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Finally,the electrocyclic ring-closure of N-vinylic ketenemine and a subsequent tautomerization lead to the formation of isoquinolines or benzoisoquinolines.

3发展了一种芳基叠氮和酰氯的AAB型串联反应,当控制芳基叠氮和酰氯的比例为2∶1时,反应生成N,N\'-二芳基脒类化合物。

Also useful are oil-soluble copper dithiocarbamates of the general formula Rc RdzCu, where z is 1 or 2, and Rc and Rd are the same or different hydrocarbyl radicals containing from 1 to 18, and preferably 2 to 12, carbon atoms, and including radical s such, for example, as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals.

通用化学式为RcRdzCu的油溶性二硫代氨基甲酸铜,也非常有用。式中,z为1或2,Rc和Rd是含有1到18个碳原子(最好含有2-12个碳原子)的相同或不同的烃基根,并且包括烷基、链烯基、芳基、芳烷基、烷芳基和环脂基等。

The first synthetic route uses 1,2,4-trimethoxybenzene and chloroacetonitrile in forming 2,4,5-trimethoxy-a-chlor-acetophenone under the anhydrous condition, then the intermediate condensates with papaverine forming the core pyrro[2,l-a]isoquinoline, followed by formation and lactonization to form the lactone ring. The second synthetic route uses prepared aldehyde with prepared ethyl nitroacetate by Knoevenagel condensation to obtain 2-Nitro-3-(2,4,5-tris-methoxy-phenyl)-acrylic acid ethyl ester and 2-Nitro-3-(2,4,5-tris-benzyloxy -phenyl)-acrylic acid ethyl ester etal intermediates. The lamellarin skeleton could arise from condensation of the papaverine and these intermediates by Michael reaction, the ester group is provided for subsequent lactonization. The third synthetic route uses coumarin or indan-l,3-dione derivatives and papaverine to form lamellarin under basic conditions.

第一条路线首先从1,2,4-三甲氧基苯出发与卤乙腈作用合成卤代芳酮中间体,然后与罂粟碱反应合成开链片螺素,最后经乙酰化、去保护、成内酯环得到片螺素;第二条路线由制备的芳醛和制备的硝基乙酸乙酯经缩合得到2-硝基-3-芳基丙烯酸乙酯,然后由该中间体与罂粟碱反应,在完成关环的同时也引入酯基,最后去保护、成内酯环得到片螺素;第三条路线是由香豆素或茚二酮出发,经溴代后的中间体与罂粟碱反应,得到片螺素的基本框架。

The mechanisms of intramolecular biaryl nonphenolic coupling were explored by reactions of different 1,4-biaryl substituted butanes with DDQ in TFA.

通过对含不同取代基的芳环化合物、1,4-二芳基丁烷链上含不同取代基化合物与DDQ在TFA中进行非酚氧化偶合和重排反应的研究,对分子内的二芳基非酚氧化偶合反应机理作了深刻的探讨。

The preferred organometallic compounds of the present invention are of the formula (R1)m M(PR23)x, where M is a metal selected from the group consisting of manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium iridium and platinum wherein m is 0, 1, 2, 3 or 4; x is 2, 3, 4 or 5 and m+x are 2, 3, 4, 5, 6, 7 or 8, m and x selected according to each metals appropriate valence; each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a variety of substituted alkyl groups; each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, and alkyl-Z, aryl-Z and arylalkyl-Z where Z is selected from the group consisting of oxy, silyl, siloxy, oxysilyl, siloxy, oxysiloxy, silyalkyl, oxysilylalkyl, siloxyalkyl, oxysiloxyalkyl, silylalkoxy, silylalkoxy, siloxyalkoxy and oxysiloxyalkoxy; and wherein when M is cobalt and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium.

有机化合物的首选本发明的配方是米(R1代)米×(pr23)、那里是一米的金属挑选出来,第一组由锰、锝、铼、铁、钴、镍、钌、铑、钯、锇、铱铂其中M是0、1、2、3或4; X是2,3, 4或5米×+有2,3,4,5,6,7或8 米和X挑选合适的价按每个金属; R1的是每一组由独立选自氢、氘、氮、氢气、 D2和各种烷基取代群体; R2中的每个组由独立选自烷基低、芳、芳基烷基、烷基的Z、芳基、芳基烷基的Z-那里的ZZ是选自组风、含硅、氧、oxysilyl、硅、oxysiloxy,silyalkyl, oxysilylalkyl,siloxyalkyl,oxysiloxyalkyl,silylalkoxy,silylalkoxy,siloxyalkoxy和oxysiloxyalkoxy;其中,M是当钴一派R1的选择是氮气、然后是2米,第二组R1的氘是氢或者。

0Mol%. The catalytic system combining Pd 〓, imidazolium salt and pyridine has been employed in the cross-coupling of unactive aryl chlorides with malononitrile.

对大多数溴代芳烃而言,无论芳环上取代基是吸电子的,还是给电子取代基,均可高产率地制备得到相应的α—芳基丙二腈化合物(产率>85%)。

Using classical diazotisation of anilines, 5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin was converted to a series of meso-tetraarylporphyrins with different substituents, including 5-(4-hydroxylphenyl)-10,15,20-triphenylporphyrin (80%), 5-(4-chlorophenyl)-10,15,20-triphenylporphyrin (74%), 5-(4-iodinphenyl)-10,15,20-triphenylporphyrin (76%), 5-(4-hydrazinephenyl)-10,15,20-triphenylporphyrin (67%) and 5-(4-bisphenyl)-10,15,20-triphenylporphyrin (32%). Therefore an efficient way of synthesizing unsymmetrically substituted TAPs was developed.

利用芳胺的重氮化及重氮盐反应,研究了5-(4-氨基苯基)-10,15,20-三苯基卟啉上氨基官能团的转化反应,以较高产率合成了5-(4-羟基苯基)-10,15,20-三苯基卟啉(80%)、5-(4-氯苯基)-10,15,20-三苯基卟啉(74%)、5-(4-碘基苯基)-10,15,20-三苯基卟啉(76%)、5-(4-肼基苯基)-10,15,20-三苯基卟啉(67%)和5-(4-联苯基)-10,15,20-三苯基卟啉(32%)等一系列含单个para-取代基的meso-四芳基卟啉,为合成不对称取代的芳基卟啉提供一条有效途径。

Base played a crucial role in this reaction: in the Pd2/L1 catalyzed α-arylation of ethyl malonate, K3PO4 is the base of choice; in the α-arylation of ethyl acetoacetate, K2CO3 is the most effective base.

在这类催化反应中,碱的选择具有重要的影响:以K3PO4为碱, Pd2/L1催化体系在丙二酸二乙酯的α-芳基化中,富电子溴代芳烃显示较好的活性; Pd2/L1催化的乙酰乙酸乙酯α-芳基化时,以 K2CO3为碱,催化体系显示较好的活性,这个催化体系可控制反应得到α-芳基乙酰乙酸乙酯,而不是脱乙酰基的产物。

Base played a crucial role in this reaction: in the Pd2/L1 catalyzed α-arylation of ethy malonate, K3PO4 is the base of choice; in the α-arylation of ethyl acetoacetate, K2CO3 is the most effectiv base.

在这类催化反应中,碱的选择具有重要的影响:以K3PO4为碱,Pd2/L1催化体系在丙二酸二乙酯的α-芳基化中,富电子溴代芳烃显示较好的活性;Pd2/L1催化的乙酰乙酸乙酯α-芳基化时,以K2CO3为碱,催化体系显示较好的活性,这个催化体系可控制反应得到α-芳基乙酰乙酸乙酯,而不是脱乙酰基的产物。

This PhD thesis mainly summarizes the original results on studies of aromatic amide-derived phosphines,including the precatalyst system consisting of Aphos and Pd_2 and the applications for promoting room temperature Suzuki cross-coupling of aryl chlorides and aryl/vinyl bromides,respectively,with aryl/vinyl boronic acids,and alkyl boranes.

本博士学位论文主要总结了对芳基酰胺衍生的膦配体的研究,以及该类型配体与Pd_2组成的催化剂在室温下催化氯代芳烃、溴代芳烃、溴代烯烃分别同芳基硼酸、烯基硼酸及烷基硼试剂进行的Suzuki偶联反应中的表现。

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