邻硝基苯甲醛的间接电解合成研究

对硫酸钴（Ⅱ）电化学制备以及用其作氧化媒质合成邻硝基苯甲醛进行了研究，结果表明，在１１℃以银离子作催化剂，用Ｐｂｏ２／Ｐｂ作阳极，在含０．４５ＭＣｏＣＯ４的５．３Ｍ硫酸溶液中进行电解反应时，可获得较高的电流效率，在温度１２℃９．２Ｍ硫酸溶液中，使用过量７０倍的邻硝基甲苯进行化学合成时，邻硝基苯甲醛的收率在７４．５％。     

3-甲基-3-乙酰基-4-乙氧甲酰-环己酮的合成

3-甲基-3-乙酰基-4-乙氧甲酰-环己酮的合成;甲基乙酰基乙氧甲酰环己酮;甲基乙氧甲酰环己烯酮;硝基乙烷;甲基硝基乙基乙氧甲酰环己酮;氟化四丁基铵;三氯化钛     

3,4-二甲氧基-6-氨基苯甲醛的合成

以藜芦醛为原料合成4,5-二甲氧基-2-硝基苯甲醛,经铁粉还原后高产率地得到了3,4-二甲氧基-6-氨基苯甲醛。     

N-乙酰基-3,3-二硝基氮杂环丁烷的合成

多硝基氮杂环丁烷及其衍生物因其四元杂环所具有很高的环张力能,赋予这类化合物优良的爆轰性能,从而成为一类重要的高能量密度材料,其中1,3,3-三硝基氮杂环丁烷(TNAZ)成为最具有应用前景的含能材料之一。N-乙酰基-3,3-二硝基氮杂环丁烷(ADNAZ),为白色或无色晶体,可溶于丙酮,二氯甲烷等有机溶剂。     

2-溴-4-甲基苯酚的合成

2-溴-4-甲基苯酚是合成许多药物及广谱型香料香兰素的重要中间体。常温下,以对甲基苯酚为原料加溴易生成2,6-二溴-4-甲基苯酚,本文在原来工作的基础上,在低温下,通过溴化氧化一步直接合成了2-溴-4-甲基苯酚,产率可达93％并通过红外光谱和核磁共振谱对产物结构进行确证。反应的最佳条件是：反应温度为-5～-10℃,反应时间为4h,搅拌速度为1000r／min,对甲基苯酚与双氧水物质的量比为1：0．85。反应方程式如下：     

4-甲基-2-硝基苯胺常压液相漆原镍催化加氢制备4-甲基邻苯二胺

甲基硝基苯胺;4-甲基-2-硝基苯胺常压液相漆原镍催化加氢制备4-甲基邻苯二胺     

2,5-二溴-4-硝基咪唑的合成

以咪唑为原料,经硝化和溴化反应合成了抗炎药物中间体——2,5-二溴-4-硝基咪唑,总收率80.3%,其结构经1H NMR和IR确认。     

2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐的合成、结构及性质的研究

在胺存在下,3,7-二硝基二苯并溴五环硫酸氢盐与二甲基亚砜反应生成2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐(3).3的X射线晶体结构分析数据表明其分子具有内盐结构但酚氧负离子的负电荷是部分离域的,分子内两苯环所成的两面角为117.3°.3在熔解时发生重排及热分解分别生成2-溴-2'-甲氧基-3'-甲硫基-4,4'-二硝基联苯(6)及3,7-二硝基-4-甲硫基-二苯并呋喃(7).3与盐酸反应生成相应的锍盐(8).     

2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯的合成

以3-硝基-2-氨基苯甲酸甲酯为原料,经三氟乙酰化、N-烷基化和脱保护反应制得坎地沙坦中间体2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯,其结构经~1H NMR,~(13)C NMR和MS(ESI)确证。     

催化分子氧氧化合成3-甲基-4-硝基苯甲酸

催化分子氧氧化合成3-甲基-4-硝基苯甲酸;液相氧化;二甲基硝基苯;甲基硝基苯甲酸;合成     

Direct Synthesis of 4-Acetyl-1-alkyl-1H-pyrrol-2(5H)-ones from Difunctionalized Allyl Bromide

We describe a simple and efficient protocol for accessing some unsaturated heterocyclic compounds in a direct evaluation of allyl bromide as Z-ethyl 3-bromomethyl-4-oxopent-2-enoate. The latter reacts with primary amines via two successive nucleophilic substitutions followed by a 5-exo-trig cyclization to produce selectively 4-acetyl-1-alkyl-1H-pyrrol-2(5H)-ones in good yields.     

The Oxidation and Reduction of 4-Formyl-and 4-Acetyl-3-Arylsydnones

A convenient method to prepare methyl 3-arylsydnonylacetate (I) from 4-acetyl-3-arylsydnone with thallium (III) nitrate by oxidative rearrangement was investigated. 4-Formyl-3-arylsydnones were reduced by sodium borohydride at room temperature to produce 4-hydroxymethyl-3-arylsydnones (II) in moderate yields (65%-85%), but the corresponding 3-aryl-4-sydnonecarboxaldehyde arylhydrazone (III) was obtained by the electrolytic reduction.     

Synthesis and Molecular Structure of 1-Acetyl-1-（4-iodophenyl）-3-cyclohexylurea

1INTRODUCTION N-acyl urea is an important class of compounds because of their various bioactivities,and they can be used as pesticides[1]and pharmaceuticals[2].On the other hand,many natural products bearing N-acylurea functionality also exhibit the inter…     

Cyclocondensation of 2-Fluoro-5-nitrobenzaldehyde with Amidines. New Synthesis of Isoquinolines

The direction of the cyclocondensation of 2-fluoro-5-nitrobenzaldehyde with five amidines having -hydrogen atoms has been studied. It was established that depending on the structure of the amidine the main products of the reaction may be not only quinazolines but also 3-aminoisoquinolines. A new convenient route has been found for the synthesis of 3-aminoisoquinolines consisting of the cyclocondensation of -acylacetamidines with 2-fluoro-5-nitrobenzaldehyde.     

3－烷基-4-羟基-2-噻唑烷硫酮-4-羧酸乙酯的一锅煮合成

Ethyl 3-alkyl-4-hydroxy-2-thioxothiazolidine-4-carboxylates were prepared in excellent yields from the reaction of corresponding primary amines with carbon disulfide and ethyl 3-bromo-2-oxopropanoate in the presence of anhydrous potassium phosphate in DMF at room temperature within 1 h. The structures of the highly functionalized products were corroborated spectroscopically （IR, ^1H NMR, ^13C NMR, EI-MS） and by elemental analyses. A plausible mechanism for such type of cyclization was proposed.     

Dehydration of 4-hydroxy-4-methyl-3-phenylamino-oxazolidin-2-ones

The dehydration of two 5,5-disubstituted 4-hydroxy-4-methyl-3-phenylaminooxazolidin-2-ones into the corresponding 4-methylene-3-phenylaminooxazolidin-2-ones has been carried out. The structure of the products was confirmed by X-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1512–1517, October, 2004.     

Synthesis of 3-acetyl-2-amino-4-pyridone

A method hxsynthesizing 3-acetyl-2-amino-4-pyyridone has been suggested. The synthesis involves the condensation of dimethylformamide dimethylacetal at the NH₂ group of diphenylboron chelate diacetylketene aminal followed by its intramolecular cyclization under the action of NaOMe in MeOH.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179. January, 1996.     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.