5-氨基-5,6,7,8-四氢-2(1H)-喹啉酮的简便合成

改进了合成5-氨基-5,6,7,8-四氢-2(1H)喹啉酮(5)的方法。以环己二酮为原料,通过亚胺化,Michael反应-环化反应,成肟反应和碱性条件下镍铝合金催化还原共四步反应合成了5,总收率19.6%,其结构经1HNMR,IR和MS确证。     

5-羟基-3,4-二氢异喹啉-1-酮的合成

以异喹啉为起始原料,经成盐、磺化得异喹啉-5-磺酸(3),3与熔融的氢氧化钠和氢氧化钾反应得1,5-二羟基异喹啉(4),以5%Pd-C为催化剂还原4得5-羟基-3,4-二氢异喹啉-1-酮(1),总收率47.6%。1的结构经1H NMR和MS确证。     

6-羟基-3,4-二氢-2(1H)喹啉酮合成新方法

提出了一种以苯胺和3-氯丙酰氯为原料，经环合、硝化、还原、重氮化水解合成目标产物6-羟基-3，4二氢-2(1H)喹琳酮的新方法。此法合成的目标产物产率高，总产率达67％以上。单步产率均在86．5—99．6％之间，反应条件温和。各步产品经MS，1HNMR进行定性及结构表征。     

3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮的合成

以苄胺为原料,经6步反应得到新型抗高血压药OPC-21268的中间体3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮,总收率13．9％．     

2-异丙基-1,3-二氢-4(1H)异喹啉酮及其衍生物的合成

异喹啉酮类化合物具有重要药理活性,本文在合成1,2,3,4-四氢-2-苄基异喹啉酮-4衍生物的基础上,参照Hinton方法制备2-异丙基-1,3-二氢-4(1H)异喹啉酮(1),用(1)进一步与芳醛、羟胺、酰氯及苯肼反应得到了相应的衍生物(3_a-6_e)。     

2-取代-3,4-二氢-1-异喹啉酮的合成及其血管舒张活性

以3-羟基-4,5-亚甲二氧基苯甲酸甲酯或5-羟基-1,3-苯二甲酸二甲酯为原料,经烯丙基醚化、Claisen重排、氧化、与伯胺反应(生成Schiff碱)、还原、分子内酯的酰化合成了4种新的2-取代-3,4-二氢-1-异喹啉酮(1a～1d),其结构经1HNMR和MS表征。离体动脉环张力实验证明1在浓度为1×10-4mol.L-1时具有明显舒张血管的作用。     

2-苄基-1,3-二氢-4-异喹啉酮及其衍生物的合成

本文合成了2-苄基-1,3-二氢-4-异喹啉酮的四种3-位亚甲基取代衍生物，四种氧酰基肟和两种6-苄基-5H-异喹啉并[4,3-b]喹啉衍生物。新化合物的结构经元素分析、红外光谱、核磁共振谱证实。     

1-甲基-3,4-二苯基喹啉-2(1H)-酮的合成和结构表征

以N-甲基苯胺和苯丙炔酸为原料,经过缩合、亲电环化、偶联反应合成了1-甲基-3,4-二苯基喹啉-2(1H)-酮;利用核磁共振谱和气相色谱-质谱表征了产物的结构.结果表明,所用合成方法具有产率高、反应条件温和、操作简单等优点,目标产物的总产率达62.7%.     

1,2,3,4—四氢—2—苄基异喹啉酮—4衍生物的合成

1,2,3,4-四氢-2-取代异喹啉酮-4衍生物中有不少具有重要的药理活性。许多学者进行了这一方面的合成工作。作者根据Hanna等     

6-羟基-3,4-二氢喹啉-1(2H)-羧酸叔丁基酯的合成研究

以6-羟基喹啉为原料,使用钯碳催化加氢和硼氢化钠还原两种方法合成了6-羟基-1,2,3,4-四氢喹啉化合物,考察反应温度与碱性条件对6-羟基-3,4-二氢喹啉-1(2H)-羧酸叔丁基酯合成收率的影响,10℃反应温度下,以碳酸氢钠作碱是合成的最佳反应条件。     

Synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones

An efficient method for the synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones from various 2-dimethylaminomethylidenecyclohexane-1,3-diones, (1,3-thiazol-2-yl)acetonitriles, and dimethylformamide dimethyl acetal was developed. These transformations proceeded through intermediate 2-[2-(4-aryl-1,3-thiazol-2-yl)-2-cyanoethenyl]-3-oxocyclohex-1-en-1-olates. They were isolated as piperidinium salts and used in further heterocyclization reactions with aromatic amines, giving novel 1-aryl-3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones. These compounds were also obtained by preparative three-step “one pot” synthesis under controlled microwave irradiation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 412–417, February, 2008.     

Synthesis,Crystal Structure and Cytotoxic Activities of 1-(Prop-2-yn-1-yl)-7,8-dihydro-1H-benzo[d][1,3]-thiazine-2,5(4H,6H)-dione Derivatives

The important synthetic precursor(Ⅲ), 1-(prop-2-yn-1-yl)-7,8-dihydro-1Hbenzo[d][1,3]thiazine-2,5(4H,6H)-dione(C_(11)H_(11)NO_2S), was prepared through a three-component reaction, which was further transferred into cytotoxic triazoles by alkylation and click synthesis in satisfactory yields of 87%~95%. Their structures were characterized by IR, H-RESI-MS and NMR analysis. Meanwhile, the crystal of Ⅲ was obtained and determined by X-ray single-crystal diffraction. Crystal data: orthorhombic system, space group P2_12_12_1, a = 5.189(4), b = 8.661(6), c = 23.498(17) ?, V = 1056.2(13) ?~3, Z = 4, F(000) = 464, D_c = 1.392 g/cm~3, μ =0.284 mm~(-1), R = 0.0637 and wR = 0.1668 for 8182 independent reflections(R_(int) = 0.1580) and 2166 observed ones(I 2σ(I)).     

Synthesis of novel 5-chloro-2-(thiophen-2-yl)-7,8-dihydroquinoline-6-carboxamides as potent inhibitors of Mycobacterium tuberculosis

A series of novel 5-chloro-2-(thiophen-2-yl)-7,8-dihydroquinoline-6-carboxamides was designed, synthesized, and evaluated for antitubercular activity. The required 5-chloro-2-(thiophen-2-yl)-7,8-dihydroquinoline-6-carboxylic acid intermediate was prepared by oxidizing the respective aldehyde with sodium chlorite and 30% H2O2. Further, the acid was coupled with various aryl, alkyl, and heterocyclic amines using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and hydroxybenzotriazole to give the desired 5-chloro-2-(thiophen-2-yl)-7,8-dihydroquinoline-6-carboxamides in excellent yields. All the new compounds were characterized by their NMR and mass spectral analysis. Screening of all new compounds for in vitro antimycobacterial activity against M. tuberculosis H37Rv (Mtb) resulted in five analogs with MIC 3.12 µg/cm3 as promising antitubercular agents with lower cytotoxicity profiles.     

Synthesis and Crystal Structure of 4-（2-Bromophenyl）-3,4,7,8-tetrahydro- 7,7-dimethyl-1-p-tolylquinoline-2,5（1H,6H）-dione

The title compound 4-（2-bromophenyl）-3,4,7,8-tetrahydro-7,7-dimethyl-1-p-tolylquinoline-2,5（1H,6H）-dione 1 （C24H24BrNO2, Mr = 438.35） was synthesized and characterized by IR, 1H NMR and elemental analysis. The crystal belongs to monoclinic, space group C2/c with a = 27.565（14）, b = 10.079（5）, c = 15.917（8） A,β = 111.059（9）°, Z = 8, V = 4127（4）A3, Dc = 1.411 g·cm^-3,μ（MoKa） = 2.011 mm^-1, F（000） = 1808, the final R = 0.0417 and wR = 0.1032 for 2393 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the pyridine ring adopts a distorted boat conformation, while another six-membered ring takes a half-chair conformation. In addition, there are non-classical hydrogen bonds of C-H…O and C-H…Br in the structure. The short distance （3.481A） between the adjacent 2-bromophenyl rings indicates the existence of π-π interaction.     

Synthesis,X-ray structure,and stevens rearrangement of 1,1-di(prop-2-yn-1-yl)-2,5-dihydro-1H-pyrrol-1-ium bromide

1,1-Di(prop-2-yn-1-yl)-2,5-dihydro-1H-Pyrrol-1-ium bromide was obtained with interaction of 3-pyrroline with propargyl bromide and its structure was studied by X-ray analysis. It has been shown that the Stevens rearrangement of obtaining salt leads to the formation of 1-(hexa-4,5-dien-1-yn-3-yl)-2,5-dihydro-1H-pyrrol.     

Aminomethylation of 6-methyl-1-(thietan-3-yl)pyrimidine-2,4(1H,3H)-dione

Mannich reactions of 6-methyl-1-(thietan-3-yl)pyrimidine-2,4(1H,3H)-dione with formaldehyde and morpholine, piperidine, N-methylpiperazine, and diethylamine gave the corresponding 5-aminomethylsubstituted pyrimidine derivatives. The title compound reacted with excess piperazine to form 3,5-bis-(piperazin-1-yl) derivative, while its reaction with an equimolar amount of piperazine afforded 5,5′-(piperazin-1,4-diylbismethylene)bis[6-methyl-1-(thietan-3-yl)pyrimidine-2,4(1H,3H)-dione].     

Synthesis of [3-(trimethylsilyl)prop-2-yn-1-yl] selenides

Efficient and selective methods have been developed for the synthesis of previously unknown organyl [3-(trimethylsilyl)prop-2-yn-1-yl] selenides, organyl prop-2-yn-1-yl selenides, and bis[3-(trimethylsilyl) prop-2-yn-1-yl] selenide by reactions of 3-bromo-1-(trimethylsilyl)prop-1-yne with the corresponding organylselenolates and sodium selenide generated from diorganyl diselenides or elemental selenium by the action of sodium tetrahydridoborate.     

Synthesis and Structural Studies of 6-（2,5-Dimethyl-1H-pyrrol-1-yl）pyridin-2-amine

6-(2,5-Dimethyl-1H-pyrrol-1-yl)pyridin-2-amine (1) was synthesized and characte-rized by elemental analyses,1H-NMR and 13C-NMR,FTIR,Uv-Vis,mass spectral studies and single-crystal X-ray diffraction.All data obtained from spectral studies support the structural properties of 1.Intermolecular N-H…N hydrogen bonds produce an R22(8) ring.An extensive three-dimensional network formed by C-H…π and N-H…π-facial hydrogen bonds is responsible for the crystal stabilization.The combination of C-H…π interactions produces R33(12),R43(19) and R44(20) rings.