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1.
Rapid and convenient methods are described for the exhaustive derivatization of carbonyl, carboxyl and hydroxyl groups of prostaglandins and related compounds to methoxime, alkyl ester and alkyl ether compounds respectively. Optimal reaction conditions were established for each group. The reactions were carried out in polar aprotic solvents. Alkyl ester alkyl ether derivatives were obtained quantitatively and rapidly in one step with n-alkyl (C1-C4) halides in the presence of sodium hydroxide. Methyl ester methyl ether derivatives have the highest volatility, but propyl ester propyl ether derivatives improved the separation of complex mixtures. The carbonyl group sometimes induced side-products, so the carbonyl group was converted into methoxime. Methoximation was achieved quantitatively by using methoxylamine in the presence of hydrochloric acid or sodium hydroxide, followed by alkylation in same reaction medium. Methoximation gave syn- and anti-isomers, which were separated chromatographically, decreasing the resolution for complex samples. 相似文献
2.
An efficient method for generation of alpha-lambda3-iodanyl ketones from (Z)-(2-acetoxyvinyl)(phenyl)-lambda3-iodanes was developed. The method involves ester exchange of (Z)-2-acetoxyvinyl-lambda3-iodanes with methanol in the presence of triethylamine. alpha-lambda3-Iodanyl ketones react with a variety of nucleophiles such as halides, thiols, phosphines, phosphinic acids, and phosphates, under the conditions which produce alpha-functionalized carbonyl compounds probably via an S(N)2 pathway. 相似文献
3.
Here we report the substitution effects of N-alkyl and N,N-dialkyl carboxamide groups on the fluorescence properties of polycyclic aromatic hydrocarbon chromophores, so as to control their fluorescence properties. The fluorescence properties of compounds obtained using solvents with different polarities showed very little change, indicating that the modified compounds do not form charge transfer states. TD-DFT calculations and measurements performed at low temperature (78 K) and in viscous solvents revealed that the N-alkyl and N,N-dialkyl carboxamide groups tend to reduce the contributions from intersystem crossing and increase those from internal conversion. Considering that the fluorescence mechanism of low-fluorescence carbonyl compounds such as aldehyde and ketone is dominated by intersystem crossing and that of high-luminescence carbonyl compounds such as carboxylic acid and ester is dominated by a radiative process, it can be said that the photophysical process of N-alkyl and N,N-dialkyl carboxamides is novel. In addition, the calculation results for excited states indicated that such contributions can be controlled by selecting the appropriate polycyclic aromatic hydrocarbon or amide structure, in addition to solvent viscosity and temperature. 相似文献
4.
Laura L. Santos Dr. Pedro Serna Dr. Avelino Corma Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(33):8196-8203
Substituted imines, α,β‐unsaturated imines, substituted secondary amines, and β‐amino carbonyl compounds have been synthesized by means of new cascade reactions with mono‐ or bifunctional gold‐based solid catalysts under mild reaction conditions. The related synthetic route involves the hydrogenation of a nitroaromatic compound in the presence of a second reactant such as an aldehyde, α,β‐unsaturated carbonyl compound, or alkyne, which circumvents an ex situ reduction process for producing the aromatic amine. The process is shown to be highly selective towards other competing groups, such as double bonds, carbonyls, halogens, nitriles, or cinnamates, and thereby allows the synthesis of different substituted nitrogenated compounds. For the preparation of imines, substituted anilines are formed and condensed in situ with aldehydes to provide the final product through two tandem reactions. High chemoselectivity is observed, for instance, when double bonds or halides are present within the reactants. In addition, we show that the Au/TiO2 system is also able to catalyze the chemoselective hydrogenation of imines, so that secondary amines can be prepared directly through a three‐step cascade reaction by starting from nitroaromatic compounds and aldehydes. On the other hand, Au/TiO2 can also be used as a bifunctional catalyst to obtain substituted β‐amino carbonyl compounds from nitroaromatics and α,β‐unsaturated carbonyl compounds. Whereas gold sites promote the in situ formation of anilines, the intrinsic acidity of Ti species on the support surface accelerates the subsequent Michael addition. Finally, two gold‐catalyzed reactions, that is, the hydrogenation of nitro groups and a hydroamination, have been coupled to synthesize additional substituted imines from nitroaromatic compounds and alkynes. 相似文献
5.
Ni-catalyzed activation of α-chloroesters: a simple method for the synthesis of α-arylesters and β-hydroxyesters 总被引:1,自引:0,他引:1
Coupling reactions of α-chloroesters with aryl halides (α-arylation) or carbonyl compounds (Reformatsky) using nickel catalyst allow, under mild conditions, the preparation of various functionalized aryl propionic acid derivatives or β-hydroxyesters. In the synthesis of aryl propionic acid derivatives, the process is efficient with aryl halides bearing either electron-withdrawing or electron-donating groups. 相似文献
6.
AI Teng ZHU Xiao-Qing CHENG Jin-Pei 《有机化学》2003,23(Z1):175-175
Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1. 相似文献
7.
Markus Neuenschwander Peter Bigler Klaus Christen Rudolf Iseli Rolf Kyburz Hansueli Mühle 《Helvetica chimica acta》1978,61(6):2047-2058
Chloroacylation and bromoacylation of carbonyl compounds: A forgotten carbonyl reaction. I. Scope of the reaction Aliphatic, α,β-unsaturated and aromatic aldehydes as well as aliphatic ketones react with acyl halides to (α-haloalkyl)esters. These bifunctional derivates contain two leaving groups of different reactivity. The scope of this scarcely of this scarcely known carbonyl reaction is discussed. 相似文献
8.
Árpád Furka 《Structural chemistry》2009,20(4):605-616
The energies of the following types of compounds are characterized by their calculated relative enthalpies: alkyl, alkenyl,
and aryl halides; carboxylic acid halides; carbonyl halides; amines; carboxylic acid amides; hydrazine derivatives; nitriles;
heteroaromatic compounds; nitro-compounds; organic nitrites and nitrates; organic sulfides; thiols; disulfides; sulfoxides;
sulfones; organic sulfites and sulfates; and selected inorganic compounds. Stabilization energy of pyrrol and thiophene has
been estimated. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(1-3):65-78
Abstract Metal carbonyl anions exhibit one- and two-electron reactions. The two-electron processes involving transfer of groups (hydrogen, alkyl, and halogen) between metal centers are related to the nucleophilicity. The one-electron processes are primarily outer-sphere electron transfer for the metal carbonyl anions. These reactions are observed in the presence of oxidants such as coordination complexes, pyridinium salts, metal carbonyl dimers and metal carbonyl clusters. However, in contrast to organic reactions, the metal carbonyl anions may undergo inner-sphere electron transfer. Reactions of metal carbonyl anions of low nucleophilicity with metal carbonyl cations or halides are best interpreted as inner-sphere, one-electron transfer. 相似文献
10.
Wang L Peng S Danence LJ Gao Y Wang J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(19):6088-6093
An enamine-catalyzed strategy has been utilized to fully promote the Huisgen [3+2] cycloaddition with a broad spectrum of carbonyl compounds and azides, thereby permitting the efficient assembly of a vast pool of highly substituted 1,2,3-triazoles. In particular, the employment of commonly used and commercially available carbonyl compounds has resulted in the introduction of a diverse set of functional groups, such as alkyl, aryl, nitrile, ester, and ketone groups, at the 1-, 4-, or 5-positions of the 1,2,3-triazole scaffold. This approach might be manipulated to access more useful and sophisticated heterocyclic compounds. Most significantly, the reaction process exhibits complete regioselectivity, with the formation of only one regioisomer. 相似文献
11.
Tomoya Fujiwara 《Journal of fluorine chemistry》2005,126(6):941-955
The chemistry of compounds containing a carbon atom bearing three or four different labile functional groups has received little attention. These compounds should be of considerable significance in theoretical and synthetic organic chemistry. Among the compounds with multifunctional structures, those having both carbonyl and halogen groups in addition to other heteroatom groups seem especially valuable from a synthetic viewpoint. Their potential use as probes in pure and applied synthetic chemistry has not been exploited, presumably because of structural instability and a paucity of synthetic approaches. Keeping this background in mind, we focused on the synthesis of a new class of multifunctional carbon compounds in which ester carbonyl, halogen, and other heteroatom-derived functional groups are directly attached to the central carbon atom. Fluorine was chosen as the halogen because of the inherent stability of the CF bond and because of the fundamental chemical and biological interest in fluorine-containing compounds. The synthesis, reactions, and some applications of various fluorine-containing multifunctional carbon compounds are described. 相似文献
12.
Lei Wang Shiyong Peng Lee Jin Tu Danence Yaojun Gao Prof. Dr. Jian Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(19):6088-6093
An enamine‐catalyzed strategy has been utilized to fully promote the Huisgen [3+2] cycloaddition with a broad spectrum of carbonyl compounds and azides, thereby permitting the efficient assembly of a vast pool of highly substituted 1,2,3‐triazoles. In particular, the employment of commonly used and commercially available carbonyl compounds has resulted in the introduction of a diverse set of functional groups, such as alkyl, aryl, nitrile, ester, and ketone groups, at the 1‐, 4‐, or 5‐positions of the 1,2,3‐triazole scaffold. This approach might be manipulated to access more useful and sophisticated heterocyclic compounds. Most significantly, the reaction process exhibits complete regioselectivity, with the formation of only one regioisomer. 相似文献
13.
A general, rapid method is described for alkylation of phenols and alcohols to give ethers, for amides to give N-substituted amides, and for acids to give esters. Differences in optimum reaction times suggest that where two or more such groups as phenol, alcohol, amide, and acid occur in the same molecule, differential alkylation could be effected with suitable substrates. Alkylation with primary alkyl halides was very effective but secondary halides showed evidence for competitive dehydrohalogenation before alkylation was complete and tertiary halides were rapidly dehydrohalogenated with no formation of alkylated derivatives. The method has been applied successfully to N,O-alkylation of peptides for mass spectrometric sequence determination. C-Methylation of peptidic amino-acid residues was observed only on carbon α to a carboxylic ester. 相似文献
14.
15.
Allylic halides react with reduced cobalt or nickel halides and with carbonyl compounds according to a pattern analogous to that of a Grignard reaction but with the difference that protic solvents can be used. 相似文献
16.
Vichai Reutrakul Chitchanun Panyachotipun Viwat Hahnvajanawong S. Sotheeswaran 《Tetrahedron letters》1984,25(17):1825-1828
Lithio iodomethyl phenyl sulfoxides reacted with alkyl halides and carbonyl compounds to give adducts in good to moderate yields. Solvolysis of the carbonyl adducts led to sulfones or the ring expanded product. 相似文献
17.
[reaction: see text] A selective and catalytic mono-N-alkylation method of both aromatic and aliphatic amines using nitriles as an alkylating agent with Pd/C or Rh/C as a catalyst is described. This method is particularly attractive to provide an environmentally benign and applicable alkylation method of amines without using toxic and corrosive alkylating agents such as alkyl halides and carbonyl compounds. 相似文献
18.
Transition‐metal‐catalyzed carbonylation with CO gas occupies a privileged position in organic synthesis for the synthesis of carbonyl compounds. Although this attractive and useful chemistry has led many researchers to investigate carbonylative transformations of various organic (pseudo)halides, C?S‐cleaving carbonylation of organosulfur compounds has been fairly limited. Recently, a broad spectrum of C?S‐cleaving transformations has been emerging in the field of cross‐coupling. In light of the importance of carbonyl compounds as well as considerable advancement for employing organosulfur compounds as competent surrogates of (pseudo)halides, carbonylative transformations of C?S bonds should be of high value. This Minireview focuses on catalytic C?S carbonylation of organosulfur compounds with CO or its equivalents. In addition, reductive carboxylation of C?S bonds with CO2 is described. 相似文献
19.
Ramasamy、Osuka等用NaHTe/EtOH研究了二卤代物的脱邻二溴、偕二溴反应和α-溴代羰基化合物的脱卤还原反应,我们选择结构不同的卤代物以NaHTe还原,发现在水介质和催化量碲代替计算量碲时也能顺利地进行这类反应,其反应条件温和,产率高,是有机官能团转化的好方法。 相似文献
20.
A direct borylation of aryl halides or triflates with dialkoxyborane was investigated. The coupling reaction of pinacolborane with aryl halides or triflates in the presence of a catalytic amount of PdCl(2)(dppf) together with a base provided arylboronates in high yields. The product distributions were strongly dependent on the base employed, and the tertiary amine, especially Et(3)N, was effective for the selective formation of the boron-carbon bond. The reaction conditions were so mild that arylboronates having a variety of functional groups such as carbonyl, cyano, and nitro groups were readily prepared. 相似文献