The stereochemistry of 4-methyl-6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides using NMR

Two isomeric 4-methyl-6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides were prepared, and their pmr and cmr spectra were examined. From the aromatic solvent shielding values and the magnitudes of the γ shifts, the title compounds are found to exist in the trans and cis forms in solution.     

Mass spectral fragmentations of 6-aryl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-Oxides

The mass spectral fragmentation of 4-, 5-, and 4,8-disubstituted derivatives of 6-aryl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides is reported.     

Synthesis of 4,8-dimethyl-6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocines

Five 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocines were synthesized by the reaction of the corresponding N,N-bis(2-hydroxypropyl)- and N,N-bis(2-hydroxyethyl)chloroanilines with paraformaldehyde in the presence of p-toluenesulfonic acid.     

Mass spectral fragmentations of 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocin-2-ones

The mass spectra of a series of 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocin-2-ones have been examined.     

Synthesis and spectral behavior of 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocines using NMR

Heterocyclic compounds of four 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocines have been synthesized by condensation of the corresponding N,N-bis(2-hydroxyethyl)- or N,N-bis(2-hydroxypropyl)anilines with aldehyde or ketone in the presence of acid. The pmr and cmr spectra of these compounds were recorded to determine their stereochemical structures. On the basis of the chemical shifts due to the γ-effects, the stereochemical structures are discussed.     

The stereochemistry of 4,8-dimethyl-6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocin-2-ones using NMR

Two isomeric 4,8-dimethyl-6-phenyl-5,6,7,8-tetrahydro-4H-1,3,6-dioxazocin-2-ones were prepared, and their pmr and cmr spectra were examined. From the tris(dipivaloylmethanato) europium (Eu(dpm)₃) shift reagent and the dihedral angle, the title compounds are found to exist in the eq-ax and eq-eq methyl groups with boat-chair form.     

3-phenyl-2H-1,4-benzoxazine-4-oxides—I : Synthesis and reduction

The title compounds were prepared by reductive cyclisation of o-nitro-phenoxy-acetophenones and characterized through a cycloadduct with acrylonitrile. Reduction of the N-oxides leads to the corresponding hydroxylamines that are highly unstable and can be transformed into the corresponding nitroxides by a variety of oxidation agents, including air. Previously unknown o-nitro-phenoxy-acetophenones were synthesized as starting materials for cyclisation reactions.     

Synthesis of 2-phenyl-3,4-dihydro-2H- and -3,4,5,6-tetrahydro-2H-1,6-benzothiazocine derivatives

The resynthesis of 2-phenyl-3,4-dihydro-2H-benzothiazocin-5(6H)-one (1) was investigated in order to prepare derivatives with potential CNS activity. Lactam 1 could be converted to amidine derivatives 6a-e via the intermediacy of the thioether 5a. Reduction of 1 with lithium aluminum hydride gave amine 8a . Reductive alkylation of 8a gave 9a and 9b while acylation of 8a gave derivatives 10a-d . No interesting biological properties were found for these compounds.     

2-氨基-3-氰基-7,7-二甲基-4-苯基-5-氧代-5,6,7,8-四氢-4H-苯并吡喃的合成和晶体结构

标题化合物C18H18N2O2是由亚苄基丙二睛和5,5-二甲基-1,3-环己酮在乙二醇中反应2小时得到,结构通过单晶X-射线衍射法确定,其晶体属单斜晶系,空间群P21/c,Mr=294.34,a = 11.3070(1), b= 9.4750(1),c = 14.919(2) ,β= 99.34(1)埃琕 = 1577.1(3) 3,Z = 4,Dc=1.240Mgm-3,μ=0.082mm-1,F(000)=624, 最终的偏离因子为R=0.0381,wR=0.0961,在分子结构中存在3个环:苯环(A)、吡喃环(B)及与吡喃环稠合的六员环(C)。A与B、A与C及B与C之间的两面角分别为 92.5°、85.7°和8.2°。     

Synthesis of 4-phenyl-1-(2-thienyl)-2,3,4,9-tetrahydro-1H-β-carboline

The Pictet-Spengler reaction involving β-phenyltryptamine was shown to be diastereo-specific with formation primarily of the (1S*,4R*) diastereomer of 4-phenyl-1-(2-thienyl)-2,3,4,9-tetrahydro-1H-β-carboline, a compound with potential GABA-receptor activity. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 468–470, September–October, 2006.     

1-甲基-5,6,7,8-四氢异喹啉酮-4-甲胺的合成研究

以环己酮为起始原料,经缩合、酰化及酸性水解反应制得2 乙酰基环己酮（1）;在三乙烯二胺催化下,1与氰基乙酰胺环化得四氢异喹啉酮（2）和四氢喹啉酮（3）混合物,在乙醇中回流并趁热过滤进行分离纯化得2和3; 2经催化加氢反应合成1-甲基-5,6,7,8-四氢异喹啉酮-4-甲胺,3步总收率39.8%,其结构经¹H NMR、¹³C NMR、 ¹H-¹⁵N HMBC和MS确证。     

6-甲氧基-1,2,3,9-四氢-4H-咔唑-4-酮肟的一锅合成

报道了6-甲氧幕-1,2,3,9-四氢-4H-咔唑-4-酮肟(3b)的一锅合成法,将Fischer吲哚合成与肟化两步反应并为一步,可简化操作,提高收率.反应可以在弱碱性且温度温和的条件下一锅合成,是由于肟化使Fischer吲哚环合变得容易,羰基与肟基在互变异构方向上的差别是影响环合反应的关键因素.     

2,4,7-三芳基-5-氧代-5,6,7,8-四氢-4H-苯并吡喃衍生物的合成

通过5-芳基-1,3-环己二酮和不同的查尔酮在酸或碱的催化下缩合,合成了7个尚未见文献报道的标题化合物(3a～3j).其结构经元素分析,IR和1H NMR证实并通过化合物3a的13C NMR分析进一步确证.     

Synthesis of 2-(p-Toluenesulfonamido)-4-phenyl-4, 5-dihydro-1H-1, 3, 4-diazaphosphole 4-oxides

Some novel unsaturated five-membered organophosphorus heterocyclic compounds, 2-(p-toluenesulfonamido)-4-phenyl-4, 5-dihydro-1H-1, 3, 4-diazaphosphole 4-oxides 8 have been synthesized by Mannich-type reaction of p-toluenesulfonylguanidine with phenyldichlorophosphine and ketones.     

Selective synthesis of some 5-hydrazono-5,6,7,8-tetrahydro-2H-1-benzopyran-2-ones

A simple, highly selective transformation of 5,6,7,8-tetrahydro-2H-1-benzopyran-2,5-diones 1–3 and 14 with some phenylhydrazines and heterocyclic hydrazines to 5-hydrazono-2H-1-benzopyran-2-ones 4–12 and 15–16 is described. Under more severe conditions the hydrazonoquinoline derivative 17 was obtained from the benzopyran derivative 3 and Phenylhydrazine.     

N-monosubstituted 6-Aminomethylene-5-oxo-2-phenyl-5,6,7,8-tetrahydroquinazolines

We have obtained the corresponding N-monosubstituted 6-aminomethylene-5-oxo-2-phenyl-5,6,7,8-tetrahydroquinazolines by transamination of 6-dimethylaminomethylene-5-oxo-2-phenyl-5,6,7,8-tetrahydroquinazoline with histamine, tryptamine, 3-(1-imidazolyl)- and 3-(4-morpholyl)-propylamines, 4-amino-1-benzylpiperidine, 2-(1-naphthylamino)ethylamine, 2-pyridylmethylamine, 4-chlorobenzylamine, ethanolamine, 1-aminoadamantane, remantadine, 2-aminodimedone, aniline, 3-trifluoromethylaniline, 4-aminoantipyrine, 2-aminobenzimidazole, 2-amino-5-methylbenzothiazole, 7-amino-4-methylcoumarin, 1-amino-4-methylpiperazine, 2-(2-aminophenyl)benzimidazole, 3-(4-aminophenylamino)-2-cyano-5,5-dimethylcyclohex-2-en-1-one, and 3-amino-2-(2-hydroxyethyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1230–1235, August, 2005.     

2-羟基-5,6,7,8-四氢-5,8-亚甲基喹啉-3-羧酸的合成

5,6,7,8-四氢喹啉及衍生物是医药和农药的重要中间体。2-羟基-5,6,7,8-四氢-5,8-亚甲基喹啉-3-羧酸是合成HIF脯氨酰羟化酶抑制剂的重要中间体,其合成方法目前无文献报道。本文以降冰片烯为起始原料,经水合、氧化、缩合、环合和水解5步反应合成目标产物,总收率43.09%,结构经¹H NMR、 ¹³C NMR和MS确证。该路线具有原料廉价易得、操作简单、后处理方便且收率较高等优点,适合工业化生产。