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1.
The oxidation of some 3-(methoxy- and ethoxycarbonyl)tetrahydro-β-carboline derivatives with sodium periodate led to the formation of 1, 4-benzodiazonine derivatives or fully aromatic β-carbolines depending on both nature and number of substituents at 1-position. 相似文献
2.
The electrochemical oxidation of 6-hydroxy-1,2,3,4-tetrahydro-β-carboline (1), an alkaloid which occurs naturally in the mammalian brain, has been studied in aqueous solution particularly at physiological pH. The first voltammetric oxidation peak of 1 observed at the pyrolytic graphite electrode generates a radical intermediate which dimerizes to give 5,5′-bi-(6-hydroxy-1,2,3,4-tetrahydro-β-carboline) (3). However, the putative radical intermediate can also be further oxidized (1e) to give a C(5)-centered carbocation which can either dimerize in an ion-substrate reaction to give 3 or be attacked by water to give 5,6-dihydroxy-1,2,3,4-tetrahydro-β-carboline (8) which is rapidly oxidized further to 1,2,3,4-tetrahydro-β-carboline-5,6-dione (9). In the presence of glutathione dione 9 forms the 8-S-glutathionyl conjugate of 8 which is easily oxidized to the 8-S-glutathionyl conjugate of 9. It is suggested that 1 might be an alkaloid which is elevated in the brain as a result of chronic alcoholism, and the roles of the oxidative transformations of this compound in some of the addictive and neurophathological consequences of ethanol consumption are discussed. 相似文献
3.
Guido Settimj Maria Rosaria Del Giudice Rosella Ferretti Franco Gatta 《Journal of heterocyclic chemistry》1988,25(5):1391-1397
Condensation of diethyl formylamino- or diethyl acetylaminomalonate with 4-, 5- or 6-nitrogramine 1 afforded the diethyl formylamino- or the diethyl acetylamino[(nitroindol)-3-ylmethyl]malonates 2 ; reduction of the nitro group followed by N-formylation or acetylation of the resulting amino compounds 3 , led to the 4-, 5-and 6-acylamino derivatives 4 . Cyclization of 4 in the presence of polyphosphoric esters gave the 3,3-bis(ethoxycarbonyl)-3,4-dihydro-β-carbolines 5 , which underwent lithium chloride/water catalyzed monodeethoxycarbonylation to the corresponding 5-, 6- and 7-acylamino-3-ethoxycarbonyl-β-carbolines 6 , whose acidic hydrolysis led finally to the 5-, 6- and 7-amino-3-ethoxycarbonyl-β-carbolines 9 . The 6-amino compounds 9b-e were obtained also by direct nitration of 3-methoxycarbonyl-β-carboline 7a and of 3-ethoxycarbonyl-β-carboline 7c , followed by the nitro group reduction of the resulting nitro carbolines 8 . Preliminary studies of the binding to rabbit brain benzodiazepine receptor sites indicate compounds 9b and 9c to inhibit the 3H-diazepam binding at 10?8 M concentrations. 相似文献
4.
Pilar De Miguel Nazario Martín Miguel F. Braa 《Journal of heterocyclic chemistry》1994,31(5):1235-1239
Novel tetrahydroimidazo[1,5-b]-β-carbolines derivatives 6 bearing complex basic chains as substituents on the imidic nitrogen have been prepared in a one-pot reaction. This simple experimental procedure overcomes the direct handle of isocyanates which can be favorably generated “in situ” from carbonyldiimidazole (CDI) and different amines. The stereochemistry of the novel compounds was determined by nmr experiments. 相似文献
5.
Maria Rosaria Del Giudice Franco Gatta Guido Settimj 《Journal of heterocyclic chemistry》1990,27(4):967-973
Oxidation of 1-methyl-3-methoxycarbonyl-β-carboline with selenium dioxide gave 1-formyl-3-methoxycarbonyl-β-carboline II . Compound II reacted with acetic or propionic anhydride to give easily the 2-methoxycarbonyl-6H-indolo[3,2,1-d,e][1,5]naphthyridin-6-ones III ; reaction of II with some primary amines led to the formation of the Schiff bases IV , which were reduced to the 1-aminomethyl-3-methoxycarbonyl-β-carbolines V with sodium borohydride. Cyclization of V with aqueous formaldehyde led to the pyrimido[3,4,5-lm]pyrido[3,4-b]indoles VI . Analogously, cyclization with formaldehyde, acetone or 1,1′-carbonyldiimidazole of the 3-aminomethyl- 1,2,3,4-tetrahydro-β-carbolines VIII , obtained by reaction of 3-methoxycarbonyl-1,2,3,4-tetrahydro-β-carboline VII with amines followed by lithium aluminium hydride reduction of the resulting amides, gave the imidazo[1′,5′-1,6]pyrido[3,4-b]indoles IX and X . Dieckmann cyclization of 3-methoxycarbonyl-2-[(3-ethoxycarbonyl)-1-propyl]-1,2,3,4-tetrahydro-β-carboline XI led to a 1:1 mixture of the β-ketoesters XII and XIII , which underwent deethoxycarbonylation to 5,6,8,9,10,11,11a,12-octahydroindolo[3,2-b]quinolizin-11-one XIV . Finally, the polyphosphoric acid (or esters) catalyzed cyclization of the N-acyl derivatives XVI of 3-hydrazinocarbonyl-β-carboline XV led smoothly to the 3-(1,3,4-oxadiazol-2-yl)-β-carbolines XVII . 相似文献
6.
7.
The 13C NMR spectra of β-carboline alkaloids were determined, and unambiguous assignments of the spectra were carried out from the long-range coupling constants. 相似文献
8.
Gilberto Spadoni Cesarino Balsamini Annalida Bedini Ermanno Duranti Andrea Tontini 《Journal of heterocyclic chemistry》1992,29(2):305-309
The ethylaluminum dichloride catalyzed Michael-type addition of indoles 1a-h to the N-(diphenylmethylene)-α,β-didehydroamino acid esters 2a-c allows a new synthesis of β-methyltryptophanes 41,m and a new route for 1,1-diphenyl-3-carbalkoxy-1,2,3,4-tetrahydro-β-carbolines 5a-m. 相似文献
9.
10.
James C. Callaway Jukka Gyntber Antti Poso Mauno M. Airaksinen Jouko Vepslinen 《Journal of heterocyclic chemistry》1994,31(2):431-435
Biogenic tryptamines 1a-c were reacted with aldehydes 2a & b and α-keto acids 2c & d to form 1,2,3,4-tetrahydro-β-carbolines (THBCs) 4d-1 , and other products, in a buffered solution at 37° and pH 7.4. These reactions were followed over time by 1H nmr through integral changes in discrete signals in the spectra. Reactions between tryptamines and acetaldchyde ( 2b ) gave the expected 1-methyl-THBCs 4d-f , while those with sodium glyoxylate ( 2c ) resulted in THBC-1-carboxylic acids 4g-1 . Surprisingly, reactions with sodium pyruvate ( 2d ) or formaldehyde ( 2a ) did not form the expected products 4a-c or 4j-1 , respectively under these conditions. In successful reactions, 5-methoxytryptamine ( 1c ) was found to be more reactive than tryptamine ( 1a ) or serotonin ( 1b ). MOPAC calculations were employed to investigate reaction intermediates. These results are applicable in research related to aberrant tryptamine metabolism; e.g. depression and alcoholism. 相似文献
11.
Jurij Svete Branko Stanovnik Miha Tiler Ljubo Goli
Ivan Leban 《Journal of heterocyclic chemistry》1989,26(1):145-153
From heteroarylaminomethyleneoxazolones 4 , obtained from N-heteroarylformamidines 2 and 2-phenyl-5-oxo-4,5-dihydro-1,3-oxazole ( 3 ), the following β-heteroarylamino-α,β-dehydro-α-amino acid derivatives were prepared: methyl 8 and ethyl esters 9 , amides 10 and 11 , hydrazides 12 , and azides 15 . By catalytic hydrogenation the compounds 4 were converted into β-heteroarylamino substituted amides 18 and β-heteroarylamino-α-amino acids 20 . 相似文献
12.
2-Alkoxy-4-heteroarylaminomethylene-5(4H)-thiazolones 4 were converted with various nucleophiles into β-heteroarylamino-α,β-dehydro-α-amino acid derivatives 11, 14, 15, 16, 17, 18 , and 19 . Reduction of 4 with sodium borohydride in ethanol saturated with gaseous ammonia afforded the corresponding β-heteroaryl-amino substituted alanyl amides 20 . Thiazoledione derivative 7a was transformed with sodium methoxide in methanol into 1-(4,6-dimethylpyrimidinyl-2)-4-mercaptocarbonylimidazol-2(3H)-one ( 8a ). 相似文献
13.
By the use of selenium dioxide as the specific oxidizing agent in the coumarin series, the 4-ethyl, 4-propyl and 4-benzyl substituents of coumarin were converted into α-alcohols 2 and/or ketones 3 , while 3-methyl- and 3-benzylcoumarins were converted into 3-acyl derivatives 7 . The methyl substituent of the analogous thiocoumarin 5 , chromones 10 or thiochromone 11 was also oxidized into the formyl functionality. Facile oxidative desulfurization into the ketone functionality, prior to methyl oxidation, was observed for the thione derivatives of 1a, 5, 6 and 10. 相似文献
14.
Yiting Zheng Yuen Tsz Cheung Lixin Liang Huiying Qiu Lei Zhang Anson Tsang Qing Chen Rongbiao Tong 《Chemical science》2022,13(35):10479
Oxidative rearrangement of tetrahydro-β-carbolines (THβCs) is one of the most efficient methods for the synthesis of biologically active spirooxindoles, including natural products and drug molecules. Here, we report the first electrochemical approach to achieve this important organic transformation in a flow cell. The key to the high efficiency was the use of a multifunctional LiBr electrolyte, where the bromide (Br−) ion acts as a mediator and catalyst and lithium ion (Li+) acts as a likely hydrophilic spectator, which might considerably reduce diffusion of THβCs into the double layer and thus prevent possible nonselective electrode oxidation of indoles. Additionally, we build a zero-gap flow cell to speed up mass transport and minimize concentration polarization, simultaneously achieving a high faradaic efficiency (FE) of 96% and an outstanding productivity of 0.144 mmol (h−1 cm−2). This electrochemical method is demonstrated with twenty substrates, offering a general, green path towards bioactive spirooxindoles without using hazardous oxidants.A zero-gap flow cell was designed for the first electro-oxidative rearrangement of tetrahydro-β-carbolines to spirooxindoles with high yield, faradaic efficiency and productivity when LiBr was discovered as a bi-functional mediator and catalyst. 相似文献
15.
16.
Takami S Oshida A Tawada Y Kashino S Satake K Kimura M 《The Journal of organic chemistry》2000,65(19):6093-6096
Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO(2)) were performed. The oxidation of 1 with SeO(2) gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1, 5-dihydro-pyrrol-2-one 4 in 13% yield, 2, 6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4, 7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO(2) gave 2, 2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative. 相似文献
17.
The first synthesis of an acetyl-α-thio-β-carboline [2-acetyl-2,9-dihydro-1,2-thiazino[6,5-b]indole ( 4 ) 28%] by the thermolysis of dithio-2,2′-di(N′-acetyltryptamine) 3 is reported. Deacetylation of 4 carried out in basic or acidic media does not lead to the free base but to a series of unidentified degradation products. This new substance 4 is therefore stabilized by the N-acetyl group. The results so far obtained are discussed and a mechanism is proposed for the cyclisation produced by the thermolysis. 相似文献
18.
Transformations of N'-heteroaryl-N,N-dimethylformamidines 1 as a general method for the preparation of β-heteroarylamino-α,β-dehydro-α-amino acids, β-heteroarylamino-α-amino acid derivatives 5–9 , and dipeptides 10 , are described. 相似文献
19.
3,4-Dihydro-β-carboline and benzo[α]-γ-carboline yielded Reissert compounds. The 3,4-dihydro-β-carboline Reissert compound, through its acid- and base-promoted reactions, was found to be a very useful intermediate in the synthesis of several β-carboline derivatives including tetracyclic compounds. Reaction of the 3,4-dihydro-β-carboline Reissert compound with dichlorodicyanobenzoquinone (DDQ) resulted in the formation of l-cyano-β-carboline thereby providing the first example of an oxidation of a Reissert compound with DDQ. α-, β- and γ-Carbolines failed to form Reissert compounds under a wide variety of conditions. 7-Azaindole also failed to yield a Reissert compound. 相似文献
20.