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1.
Chloromethylation of N-acetyl-2,3,4,5-tetrahydro-7,8-methylenedioxy-1H-3-benzazepine ( 4 ) proceeded, depending on reaction conditions, at the 6- or 6,9- positions. Subsequent transformation of these intermediates provided a series of mono and bis aromatic-substituted derivatives of the parent benzazepine 3 . 相似文献
2.
Jonathan B. Ball Margaret G. Wong Benny Capuano Jacqueline M. Gulbis Maureen F. Mackay Paul F. Alewood 《Journal of heterocyclic chemistry》1990,27(2):279-286
The constrained dipeptide mimic 1 was synthesized from 2 in three steps with 65% overall yield. Analyses of the 1H nmr data of a number of 3-amino-2,5-dioxo-2,3,4,5-tetrahydro-1H-1-benzazepine derivatives led to the conclusion that these compounds adopt a similar conformation and that this ring system is rigid. X-ray crystallography was used to define the structure of 3 , and computer-aided energy minimization of 6 gave a preferred conformation similar to that observed in the crystal of 3 . 相似文献
3.
The syntheses of the B-norbenzomorphans, 1,5-methano-2,3,4,5-tetrahydro-1H-2-benzazepine (1a) and its N-methyl derivative (Ib) were accomplished. Phenylsuccinic anhydride (III) was cyclized to 3-carboxy-1-indanone (IVa), which was converted by the Arndt-Eistert method to the homologous methyl indanone-3-acetate (V). One experiment in the synthesis of V led to the by-products 3-carboxamido-1-indanone (IVd) and 3-(N-methylcarboxamido)-1-indanone (IVe), identified by physical and chemical means. Methyl 1-aminoindan-3-acetate (VII) was prepared by catalytic reduction of methyl indanone-3-acetate oxime (VI). Hydrolysis of VII afforded 1-aminoindan-3-acetic acid (VIII), which was cyclized with dicyclohexylcarbodiimide to 1,5-methano-2,3,4,5-tetrahydro-1H-2-benzazepin-3-one (IX). Reduction (lithium aluminum hydride) of IX gave amine Ia which was then methylated to Ib. The mass spectral fragmentation patterns of IX and Ia are discussed. 相似文献
4.
A new synthesis of aromatic methoxy and methylenedioxy substituted 2,3,4,5-tetrahydro-1H-3-benzazepines is described. Suitably substituted phenethylamines and their α-methyl homologs in the form of their N-acetyl derivatives are chloromethylated, the resulting benzyl chlorides are reacted with cyanide and hydrolysis of the latter yields 2-(2-aminoethyl)phenylacetic acid derivatives. Thermal cyclization yields the corresponding lactams. Hydride reduction of these lactams furnishes the substituted 2,3,4,5-tetrahydro-1H-3-benzazepines which may be methylated on nitrogen by formaldehyde and hydrogen. By this sequence a number of previously unde-scribed compounds have been prepared. 相似文献
5.
George Bobowski Jeffrey M. Gottlieb Barbara West John Shavel 《Journal of heterocyclic chemistry》1979,16(8):1525-1534
The multi-step synthetic procedures to prepare a number of 2,3,4,5-tetrahydro-1H-benzazepine derivatives 1 through a series of intermediates are described. The condensation of arylaldehydes 2 with 2-nitropropanes 3 gave nitroalcohols 4 which were reduced to alcohol amines 5 . The condensation of 5 with arylacetaldehydes 6 gave imino derivatives 7 which on reduction with borohydride gave secondary amines 8 . By employing different methods, alcohol amines 5 were condensed with arylacetic acids 9 to give amides 10 which were then reduced to amines 8 . On treatment with mineral acids, amines 8 were cyclized to the target compounds 1 . Biological activities of 1 are also briefly discussed. 相似文献
6.
Jotham W. Coe Paige R. BrooksMichael G. Vetelino Crystal G. BashoreKrista Bianco Andrew C. Flick 《Tetrahedron letters》2011,52(9):953-954
Concise syntheses of 1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocine (12) and 2,3,4,5-tetrahydro-1,5-methano-1H-2-benzazepine (18) are described and involve an intramolecular Friedel-Crafts alkylation and an intramolecular Heck cyclization as their respective key ring-forming steps. 相似文献
7.
BECKMANN or SCHMIDT rearrangement of ethyl trans-4-oxo-1-phenyl-2-tetralincarboxylate ( 2 ) affords ethyl trans-2,3,4,5-tetrahydro-2-oxo-5-phenyl-1H-benzo [b] azepine-4-carboxylate ( 4 ). Mild treatment of trans-2,3,4,5-tetrahydro-1-methyl-2-oxo-5-phenyl-1 H-benzo-[b] azepine-4-carboxylic acid ( 7 ) with thionyl chloride and pyridine in dimethylformamide and subsequent reaction with an amine yields the corresponding benzazepine-4-carboxamide. If he it is applied during the preparation of the acid chloride, rearrangement occurs yielding cis and trans derivatives of hydrocarbostyril. 2,3,4,5-Tetrahydro-1,4-methano-1-methyl-5-phenyl-1 H-benzo-[b] azepinium chloride ( 25 ) reacts with primary or secondary amines to cis-tetrahydroquinoline derivatives. When heated above its melting point, trans-4,5-dihydro-2-methylamino-5-phenyl-3H-benzo-[b] azepine-4-carboxylic acid ( 29 ) rearranges with elimination of water to a mixture of cis-and trans-2,3,3a,4-tetrahydro-1-methyl-2-oxo-4-phenyl-1H-pyrrolo [2,3-b] quinoline ( 32 and 31 ). The reduction of 31 was investigated. The mechanisms of the rearrangements are discussed. 相似文献
8.
Ioannis M. Takakis Phaedon M. Hadjimihalakis Michael L. Gross Roger N. Hayes George W. Haas 《Journal of mass spectrometry : JMS》1993,28(2):95-100
Electron impact ionization of the five isomeric 2,3,4,5-tetrahydro-9-azido-7,8-dinitro-, 2,3,4,5-tetrahydro-8-azido-7,9-dinitro-, 2,3,4,5-tetrahydro-8-azido-7,10-dinitro-, 2,3,4,5-tetrahydro-7-azido-8,9-dinitro-, 2,3,4,5-tetrahydro-7-azido-8,10-dinitro- and the related 2,3,4,5-tetrahydro-7-acetamido-8-azido-9-nitro-, 2,3,4,5-tetrahydro-7-acetamido-9-azido-8-nitro-, 2,3,4,5-tetrahydro-9-acetamido-7-azido-8-nitro-, 2,3,4,5-tetrahydro-10-acetamido-7-azido-8-nitrobenzo[b] [1,4]dioxocin derivatives furnished, after elimination of nitrogen, the corresponding nitro and acetamido dioxocino-annelated benzofuroxans. Further loss of oxygen from the latter afforded the corresponding benzofurazans. It was shown in two cases that these processes occur primarily upon electron impact ionization, without excluding some small fraction undergoing a thermal degradation process. The proposed fragmentation patterns are supported by high-resolution and mass-analyzed ion kinetic energy spectroscopic data. Similar work on the unsubstituted 6,7-dihydro[1,4]dioxino[2,3-f]- and 7,8-dihydro-6H-[1,4]dioxepino[2,3-f]-2,1,3-benzoxa-diazole 1-oxide reveal that loss of oxygen from the molecular ion to furnish the corresponding benzofurazans is the result of electron impact ionization (at least in part). 相似文献
9.
The p-toluenesulfonate of 7,8-dihydro-5(6H)quinoloneoxime( 3 ) was subjected of a Beckmann rearràngement. The resulting 2,3,4,5-tetrahydro-1H-pyrido[3,2-b]azepin-2-one ( 4 ) was reduced with lithium aluminum hydride affording 2,3,4,5-tetrahydro-1H-pyrido[3,2-b] azepine ( 5 ). 5,6-l)ihydro-8(7H)quinolone ( 7 ), obtained by oxidation of 5,6,7,8-tetrahydro-8-quinolinol ( 6 ), was converted into the p-toluenesulfonate of 5,6-dihydro-8(7H)quinolone oxitne ( 9 ). Similarly the latter compound could be rearranged into 2,3,4,5-letrahydro-1H-pyrido [2,3-b] azepin-2-one ( 10 ) which on reduction produced 2,3,4,5-tetrahydro-1H-pyrido [2,3-b] azepine ( 11 ). 相似文献
10.
Bradshaw B Evans P Fletcher J Lee AT Mwashimba PG Oehlrich D Thomas EJ Davies RH Allen BC Broadley KJ Hamrouni A Escargueil C 《Organic & biomolecular chemistry》2008,6(12):2138-2157
Two approaches to tetrahydro-[1H]-2-benzazepin-4-ones of interest as potentially selective, muscarinic (M(3)) receptor antagonists have been developed. Base promoted addition of 2-(tert-butoxycarbonylamino)methyl-1,3-dithiane with 2-(tert-butyldimethylsiloxymethyl)benzyl chloride gave the corresponding 2,2-dialkylated 1,3-dithiane which was taken through to the dithiane derivative of the parent 2,3,4,5-tetrahydro-[1H]-2-benzazepin-4-one by desilylation, oxidation and cyclisation via a reductive amination. After conversion into the N-tert-butyloxycarbonyl, N-toluene p-sulfonyl and N-benzyl derivatives , hydrolysis of the dithiane gave the N-protected tetrahydro-[1H]-2-benzazepin-4-ones . However, preliminary attempts to convert these into 5-cycloalkyl-5-hydroxy derivatives were not successful. In the second approach, ring-closing metathesis was used to prepare 2,3-dihydro-[1H]-2-benzazepines which were hydroxylated and oxidized to give the required 5-hydroxy-2,3,4,5-tetrahydro-[1H]-2-benzazepin-4-ones. Following preliminary studies, ring-closing metathesis of the dienyl N-(2-nitrophenyl)sulfonamide gave the dihydrobenzazepine which was converted into the 2-butyl-5-cyclobutyl-5-hydroxytetrahydrobenzazepin-4-one by hydroxylation and N-deprotection followed by N-alkylation via reductive amination, and oxidation. This chemistry was then used to prepare the 2-[(N-arylmethyl)aminoalkyl analogues , , and . N-Acylation followed by amide reduction using the borane-tetrahydrofuran complex was also used to achieve N-alkylation of dihydrobenzazepines and this approach was used to prepare the 5-cyclopentyl-5-hydroxy-2,3,4,5-tetrahydro-[1H]-2-benzazepin-4-one and the 5-cyclobutyl-8-fluoro-5-hydroxy-2,3,4,5-tetrahydro-[1H]-2-benzazepin-4-one . The structures of 2-tert-butyloxycarbonyl-4,4-propylenedithio-2,3,4,5-tetrahydro-[1H]-2-benzazepine and (4RS,5SR)-2-butyl-5-cyclobutyl-4,5-dihydroxy-2,3,4,5-tetrahydro-[1H]-2-benzazepine were confirmed by X-ray diffraction. The racemic 5-cycloalkyl-5-hydroxy-2,3,4,5-tetrahydro-[1H]-2-benzazepin-4-ones were screened for muscarinic receptor antagonism. For M(3) receptors from guinea pig ileum, these compounds had log(10)K(B) values of up to 7.2 with selectivities over M(2) receptors from guinea pig left atria of approximately 40. 相似文献
11.
A novel synthesis of 2,3-dihydro-1H-1,3-diazepin-2-ones based on thermal elimination of methanol from 4-methoxy-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones has been developed. The prepared dihydrodiazepinones underwent two new rearrangements under basic or acidic conditions to give the pyrrole derivatives, 3-(aminomethylene)-2,3-dihydro-1H-pyrrol-2-ones and 1-carbamoyl-1H-pyrroles, respectively. Plausible mechanisms for the rearrangements are proposed. 相似文献
12.
[reaction: see text] A new iridium-catalyzed oxidative cyclization of amino alcohols has been revealed. Indole derivatives are synthesized in good to excellent yields from 2-aminophenethyl alcohols by means of a [CpIrCl(2)](2)/K(2)CO(3) catalytic system. The present catalytic system is also effective for syntheses of 1,2,3,4-tetrahydroquinolines from 3-(2-aminophenyl)propanols and 2,3,4,5-tetrahydro-1-benzazepine from 4-(2-aminophenyl)butanol. 相似文献
13.
Regina Janciene Ausra Vektariene Zita Stumbreviciute Lidija Kosychova Kazimieras Konstantinavicius Benedikta D. Puodziunaite 《Monatshefte für Chemie / Chemical Monthly》2003,44(1):1629-1639
Highly substituted, novel, 8- and 9-nitro-2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones were obtained by direct nitration of the 7-bromo-5-trifluoroacetyl (or formyl)-substituted tetrahydrobenzodiazepinones. Alkaline and acidic hydrolysis of the novel mononitro derivatives was examined. Semiempirical AM1 calculations of aromatic substituents orientation in the nitration products are presented. 相似文献
14.
Reaction of 2-acylcyclohexane-1,3-diones with 5- and 6-membered cyclic azomethines (3,4-dihydro-2H-pyrrole and 2,3,4,5-tetrahydropyridine) furnished derivatives of 2,3,3a;,4,8,9-hexahydropyrrolo[1,2-a]quinoline-5,6(1H,5aH)-dione and 3,4,4a,5,9,10-hexahydro-1H-pyrido[1,2-a]quinoline-6,7(2H,8H)-dione respectively. In reaction with 7-membered 3,4,5,6-tetrahydro-2H-azepine we failed to isolate polycyclic nitrogen-containing products. 相似文献
15.
Summary. Highly substituted, novel, 8- and 9-nitro-2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones were obtained by direct nitration of the 7-bromo-5-trifluoroacetyl (or formyl)-substituted tetrahydrobenzodiazepinones. Alkaline and acidic hydrolysis of the novel mononitro derivatives was examined. Semiempirical AM1 calculations of aromatic substituents orientation in the nitration products are presented. 相似文献
16.
DFT B3LYP calculation study was employed to estimate the regioselectivity of an electrophilic aromatic substitution in functionalized 2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones. Charge density, frontier molecular orbital study, energetics of σ-complex intermediates of electrophilic substitution reactions in the 2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones yield information on different reactivity of aromatic sites. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:263–270, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20015 相似文献
17.
Pierfrancesco Bravo Massimo Frigerio Calimero Ticozzi 《Journal of heterocyclic chemistry》1988,25(2):647-649
Through an anti-Markovnikow hydration of some olefin derivatives of 4-hydroxy-2-pyrones, and 4-hydroxy-coumarins, followed by a regioselective intramolecular dehydration, involving the primary alcohols obtained and the enolic oxygen of the rings, promoted by Amberlyst 15 in boiling toluene, the new heterocycles 2,3,4,5-tetrahydro-6H-oxepino[3,2-c]pyran-6-one ( 3 ) and [1]benzopyran-6-ones ba,c were obtained in fair yields. 相似文献
18.
Giovanni Orzalesi Renato Selleri Rodolfo Landi Vittory Franco Innocenti Giuliano Grandolini 《Journal of heterocyclic chemistry》1977,14(5):733-738
2-Amino-5-chloro-α-phenylbenzylidene hydrazone ( 1 ) or its methyl derivative 2 or acetyl derivative 10 react with diethylmalonic esters to give the corresponding malonyl derivatives 3, 4 and 8 . These esters were hydrolyzed to the acids 5 and 6 . Treating 5 with dehydrating agents the mesoionic compound 7-chloro-9-phenyl-3,3-diethyl-3H-pyrazolo[5,1-b]quinazolin-10-ium-2-olate (14) was obtained, while the methyl derivative 6 afforded the desired 9-chloro-2,3,4,5-tetrahydro-1-methyl-3,3-diethyl-7-phenyl-1H-benzo-1,5,6-triazonine-2,4-dione ( 17 ). Some derivatives of these compounds were also described. The structures of the new compounds were confirmed by an alternative synthesis and by mass and prnr spectral data. 相似文献
19.
O. Hromatka M. Knollmüller H. Deschler 《Monatshefte für Chemie / Chemical Monthly》1969,100(2):469-478
Zusammenfassung Beim Erhitzen von (2-Aminophenyl)acetamiden mit Formaldehyd in Äthanol oder Diäthylenglykoldimethyläther erhält man 2,3,4,5-Tetrahydro-1H-1,3-benzodiazepin-4-one; 2,3,4,5-Tetrahydro-1H-1,3-benzodiazepin-2-one entstehen beim Einwirken von Phosgen auf -(2-Aminophenyl)äthylamine. Die als Zwischenprodukte benötigten (2-Nitrophenyl)acetamide wurden aus den entsprechenden Nitrobenzoesäuren durchArndt—Eistert-Reaktion hergestellt.
Syntheses of New 2.3.4.5-tetrahydro-1H-1-3-benzodiazepinones
Heating (2-aminophenyl)acetamides with formaldehyde in ethanol or diethylene glycol dimethylether yields 2.3.4.5-tetrahydro-1H-1,3-benzodiazepine-4-ones; 2.3.4.5-tetrahydro-1H-1.3-benzodiazepine-2-ones are formed by reaction of phosgene with -(2-aminophenyl)ethylamines. The (2-nitrophenyl)acetamides needed as intermediate compounds were synthesized from the corresponding nitrobenzoic acids byArndt—Eistert reaction.相似文献
20.
Several hexahydroisoquino[2,3-b][2]benzazepines 1b-e variously substituted at positions 9,10,11 by alkoxy groups have been prepared by the Pictet-Spengler cyclization between formaldehyde and 3-alkoxybenzyl-2,3,4,5-tetrahydro-1H-2-benzazepines 12b-e. The compounds did not show any antitumor activity against leukemia L-1210 cells. 相似文献