro[18]annulenes 4 and 5 were prepared by oxidative Hay coupling. X-Ray crystal-structure analyses of (i-Pr)3Si-protected 2 and Me3Si-protected 4 showed that both annulene perimeters are perfectly planar. Electronic absorption spectral comparisons provided strong evidence that the macro rings in the deep-purple-colored 1 and 2 are antiaromatic (4n π-electrons), whereas those in yellow 4 and 5 are aromatic ((4n + 2) π-electrons). Although unstable in solution, the antiaromatic compound 2 gave high-melting crystals in which the individual octadehydro[12]annulene chromophores are isolated and stabilized in a matrix-type environment formed by the bulky (i-Pr)3Si groups. Electrochemical studies demonstrated that the antiaromatic octadehydro[12]annulene 2 undergoes two stepwise one-electron reductions more readily that the aromatic chromophore 5 . This redox behavior is best explained by the formation of an aromatic (4n + 2) π-electron dianion from 2 , whereas 5 loses its aromaticity upon reduction. The Me3Si derivative 4 was deprotected with borax in MeOH/THF to give the highly unstable hexaethynyl-dodecadehydro[18]annulene 6 , a C30H6 isomer and macrocyclic precursor to a two-dimensional all-C-network. Deprotection of 2 did not give isolable amounts of tetraethynyl-octadehydro[12]annulene 3 due to the extreme instability of the latter. Starting from dimeric and trimeric acyclic tetraethynylethene oligomers, a series of expanded radialenes were obtained. They possess large C-cores with silylethynyl-protected peripheral valences and can be viewed as persilylated C40 ( 7 ), C50 ( 8 ), and C60 ( 9 ) isomers. These expanded C-sheets are high-melting, highly stable, soluble materials which were readily characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry. Due to inefficient macrocyclic cross-conjugation and/or non-planarity, the extent of π-electron delocalization in 7 – 9 is limited to the longest linearly conjugated π-electron fragment. In agreement with these properties, all three expanded radialenes exhibited similar redox behavior; they are difficult to oxidize but undergo several reversible one-electron reductions in similar potential ranges. Presumably, the reduced π-electron delocalization is also at the origin of the particularly high stability of 7 – 9 . 相似文献