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Part 2. Annulation reaction of 3, 4-dichlorocoumarin (1) and 3, 4-dichloromaleimide (8) by a new general annulation strategy developed in this group with 2-phenylbenzofuran (15), 3-phenylbenzofuran (16), 2, 5-diphenyloxazole (17), 2, 5-diphenylthiazole (18), 2-methyl-4-phenylthiazole (19) and 2, 3-dimethoxy-1, 3-butadiene (40) were investigated.

二。在本课题组前一阶段提出的从二氯代环烯酮与1,1-二芳基乙烯的光化反应以及光化反应中得到的环丁烷产物的连续电环化反应对3,4-二氯马来酰亚胺以及3,4-二氯香豆素进行增环反应的工作基础上,研究了3,4-二氯香豆素(1)和3,4-二氯马来酰亚胺(8)与5个α-苯基取代的环烯烃2-苯基苯并呋喃(15),3-苯基苯并呋喃(16),2,5-二苯基噁唑(17),2,5-二苯基噻唑(18),2-甲基-4-苯基噻唑(19),以及一个丁二烯——2,3-二甲氧基丁二烯(40)进行的芳香族增环反应。

Two haptens of MCPA, 6-[(2-methyl-4-chlor phenoxy aceto amino] hexanoic acid and 4-[(2-methyl-4-chlor phenoxy aceto amino]butanoic acid were synthesized with MCPA and amino-hexanoic acid or amino-butanoic acid.

以除草剂2甲4氯、氯化亚砜、氨基己酸和氨基丁酸等为起始原料,经两步化学反应分别合成了两种MCPA半抗原:6-(2-甲基-4-氯苯氧乙酰基)氨基己酸和4-(2-甲基-4-氯苯氧乙酰基)氨基丁酸。

During the manufacturing of the critical intermediate cephalosporin nucleus --7-amino-3-chloro-cephalosporanic acid diphenylmethyl ester hydrochloride salt, first the feasibility of the one-pot synthetic route of open loop, closed loop and ozonization when chlorine is passed over is qualified by experiments. Then the critical factors that will influence this reaction are studied as follows: the mol ratio of triphenyl phosphite and Diphenylmethyl 3-hydroxy-7-phenylacetaminoceph-3-em-4-carboxylate-l-oxide is four to one; the quantity of the stablizer should be at least more than two to one. The temperature of the system must be 25℃ when chlorine is passed over so that the hydrochloride can be precipitated to obtain cephalosporin nucleus of cefaclor--7-amino-3-chloro-cephalosporanic acid diphenylmethyl ester hydrochloride salt.

在制备关键中间体头孢母核7-氨基-3-氯头孢烷酸二苯甲酯盐酸盐时,先通过实验验证把开环、闭环、臭氧化三步在通入氯气时并为一锅煮的合成路线的可行性之外,又研究了影响该反应的几个重要因素:亚磷酸三苯酯与3-羟基-7-头孢烷-5-亚砜-2-甲酸二苯甲酯的摩尔比为4:1;稳定剂2-甲基-2-丁烯的用量至少大于2:1,通入氯化氢气体时体系温度在25℃时盐酸盐则能够顺利析出,获得头孢克洛的头孢母核—7-氨基-3-氯头孢烷酸二苯甲酯盐酸盐。

Study on an efficient process for the preparation of trifloxystrobin starting from 2-methylacetophenone bypartial oxidation,esterification,reaction with methoxyamine,bromization and condensation with 3'- acetophenone oxime.

以邻甲基苯乙酮为原料,经过高锰酸钾的碱性氧化,甲醇酯化,再与甲氧基胺盐酸盐肟化后,用N-溴丁二酰亚胺溴化,最后和间三氟甲基苯乙酮肟缩合得到目标产物肟菌酯。

Compounds were determined from more than 3 stages, including germacrene D, caryophyllene, phenol, 2, 6-bis (1, 1-dimethylethyl)-4-methyl-,β-elemene,γ-elemene, 1-octanol, 2-butyl-, dibutyl phthalate, cyclohexane, 1-ethenyl-1-methyl-2-(1-methylethenyl)-4(1-methylethylidene)-and butyl caprylate.

其中,3个时期以上能检测到相同的化学成分有9种,分别是大牻牛儿烯D、丁香烯、2,6-二叔丁基-4-甲基苯酚、β-榄香烯、γ-榄香烯、2-丁基-1-辛醇、邻苯二甲酸二丁酯、1-乙烯基-1-甲基-2-(1-甲基乙烯基)-4-(1-甲基亚乙烯基)环己烷和辛酸丁酯。

With benzoic acid, terephthalic acid, 2. 6naphthalene dicarboxylic acid, dimethyl-2, 6-naphthalene dicarboxylate as solutes, water, acetic acid, N, N-dimethylformamide, N, N-dimethylacemide, dimethyl sulphoxide, N-methl2-ketopyrolidine, and the mixture of water and acetic acid as solvents respectively, the solubilities of 15 binary systems and 4 ternary systems were determined.

实验以苯甲酸、对苯二甲酸、2,6-NDCA、2,6-萘二甲酸二甲酯为溶质,以水、醋酸、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮以及水和醋酸的混合溶液为溶剂,测定了十五个二元物系和四个三元物系的溶解度数据。

The copolycondesation type polyamic acid was synthesized by using pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride as the dianhydride monomers, 4,4'-diamino diphenylmethane and 4,4'-oxydianiline as the diamine monomers under microwave irradiation in dimethylformamide.

在N,N'-二甲基甲酰胺溶剂中,以均苯四甲酸酐和3,3',4,4'-二苯酮羧酸二酐为二酐单体,4,4'-二氨基二苯醚和4,4'-二氨基二苯甲烷为二胺单体,采用微波辐射低温溶液共缩聚,合成了聚酰胺酸预聚体,然后亚胺化脱水、环化,生成共缩聚聚酰亚胺。

In order to check the corresponding compound at 31P NMR –45.4 ppm, stable pentacoordinate spirobicyclic 2-phenoxy-1,3-phenylene-dioxo-1,3,2-iminoacetoxyphosphoranes were synthesized through a new and efficient method whereby phosphorus pentachloride was displaced stepwise by catechol, N,O-bisamino acid and phenol, or catechol, phenol and N,O-bisamino acid, their 31P NMR chemical shifts are at about 31P NMR –45.0 ppm, the results showed that the compound 4 at 31P NMR –45.4 ppm was pentacoordinate phosphorane containing amino acid residue.

采用磷谱跟踪来研究上述成肽反应机理。例如在氮气保护下,0.1mmol O,O-亚苯基磷酰氯(1)和0.15mmol N,O-二苯丙氨酸(2)苯溶液加入0.6ml核磁管中,混合均匀,反应过程用磷谱检测。反应1分钟后,起始原料1(δp=19ppm)很快转变成N-磷酰苯丙氨酸的三甲基硅基酯(3)(δp=19.8ppm),在8分钟内,3完全转变成苯丙氨酸磷烷4(δp =-45.4ppm),同时出现环磷三酯(6)(δp=3.5ppm)。随着反应的进行,对应于化合物4的峰逐渐变小,而6逐渐变大。

The stereochemical structures of two new compounds, 5-(3-chlorophenyl)-2-furfur-aldehyde-N-4-methylphenyloxyacetylhydrazone and 5-(3-chlorophenyl)-2-furfuraldehyde-N-4-nitrophenyloxyacetylhydrazone, were determined by DPFGSE-NOE experiments performed in DMSO-d\-6 at 25 ℃ and variable-temperature ~1H NMR The ~1H chemical shifts of the compounds were completely assigned at 25 ℃ and 90

利用变温实验和DPFGSE NOE实验,确定了 5 (3 氯苯基) 2 呋喃甲醛 N 4 甲基苯氧乙酰腙和5 (3 氯苯基) 2 呋喃甲醛 N 4 硝基苯氧乙酰腙两个新化合物25 ℃时在二甲基亚砜中的空间构型,并对这两个新化合物在 25 ℃和 90 ℃时的质子的化学位移进行了全归属。

Two new active esters of acrylic acids monomers, N-p-acryloxybenzoyloxy succini-mide and N-p-methacryloxybenzoyloxy succinimide have been synthesized and polymerized.ABOSu and MBOSu were prepared by coupling of p-acryloxybenzoic acid or p-methacryloxybenzoie acid with N-hydroxy succinimide in the presence of dicyclohexylcarbodimide.

新的丙烯酸活性酯,N-(对甲基丙烯酰氧苯甲酰氧基)丁二酰亚胺及N-丁二酰亚胺单体分别由对甲基丙烯酰氧基苯甲酸、对丙烯酰氧基苯甲酸与N-羟基丁二酰亚胺在环已基羰二亚胺存在下经偶联反应合成。

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然而现在,所有的孩子都要在综合学校继续学习,所以这次考试只是决定他们将要学习哪些课程。

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Detailed Intrinsic Reaction Coordination calculations were carried out to guarantee the optimized transition-state structures being connected to the related tautomers.

同时,做了详尽的内禀反应坐标计算,以保证所得到的过渡态连接相应的始末异构体。