经由胂叶立德立体有择合成仿保幼激素──增丝素（ZR—512）…

３－甲基－２－丁烯酸乙酯４经ＳｅＯ２反式氧化，还原，溴化得到关键中间体４－溴－３－甲基－（２Ｅ）－丁烯酸乙酯７．７与三苯基胂反应生成季Ｓｅｎｇ盐８。二氢香茅醛与８在Ｋ２ＣＯ３－乙醇－微量水的存在下反应，得到（２Ｅ，４Ｅ）－３，７，１１－三甲基－２，４－十二碳二烯酸乙酯１ａ及其（２Ｚ，４Ｅ）－异构体１ｂ，产率７４％，该反应具有（４Ｅ）－立体选择性，同时Ｃ－２双键发生部分构型转化。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

新型四胺大环锌（Ⅱ）配合物的晶体结构

１，４，７，１０－四氮杂环十二烷（ｃｙｃｌｅｎ）与２－氯甲基吡啶反应获得新型八齿配体１，４，７，１０－四（２－甲基吡啶基）－１，４，７，１０－四氮杂环十二烷（Ｌ）。该配体与Ｚｎ（ＣｌＯ＿４）＿２在水溶液中反应生成无色晶体ＺｎＬ（ＣｌＯ＿４）＿２（１）。晶体结构测定表明：化合物１，Ｃ＿３２Ｈ＿４０－Ｃｌ＿２Ｎ＿８Ｏ＿８Ｚｎ，属单斜晶系，空间群Ｐ２＿１／ｃ，α＝９．８２２（５），ｂ＝１０．７２１（３），ｃ＝３３．９００（２）Ａ，β＝９０．５４（４）°，Ｖ＝３５７０（４）Ａ３，Ｄ＿ｃ＝１．４９ｇ／ｃｍ￣３，Ｚ＝４，Ｆ（０００）＝１６６４，Ｍｒ＝８０１．０。１８８８个可观测衍射点参与修正，Ｒ＝０．０６９，Ｒｗ＝０．０７２。在化合物１中，Ｚｎ原子采取六配位的变形八面体构型，在４个吡啶侧臂之中，只有相对的两个参与配位，而另外的两个有一个远离配位中心，另一个吡啶上的氮原子与锌原子之间存在因二级化学键而引起的弱相互作用。     

2－氯／2－甲磺酰基－5－（2－苯基－4－喹啉基）－1，3，4－噁二唑化合物的合成及其亲核取代的研究

借处理２－羟基－５－（２－苯基－４－喹啉基）－１，３，二唑同ＰＣｌ＿５／ＰＯＣｌ＿３之间的反应合成了２－氯－５－（２－苯基－４－喹啉基）－１，３，４－二唑（３）和通过２－基－５－（２－苯基－４－喹啉基）－１，３，４－二唑的甲基化，然后氧化制得２－甲磺酰基－５－（２－苯基－４－喹啉基）－１，３，４－二唑（６）．并分别研究了３和６同胺、叠氮及肼的反应，得到２，５－二取代的二唑新衍生物．初步观察了部分化合物的抗菌活性．     

三环己基锡O，O＇－二（4－氯苯基）二硫代磷酸酯和二丁基锡双［O，O＇－二（4－甲基苯基）二硫代磷酸酯］的分子和晶体结构

三环己基锡Ｏ，Ｏ＇－二（４－氯苯基）二硫代磷酸酯（Ⅰ），Ｃ＿（３０）Ｈ＿（４１）Ｃｌ＿２Ｏ＿２ＰＳ＿２Ｓｎ，Ｍ＿ｒ＝７１８．３６，单斜晶系，Ｐ２＿１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５（１），ｃ＝２２．９８７（３），β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ·ｃｍ￣（－３），Ｒ＝０．０６３；二丁基锡双［Ｏ，Ｏ＇－二（４－甲基苯基）二硫代磷酸酯］（Ⅱ），Ｃ＿（３６）Ｈ＿（４６）Ｏ＿４Ｐ＿２Ｓ＿４Ｓｎ，Ｍ＿ｒ＝８５１．６６，单斜晶系，Ｐ２＿１／ｃ，ａ＝１２．２８４（４），ｂ＝９．８０７（１），ｃ＝３４．４７１（８），β＝９９．０２（２）°，Ｚ＝４，Ｄ＿ｃ＝１．３７９ｇ·ｃｍ（－３），Ｒ＝０．０４２。化合物Ⅰ具有单分子的四配位变形四面体结构。其Ｓｎ－Ｓ（１）键长为２．５０１（２）；而Ｓｎ与Ｓ（２）的原子间距则为３．５９７；化合物Ⅱ具有单分子的六配位变形八面体结构，其Ｓｎ－Ｓ（１），Ｓｎ－Ｓ（２），Ｓｎ－Ｓ（３）和Ｓｎ－Ｓ（４）的键长分别为２．４９５（３），２．４９３（２），３．２４４（４）和３．２２８（３）。     

稀土（Ⅲ）（4＇－溴－5＇－硝基苯并－15－冠－5）配合物的制备与表征

在乙腈和丙酮介质中合成了６种轻稀土硝酸盐与４＇－溴－５＇－硝基苯并－１５－冠－５（Ｌ）的固体配合物，经元素分析确定其组成为ＲＥ（ＮＯ＿３）＿３·Ｌ（ＲＥ＝－Ｌａ～Ｎｄ），Ｓｍ（ＮＯ＿３）＿３·Ｌ·Ｈ＿２Ｏ和Ｅｕ（ＮＯ＿３）＿３·Ｌ·ＣＨ＿３ＣＮ·４Ｈ＿２Ｏ，并进行了ＩＲ、ＵＶ、ＴＧ－ＤＴＡ、摩尔电导及Ｘ－射线粉末衍射物相分析等表征，探讨了冠醚苯基上引入双取代基（－Ｂｒ，－ＮＯ＿２）后对稀土离子配位作用的影响．     

4－氨基－3，5－二甲基－1，2，4－三唑水杨亚胺合铜〔Ⅱ〕配合物合成及其单晶结构

４－氨基－３，５－二甲基－１，２，４－三唑（ＴＺ）与水杨醛缩合形成４－（邻羟苯基亚甲基）－亚胺－３，５－二甲基－１，２，４－三唑Ｓｃｈｉｆｆ碱（ＳＡＴＺ），该Ｓｃｈｉｆｆ碱与Ｃｕ（ＣｌＯ＿４）＿２·６Ｈ＿２Ｏ形成配合物Ｃｕ（ｓａｔｚ）＿２·６Ｈ＿２Ｏ，分子式为Ｃ＿（２２）Ｈ＿（２２）ＣｕＮ＿８Ｏ＿２·６Ｈ＿２Ｏ。经Ｘ射线晶体结构分析表明，晶体属于单斜晶系，空间群Ｐ２＿１／ｃ，Ｚ＝２，α＝８．２０２（１），ｂ＝１９．５６９（４），ｃ＝８．９７２（８）Ａ，β＝１０７．７２°（２），Ｖ＝１３７１．８（５）Ａ３，Ｄｃ＝１．４６ｇ／ｃｍ￣３，μ＝０．８５３ｍｍ￣（－１），Ｆ（０００）＝６３０，Ｒ＝０．０５１，Ｒ＿ｗ＝０．０６２。分子中２个偶氮甲碱（－Ｃ＝Ｎ－）中　　　的Ｎ原子及２个酚氧原子与中心Ｃｕ原子形成规则的菱形平面结构。     

μ－4，4＇－联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４＇－联吡啶为桥联配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·２Ｈ＿２Ｏ（１）、［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３］（ｂｐｙ）＿３］（ＣｌＯ＿４）＿６·Ｈ＿２Ｏ（２）和［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ＮＯ＿２－ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·６Ｈ＿２Ｏ（３）。经元素分析、电导、ＩＲ、电子光谱、ＥＳＲ、磁化率等方法进行了表征，推定该配合物具有以４，４＇－联吡啶为扩展桥的结构。利用Ｈｅｉｓｅｎｂｅｒｇ模型求得交换参数Ｊ值为－０．２３ｃｍ－１（１）和－０．９０ｃｍ－１（３），表明配合物中金属离子间仅有很弱的反铁磁交换作用．     

铜（Ⅱ）－聚丙烯酰胺和铜（Ⅱ）－聚乙烯醇配位聚合物的配位数

配位聚合物ＰＡＡｍ－ＣｕＣｌ＿２和ｃｕＣｌ＿２·２Ｈ＿２Ｏ的Ｃｕ￣（２＋）２ｐＸＰＳ谱上都有Ｓｈａｋｅ－ｕｐ峰，其与各自的Ｃｕ￣（２＋）２ｐ３／２肩峰或主峰距离ΔＥｓ２或ΔＥｓ分别为８．７和８．６ｅＶ；但配位聚合物Ｃｕ（Ⅱ）－ＰＶＡ却无此峰．由此推定，前者的Ｃｕ￣（２＋）是以ｓｐ￣３杂化轨道接受ＰＡＡｍ４个链节单元Ｃ－Ｎ上Ｎ的孤对电子部分转移形成配位键；而Ｃｕ（Ⅱ）－ＰＶＡ配位聚合物中的Ｃｕ￣（２＋）却以ｄｓｐ￣２杂化轨道接受ＰＶＡ４个链节单元侧基Ｏ的孤对电子部分转移，产生配位键，即Ｃｕ￣（２＋）与ＰＡＡｍ或ＰＶＡ的链节单元配位比均是１：４，此结果与电导率法测定ＰＡＡｍ－ＣｕＣｌ＿２的配位比相同．     

2—取代—1,7—二氧螺（4.4）壬—8—酮的合成研究

分别用Ｋ２ＣＯ３，１，５－二氮双环（４．３．０）壬－５－烯（ＤＢＮ）和四丁基氟化铵（ＴＢＡＦ）等碱催化３－（３－羟基丙基）－γ－丁烯酸内酯的分子内Ｍｉｃｈｅａｌ加成反应合成了２－取代－１，７－二氧螺（４．４）壬－８－酮     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Enamine chemistry—XVIII: The formation of hexahydrochromane-8a-amines by reductive cyclisation of enamines

Enamines (1) derived from cyclohexanone or cyclopentanone are reacted with electrophilic olefins (ethyl acrylate, ethyl 2-methylacrylate, ethyl 2-butenoate) to give the new enamines, 2. When 2 is reacted with LiAlH₄, reductive cyclisation takes place giving hexahydrochromane-8a-amines of octahydrocyclopentapyrane-7a-amines, 3, in quantitative yields. 3 is hydrolyzed with dilute aqueous hydrochloric acid to hexahydrochromane-8a-ols of octahydrocyclopentapyrane-7a-ols (4) and reacts also with oxalic acid in refluxing dioxane to form the condensed dihydropyranes, 5.     

Stereospecific substitution of enantiomerically pure 1-(2-pyridinyl)ethyl methanesulfonate with beta-dicarbony compounds

The alkylation of the sodium salt of the malonic acid diester with (R)-1-(2-pyridinyl)ethyl methanesulfonate (2) gave the dimethyl (R)-[1-(2-pyridinyl)ethyl]malonate (3a), stereospecifically. The alkylation reaction of methyl acetoacetate gave the methyl (2'S,2R/2S)-3-oxo-2-[1-(2-pyridinyl)ethyl]butanoate (3d) along with the methyl (S)-3-[1-(2-pyridinyl)ethoxy]-2-butenoate (4d). The acid hydrolysis and decarboxylation of 3d under acidic conditions gave (R)-4-(2-pyridinyl)pentan-2-one (6), and the alkylation of methyl (R)-[1-(2-pyridinyl)ethyl]acetoacetate with benzyl bromide gave a mixture of C-benzylated and O-benzylated products 7 and 8.     

冠醚苯并恶唑菁染料的合成

本文报道含冠迷苯并恶唑菁染料及半菁染料的合成,采用一种简便方法合成了关健中间体2-甲基6,7-二羟基苯并恶唑:从2,3,4-三羟基苯乙酮肟经beckmann重排而得到,将它再与三甘醇或四甘醇二氯化物反应 ,分别得到相应的冠醚化合物:2-甲基-6,7-并(12-冠-4)苯并恶唑和2-甲基-6,7-并(15-冠-5)苯并恶唑,将它们制成相应的季铵盐 ,然后分别与原甲酸乙酯或对二甲胺基甲醛作用,得到相应的冠醚恶唑菁染料,或半菁染料.     

Expeditious photochemical reaction toward the preparation of substituted chroman-4-ones

A facile photochemical preparation of 5-, 6-, and 7-substituted chroman-4-ones from aryl 3-methyl-2-butenoate esters is described. The two-phase base-catalyzed method relies upon two consecutive processes in one-pot reaction through a photo-Fries rearrangement and a based-catalyzed intramolecular oxa-Michael addition to afford the desired products.     

Synthesis of New Pyrido[4″,3″:4″,5″]thieno[2″,3″:4,5]pyrimido[2,1-b][1,3,4]thiadiazine Derivatives

Ethyl 2-methyl-11-oxo-9, 10-dihydro-1 H , 11 H -pyrido[4",3":4',5']thieno[2',3':4,5]pyrimido[2,1-b][1,3,4]thiadiazine-8(7 H )-carboxylate 7 has been synthesised by the reaction of ethyl 3-amino-4-oxo-2-thioxo-1,3,4,5,6,8-hexahydropyrido[4',3':4,5]thieno[2,3-d]pyrimidine-7(2 H )-carboxylate 2 with allylbromide followed by treatment with bromine and subsequent dehydrobromination of the brominated product 5 with ethanolic sodium hydroxide. Its isomeric ethyl 2-methyl-11-oxo-9,10-dihydro-3 H ,11 H -pyrido[4",3Prime;:4',5']thieno[2',3':4,5]pyrimido[2,1-b][1,3,4]thiadiazine-8(7 H )-carboxylate 8 has been obtained by condensation of 2 with chloroacetone followed by cyclization of the intermediate 9 with p -toulenesulfonic acid. The thiadiazino derivatives 11 , 13 , 15 were prepared through the reaction of 2 with the appropriate f -halocarbonyl compounds followed by cyclization reactions of the intermediates 10 , 12 , 14 .     

3,5—二甲氧基苯乙醛和丙二酸单乙酯的Knoevenagel缩合

从３,５－二甲基苯乙醛和丙二酸单乙酯的Ｋｎｏｅｖｅｎａｇｅｌ缩合反应得到２个产物,其一经证实是重排生成的４－（３,５－二甲氧苯基）－３－丁烯酸乙酯,另一个是２＇,４＇,２″,４″－四甲氧基－２,３：６,７－二苯并－９－氧杂双环［３．３．１］壬－２,６－二烯。经元素分析、ＩＲ、ＮＭＲ、ＭＳ、和Ｘ射线衍射证实前者不发生可逆重排为其２－烯酸酯异构体的反应。     

Phospha-Michael additions to activated internal alkenes: steric and electronic effects

The addition of P(O)-H bonds to internal alkenes has been accomplished under solvent-free conditions without the addition of a catalyst or radical initiator. Using a prototypical secondary phosphine oxide, a range of substrates including cinnamates, crotonates, coumarins, sulfones, and chalcones were successfully functionalized. Highly activated acceptors such as isopropylidenemalononitrile and ethyl 2-cyano-3-methyl-2-butenoate underwent the phospha-Michael reaction upon simple trituration of the reagents at room temperature, whereas less activated substrates such as ethyl cinnamate and methyl crotonate required heating (>150 °C) in a microwave reactor to achieve significant consumption of the starting alkenes. For the latter alkenes, a competing reaction involving disproportionation of the ditolylphosphine oxide into ditolylphosphinic acid and ditolylphosphine was observed at the high temperatures needed to promote the addition reaction.     

A novel pentacyclic pyridine dilactone. 7-methyl[1]benzopyrano[4,3-d][1]benzoxacino[4,3-b]pyridine-6,16-dione

When equimolar quantities of salicylaldehyde 2 and ethyl 3-amino-2-butenoate 3 or its constituents (ethyl 3-oxobutanoate and ammonia) were refluxed on a steam-bath for 6 hours with a trace of acetic acid, two products, a pentacyclic pyridine dilactone 4 and 3-acetyl coumarin 5 , resulted in 15% and 45% yields, respectively. The structure of 4 was elucidated as 7-methyl[1]benzopyrano[4,3-d][1]benzoxacino[4,3-b]-pyridine-6,16-dione on the basis of its spectral data. The mechanism of its formation has been discussed. The reaction has been extended to three more substituted salicylaldehydes.     

Synthesis and Some Transformations of Ethyl 5-Alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates

Michael reaction of ethyl 5-alkoxymethyl-2-oxotetrahydrofuran-3-carboxylates with 3-methyl-3-buten-2-one gave ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates. Alkaline hydrolysis of the latter, followed by decarboxylation afforded 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)tetrahydrofuran-2-ones. The bromination of ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates provides a convenient method for the preparation of 3-acetyl-8-alkoxymethyl-3-methyl- and 8-alkoxymethyl-3-bromoacetyl-3-methyl-2,7-dioxaspiro[4.4]nonane-1,6-diones in high yields.