5-丁基-9-苯基-4,5,6,9-四氢苯并[d.e]噁唑[5,4-g]-异喹啉-4,6-二酮的合成

本文给出了一条较好的制备5-丁基-9-苯基-4,5,6,9-四氢苯并[d.e]吣唑[5,4-g]-异喹啉-4,6-二酮的反应路线,即:先由4-溴-1,8-萘酐经亚胺化、硝化、水解和还原等反应制得N-丁基-3-硝基-4羟基-1,8萘酰亚胺,再在硼酸的存在下,将亚胺与苯甲酰氯反应可得到目标化合物。文中给出了该化合物的质谱、核磁共振、红外、紫外和荧光等光谱数据。     

2-[2-(4, 6-二甲基)-嘧啶基]-4-苯基-1, 2, 4-恶二唑烷-3, 5-二酮的合成

异氰酸苯酯和N-[2-(4, 6-二甲基)-嘧啶基]-羟胺(5)反应生成1-[2-(4, 6-二甲基)-嘧啶基]-1-羟基-3-苯基脲(6)。化合物(6)在三乙胺存在下和氯甲酸乙酯反应生成2-[2-(4, 6-二甲基)-嘧啶基]-4-苯基-1, 2, 4-恶二唑烷-3, 5-二酮(1)。     

4-羟基偶氮苯与6-氯-5, 12-萘并萘醌反应产物的NMR分析

无水碳酸钾存在下6-氯-5, 12-萘并萘醌与4-羟基偶氮苯在干燥DMF中反应的主要产物在某些反应条件下不是6[4-(苯基偶氮基)苯氧基]-5, 12-萘并萘醌(1)。该未知反应产物2经核磁共振方法研究证实是6-(N, N-二甲氨基)5, 12-萘并萘醌。本文对化合物2的1H-和13C化学位移、偶合信息和结构作了详细归属, 并推测其反应进程, 实验结果表明, 化合物2是由化合物1与溶剂DMF反应生成。     

酰氨基硫脲及其相关杂环衍生物的研究II.1-[5-(α-萘)-2H-四唑-2-乙酰[-4-苯基氨基硫脲及其相关环衍生物的合成

本文合成了1-[5-(α-萘)-2-H-四唑2-乙酰]-4-苯基氨基硫脲5,以及由5衍生的环化产物3-[5-(α-萘)-2H-四唑2-甲撑]-4-苯基-1,2,4-三咪啉-5-硫酮6,2-苯胺基-5-[5-(α-萘)-2H-四唑-2-甲撑]-1,3,4-噻二唑7及2-苯胺基-5-[5-(α-萘)-2H-四唑-2-甲撑]-1,3,4-二唑8.它们的结构均通过元素分析,红外光谱,核磁共振及质谱鉴定.其药理实验正在进行中.初步实验表明,5及6对小麦生长有较强的促进作用.     

2, 5-二[2'-(4'-氯代苯氧乙酸)基]-1, 3, 4-噻二唑的合成

通过对称双酰肼与P2S5的缩合反应合成2, 5-二-羟苯基-1, 3, 4-噻二唑。并由此制备了2, 5-二[2'-(4'-氯代苯氧乙酸)基]-1, 3, 4-噻二唑及其相关化合物, 同时测定了它们的生物活性。     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

1，4-双{2-[4-[2-苯并恶唑)苯基]乙烯基}苯及衍生物的合成

通过Wittig-Horner反应，以对苯二甲醛和2—(4-氯甲基苯基)苯并恶唑为主要 原料，合成了八个新型1，4-双{2-[4-(2—苯并恶唑)苯基]乙烯基}苯及衍生物．通 过IR，^1H NMR,UV-vis和元素分析等方法确认了它们的化学结构，分析数据表明各 标题化合物分子结构中的C=C双键均为反式结构特．     

含混合价态钒的晶体[N(CH3)4]4[H5PMo5V9O42]·3.5H2O的合成与结构

含有钒和钼的化合物在催化、抗病毒药物、功能材料等领域具有广阔的应用前景 [1～ 4 ] .近年来 ,钒取代的杂多化合物或金属 -氧簇的合成与表征已引起人们的广泛关注 ,许多新的化合物已被合成 ,如含五价钒的化合物 K7[Mo8V5O4 0 ]· 8H2 O和 Na3[VMo12 O4 0 ]· 1 9H2 O[5,6 ] ,含有混合价态钒的簇阴离子[( V V Mo10 ) VO4 0 ]6 - 和 [Mo8V V4 O4 0 ]8- 的化合物 [7,8] ,含双帽 Keggin 结构的簇阴离子[PMo6 VMo6 O4 0 ( V O) 2 ]5- 和 [PMo8V 4 V 2 O4 2 ]5- 的化合物 [9,10 ] 等 ,但所报道的含混合价态钒的 V- Mo化合物中含…     

2',5'-二氢-1'H-吡咯骈[3',4':1,2][60]富勒烯衍生物的合成

以甘氨酸乙酯盐酸与取代的苯甲醛为原料,制得了一系列亚胺,然后用亚胺与C~6~0反应,得到带有不同取代基的吡咯烷骈[60]富勒烯衍生物.经^1HNMR,^1^3CNMR,FT-IR,UV-vis以及TOF-SMS等方法对所得化合物结构进行了表征,并进行了产物的生物活性测试。     

6-羟基富烯及环戊二烯并[d]哒嗪的合成

本文以6, 6-二烷基富烯与烯丙基格氏试剂反应所得的取代环戊二烯基负离子与芳酰氯反应, 合成了5个新的6-羟基富烯化合物(1-5)。用此化合物与肼反应, 合成了5个新的环戊二烯并[d]哒嗪化合物(6-10)。通过^1H NMR、IR及元素分析确定了它们的结构。     

面包酵母对1, 4, 4α, 8α-四氢-1, 4-亚甲基萘-5, 8-二酮的催化异构化

文章描述了面包酵母将1, 4, 4α, 8α-四氢-1, 4-亚甲基萘-5, 8-二酮催化异构化为1, 4-二氢-5, 8-二羟基-1, 4-亚甲基萘, 而不是还原为相应的羟基化合物。     

Synthese von Tricyclo[4.4.1.13, 8]dodecan-4, 9-dion und Tricyclo[4.4.1.13, 8]dodeca-4, 9-dien

Treatment of 2, 6-bis-aminomethyladamantane-2, 6-diol (II) with nitrous acid gives tricyclo[4.4.1.1^{3, 8}]dodecane-4, 9-dione (III), which is converted into the tricyclo[4.4.1.1^{3, 8}]dodeca-4, 9-diene (V) by reduction to the corresponding diols (IV, R = H) and pyrolysis of their O-4-methylphenyl thiocarbonate O-esters. II is accessible from 2, 6-adamantanedione by reaction with diethyl aluminium cyanide and subsequent reduction with lithiumaluminium hydride. The physical properties of the new compounds including ¹³C NMR. spectra of III, V and tricyclo-[4.4.1.1^{3, 8}]dodecane are given.     

3,3,6,6-四甲基-4a-羟基-9-邻甲氧基苯基-1,8-二氧代-2,3,4,4a,5,6,7,8,9,9a-十氢化-1H-氧杂蒽的合成和晶体结构

标题化合物C24H30O5是由邻甲氧基苯甲醛与5，5-二甲基-1，3-环己二酮在N，N-二甲基甲酰胺中反应而得。结构通过单晶X-射线衍射法确定，其晶体属于单斜晶系，空间群C2／c，a=33．942（6），b=7273（1），c=22667（4）A，β=128．989（9）°，Mr=398．50，V=4349（1）A3，Dc=1．2179·cm-3，Z=8，μ（MoKa）=840mm－1，F（000）=1712。晶体结构用直接法解出，经用全矩阵最小二乘法对原子参数进行修正，最后的偏离因子为R=0.043，Rw=0．052。在晶体结构中，存在一个分子间氢键。     

SYNTHESIS AND CRYSTAL STRUCTURE OF A MOLYBDENUM-COPPER-SULFUR CLUSTER COMPLEX WITH DITHIOBENZOATE LIGAND [Bu_4N]_2[MoCu_2S_4(C_6H_5CS_2)_2]

<正> The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021 (6), b = 17.045(8), c=17. 136(7)(?) , α=110.05(3), β=108.64(4), γ=103.87 (4)°, V = 2873(3)(?)3, Dc=1. 321gcm-3, Z = 2. The structure was refined to R = 0. 065 for .4783 reflections. The anion of the title compound can be described as a MoS42- tetrahedron coordinated by two [Cu(C6H5CS2)] units with the three metal atoms lying on a line. The coordination number of each Cu atom is three.     

异苯并二氢吡喃并吡唑类化合物的合成

本文通过异苯并二氢吡喃酮-4的克莱森缩合反应得β-二酮衍生物, 并由此合成出一系列标题化合物。所合成的新杂环化合物均经核磁共振光谱, 红外光谱及元素分析证明其分子结构。     

Studies on quinazolinones. 2. Synthesis of 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-oxazolo[2,3–6]quinazolin-5-one and -2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one

To search for novel antihypertensive heterocycles in the condensed quinazoline series, two representative compounds were synthesized via a suitable reaction sequences. Treating anthranilonitrile with allyl isocyanate gave 2-(allylureido)benzonitrile ( 10 ) in a quantitative yield. Compound 10 was cyclized to 3-allylquinazoline-2(1H, 4(3H)-dione ( 11 ). Bromination of 11 in carbon tetrachloride converted it into the corresponding 3-(2,3-dibromopropyl) derivative ( 12 ) in 92% yield. Ring closure of 12 was effected by the action of alkali to afford 2-bromomethyl-2,3-dihydro-5H-oxazolo[2,3-b]quinazolin-5-one ( 13 ). The title compound, 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-oxazolo[2,3-b]quinazolin-5-one ( 7 ) could be obtained by a reaction of either 12 or 13 with 1-benzylpiperazine respectively. Starting from the readily available 3-allyl-2H-thioxoquinazolin-4(3H)-one ( 16 ) via the analogous reactions gave the 2-bromomethyl-2,3-dihydro-5H-thiazolo[2,3-b]-quinazolin-5-one ( 19 ) in good yield. However, the reaction of 19 with 1-benzylpiperazine provided another target compound, 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one ( 8 ) only in poor yield (8%). As major product, the dehydrobrominated compound, 2-methylene-2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one ( 22 ) was isolated. A preliminary pharmacological evaluation revealed that both compounds 7 and 8 are devoid of the antihypertensive activity.     

Cyclization reactions of 3-hydrazino[1, 2, 4]triazino[5, 6-b]indole

The reaction of 3-hydrazino[1, 2, 4]triazino[5, 6-b]indole I with nitrous acid affords the azide III which could be cyclized with acetic anhydride to 10-acetyl-10H-tetrazolo[5′,1′:3, 4][1, 2, 4]triazino[5, 6-b]indole IIb . Cyclization reactions of I with acetic anhydride, ethyl chloroformate, carbon disulphide and aromatic aldehydes to the corresponding fused triazolo derivatives V–VIII are reported. On the other hand cyclization reactions of I with malononitrile, ethyl cyanoacetate, ethyl acetoacetate and acetylacetone to the corresponding condensed pyrazolino derivatives IX–XI are also reported. The reaction of I with α-dicarbonyl compounds to form mono and dihydrazones are reported. The structure of the compounds prepared and their cyclization mechanisms are reported.     

Synthesis of 4H-1,3,4-oxadiazino[5,6-b]quinoxalines from 2-substituted quinoxaline 4-oxides

The reaction of 6-chloro-2-(1-methylhydrazino)quinoxaline 4-oxide 8 with acetic anhydride resulted in the intramolecular cyclization to give 8-chloro-2,4-dimethyl-4H-1,3,4-oxadiazino[5,6-b]quinoxaline 7a , while the reaction of compound 8 with acetic anhydride/pyridine or acetic anhydride/acetic acid afforded 3-(2,2-diacetyl-1-memymydrazmo)-7-chloro-2-oxo-1,2-dihydroquinoxaline 9 , effecting no intramolecular cyclization. The reaction of 2-(2-acetyl-1-methylhydrazino)-6-chloroquinoxaline 4-oxide 10a or 6-chloro-2-(1-methyl-2-trifluoroacetylhydrazino)quinoxaline 4-oxide 10b with phosphoryl chloride provided compound 7a or 8-chloro-4-memyl-2-trifluoromethyl-4H-1,3,4-oxadiazino[5,6-b]quinoxaline 7b , respectively. The reaction of compound 7b with phosphorus pentasulfide gave 7-chloro-3-(1-methyl-2-trifluoroacetylhydrazino)-2-thioxo-1,2-dihydroquinoxaline 11 , whose dehydration with sulfuric acid in acetic acid afforded 8-chloro-4-methyl-2-trifluoromemyl-4H-1,3,4-thiadiazino[5,6-b]quinoxaline 12 .     

Facile synthesis of 5, 6, 7, 8-tetrahydropyrimido [4, 5-b]-quinoline derivatives

2-Amino-4-phenyl-5,6,7,8-tetrahydroquinoline-3-carbonitrile (3) was synthesized by treating cyclohexanone (1) with 2-benzylidenemalononitrile (2) in the presence of ammonium acetate. The reactivity of compound 3 towards dimethylformamide dimethyl acetal (DMF-DMA), carbon disulfide, urea, thiourea, formamide, formic acid, acetyl chloride and isothiocyanate were studied. In addition, the antimicrobial activity of some selected derivatives is reported.