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11.
12.
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst for carboxylic acid esterification with dimethyl carbonate (DMC). The reaction pathway of this new class of nucleophilic catalysis has been studied. A plausible, multistep mechanism is proposed, which involves an initial N-acylation of DBU with DMC to form a carbamate intermediate. Subsequent O-alkylation of the carboxylate with this intermediate generates the corresponding methyl ester in excellent yield. In the absence of DBU or in the presence of other bases, such as ammonium hydroxide or N-methylmorpholine, the same reaction affords no desired product. This method is particularly valuable for the synthesis of methyl esters that contain acid-sensitive functionality. 相似文献
13.
Karl O. Gelotte David N. Mason Harold Meckler Wen-Chung Shieh Colleen M. Starkey 《Journal of heterocyclic chemistry》1990,27(6):1549-1552
An efficient synthesis of the novel triazoloquinazoline adenosine antagonist, CGS 15943, is reported in five steps in approximately 50% overall yield. A key reaction in the synthetic sequence is the double cyclization of an N-(substituted-2-cyanophenyl)carbamate with a carboxylic acid hydrazide to afford a [1,2,4]triazolo-[1,5-c]quinazolin-5(6H)-one in high yield without either a Dimroth or “translocative” rearrangement occurring. Another key reaction is the condensation of a 2-(1H-1,2,4-triazol-5-yl)benzenamine with cyanamide under acidic conditions to prepare a guanidine. 相似文献
14.
A new general synthesis of substituted coumarins is described. The in situ cycloaddition of chloroketenes with α-methoxymethylenecyclohexanones yields (4 + 2) cycloaddition products, 3,4-dihydro-2-pyranones. The chlorine atom is reductively removed and methanol is spontaneously eliminated to yield the 5,6,7,8-tetra-hydrocoumarins. Dehydrogenation of these compounds results in good yields of the substituted coumarins. 相似文献
15.
Shieh M Cherng JJ Lai YW Ueng CH Peng SM Liu YH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(19):4522-4527
We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO(3) with [Cr(CO)(6)] in KOH/MeOH solutions. When the reaction was carried out at room temperature, the highly charged [Bi[Cr(CO)(5)](4)](3-) (1) was obtained, whose structure was shown by X-ray analysis to possess a central bismuth atom tetrahedrally coordinated to four [Cr(CO)(5)] groups. As the reaction was heated at 80 degrees C, the methyl-substituted complex [MeBi[Cr(CO)(5)](3)](2-)(2) was obtained, presumably via the CbondO activation of MeOH. Further reactions of 1 with CH(2)Cl(2) or CHtbondCCH(2)Br form the halo-substituted complexes [XBi[Cr(CO)(5)](3)](2-)(X=Cl, 3; Br, 4), respectively. On the other hand, the reactions of 1 with RI (R=Me, Et) led to the formation of the alkyl-substituted complexes [RBi[Cr(CO)(5)](3)](2-)(R=Me, 2; Et). The formation of complexes 1-4 is discussed, presumably via the intermediate bismuthinidene [Bi[Cr(CO)(5)](3)](-) or the trianion [Bi[Cr(CO)(5)](3)](3-). 相似文献
16.
We have synthesized a new series of chromium-group 15 dihydride and hydride complexes [H(2)As(Cr(CO)(5))(2)](-) (1) and [HE(Cr(CO)(5))(3)](2)(-) (E = As, 2a; E = Sb, 2b), which represent the first examples of group 6 complexes containing E-H fragments. The contrasting chemical reactivity of 2a and 2b with organic halogen derivatives is demonstrated. The reaction of 2a with RBr (R = PhCH(2), HC triple bond CCH(2)) produces the RX addition products [(R)(Br)As(Cr(CO)(5))(2)](-) (R = PhCH(2), 3; R = C(3)H(3), 4), while the treatment of 2b with RX (RX = PhCH(2)Br or HC triple bond CCH(2)Br, CH(3)(CH(2))(5)C(O)Cl) forms the halo-substituted complexes [XSb(Cr(CO)(5))(3)](2-) (X = Br, 5; X = Cl, 6). Moreover, the dihaloantimony complexes [XX'Sb(Cr(CO)(5))(2)](-) can be obtained from the reaction of 2b with the appropriate organic halides. In this study, a series of organoarsenic and antimony chromium carbonyl complexes have been synthesized and structurally characterized and the role of the main group on the formation of the resultant complexes is also discussed. 相似文献
17.
18.
Prof. Dr. Minghuey Shieh Chun‐Hsien Yu Yen‐Yi Chu Yu‐Wen Guo Chung‐Yi Huang Kai‐Jieah Hsing Pei‐Chi Chen Chung‐Feng Lee 《化学:亚洲杂志》2013,8(5):963-973
The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr? Mn? carbonyl clusters, [E2CrMn2(CO)9]2? (E=S, 1 ; Se, 2 ). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal‐bipyramidal structure, with the CrMn2 triangle axially capped by two μ3‐E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9]2? ( 3 ), was obtained from the ring‐closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18]2? ( 4 ). Upon bubbling with CO, clusters 2 and 3 were readily converted into square‐pyramidal clusters, [E2CrMn2(CO)10]2? (E=Se, 5 ; Te, 6 ), accompanied with the cleavage of one Cr? Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue ( 5 ) was spectroscopically proposed to be diamagnetic, as verified by TD‐DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn? Mn bond to produce a new arachno‐cluster, [Te2CrMn2(CO)11]2? ( 7 ). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. 相似文献
19.
3, 4′-Bipyridine was synthesized from 6-methoxy-3, 4′-bipyridine or 6-benzyloxy-3, 4′-bipyridine via 6-chloro-3, 4′-bipyridine. The chloro derivative was catalytically dechlorinated into the corresponding 3, 4′ -bipyridine. 相似文献
20.
Spencer Knapp Andrew B. J. Naughton Paivi J. Kukkola Wen-Chung Shieh 《Journal of carbohydrate chemistry》2013,32(6):981-993
ABSTRACT For five carbohydrate substrates [methyl 4,6-O-(phenylmethylene)-1-thio-α-D-glucopyranoside 1a, 1-cyano-1-deoxy-4,6-O-(phenylmethylene)-α-D-galactopyranose 2a, methyl α-D-xylopyranoside 3a, methyl β-D-arabinopyranoside 4a, and methyl 5-O-(tert-butyldiphenylsilyl)-α-D-ribofuranoside 5a], selective mono-triflation was achieved where the reacting hydroxyl is cis and vicinal to a heteroatom. 相似文献