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1.
Summary The formation of the acetic esters of tri- and di-bromo ketols by the action of HOBr on the acetic esters of secondary and tertiary acetylenic alcohols is due to the particularly strongly protonized (acidic) hydrogen atom of the methylidyne group=C-H, which results from profound frequency modulation of the vibrations of the latter by the low-frequency intermolecular vibrations at the hydrogen bonds.  相似文献   

2.
Acetoxy and propionoxy esters of 1-phenethyl-4-(2′-furyl)-4-piperidinol hydrochlorides, upon treatment with one mole excess of hydrogen chloride in an alkanol, were converted into corresponding 4-alkoxy ethers and elimination products. These results are interpreted in terms of reactions of carbonium ions, produced from the esters by alkyl-oxygen heterolysis. Factors affecting carbonium ion generation and fate have been studied and include the electronic character of the 4-aryl substituent, nature and size of the nucleophile, degree of acidity and role of the piperidine nitrogen atom.  相似文献   

3.
A catalytic amount of Hantzsch ester that could be regenerated in situ by Ru complexes under hydrogen gas has been employed in the biomimetic asymmetric hydrogenation of benzoxazinones with up to 99% ee in the presence of chiral phosphoric acid. The use of hydrogen gas as a reductant for the regeneration of Hantzsch esters makes this hydrogenation an ideal atom economic process.  相似文献   

4.
Rajaram AR  Pu L 《Organic letters》2006,8(10):2019-2021
[reaction: see text] The optically active gamma-hydroxy-alpha,beta-acetylenic esters are obtained from the enantioselective reaction of methyl propiolate with both aliphatic and aromatic aldehydes. These compounds can undergo regiospecific hydration in the presence of Zeise's dimer, [PtCl(2)(C(2)H(4))](2), to generate the optically active tetronic acids.  相似文献   

5.
A review of the literature indicates compelling evidence that: (1) loss of ROH from esters requires protonation of the alkoxy oxygen; (2) the (symmetry forbidden) [1,3] hydrogen migration from protonated carbonyl to alkoxy oxygen does not occur in the mass spectra of esters; (3) hydrogen abstraction in esters occurs almost exclusively to the carbonyl oxygen. Mechanisms are proposed which account for all examples of ROH loss from esters. Alkanol loss from molecular ions in esters requires the presence of a second functional group to act as an intramolecular catalyst, either as a general acid in transferring a proton to the alkoxy oxygen, or as a general base in assisting the [1,3] carbonyl oxygen to alkoxy oxygen proton transfer. Loss of ROH from fragment ions requires proton transfer from an atom α to the positive charge to the alkoxy oxygen. These mechanisms are generalized to include a wide class of bifunctional esters and a selection of natural products.  相似文献   

6.
The temperature effect on the single and double hydrogen atom transfer reactions in o-, m- and p-toluic acid n-butyl esters and isobutyl esters has been investigated. For the meta and para isomers, the abundance of the m/z 137 ion [C8H9O2]+ generated by a double hydrogen atom transfer reaction increases relative to the m/z 136 ion [C8H8O2]+˙ generated by a single hydrogen atom transfer reaction upon lowering the temperature of the ionization chamber. On the other hand, the ratio of the peak abundances [137]+/[136]+ for the ortho isomers is nearly constant when the temperature is changed. It is shown that this is due to the difference between the appearance energies of the m/z 136 and m/z 137 ions.  相似文献   

7.
The mass spectra of several para-substituted benzenesulfonic and benzoic esters of unlabelled and 1,1-d2-neopentyl alcohol are examined and compared. Evidence is presented of migration of the aryl group from the sulfur to an oxygen atom in the molecular ions of the sulfonic esters. The nature of the fragmentation processes and the occurrence of metastable ions for these processes are both much more dependent upon the polarity of the para substituent in the case of the sulfonates than for the benzoates. Elimination of C5H10 occurs from the molecular ion of the p-methoxysulfonate with transfer to the residual ion of a hydrogen atom selected randomly from the alkyl fragment, while in the case of the p-aminosulfonate, incomplete randomization is demonstrated.  相似文献   

8.
The substituent effect on the single and double hydrogen atom transfer reactions in para-substituted benzoic acid isobutyl esters has been investigated by electron impact mass spectrometry. Electron-donating substituents favour formation of the [M? C4H8]+˙ ion generated by single hydrogen atom transfer reaction (McLafferty rearrangement), whereas electron-withdrawing substituents favour formation of the [M? C4H7]+ ion generated by double hydrogen atom transfer reaction. In the case of the latter compounds, the m/z56 ([C4H8]+˙) ion, which is generated by single hydrogen atom transfer reaction with charge migration, is very intense, while in the former compounds, the m/z56 ion is very weak. These observations can be reasonably explained on thermochemical grounds based on the sum of the standard heats of formation of the fragments.  相似文献   

9.
It is shown that both electrospray and fast atom bombardment mass spectrometry provide excellent negative-ion mass spectra of the anionic esters of boric, boronic and borinic acids. For electrospray, contact of the esters with water causes some hydrolysis but, in most cases, spectra of the intact molecular anions are readily obtained. For fast atom bombardment, solvents that chelate with the boron esters must be avoided, Tetraethylene glycol diethyl ether, pentaethylene glycol dimethyl ether or hexaethylene glycol dimethyl ether are suitable solvents. Negative-ion electrospray mass spectra showed few, if any, fragment ions, whereas fast atom bombardment generally produced abundant M? ions and several fragment ions of low abundance. It is shown that a simple reaction with dibenzene-borinic acid converts diols such as monoglycerides and monoalkyl glyceryl ethers into anionic borinate esters as a pre-ionization procedure for analysis by electrospray or fast atom bombardment mass spectrometry.  相似文献   

10.
β-Nitro acrylic esters, obtained by the reaction of nitroalkanes and ethyl glyoxalate, are the key building blocks for the immediate synthesis of both the title compounds. In fact, their treatment with titanium trichloride produce the direct conversion to the β-keto esters, while their reaction with sodium boron hydride gives the one-pot synthesis of α,β-unsaturated esters through formal substitution of the vinylic nitro group with an hydrogen.  相似文献   

11.
Conclusions The hydroxy-thiol rearrangement of the 2-hydroxyalkyl esters of dialkylthiophosphoric acids is retarded when one bulky substituent, and specifically the 1,1-dimethyl-2,2,2-trichloroethoxy group, is inserted on the phosphorus atom. Stabilization fails to occur when one phenoxyl substituent in the 2-hydroxyalkyl esters of diphenylthiophosphoric acid is replaced by this group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 429–431, February, 1984.  相似文献   

12.
The synthesis and chemical properties of aziridine-2,2-dicarboxylic acid esters were investigated. The activation parameters of the inversion of the nitrogen atom in 1-substituted aziridine-2,2-dicarboxylic acid esters were determined. The inv values of a number of substituents attached to the nitrogen atom were established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 346–351, March, 1985.  相似文献   

13.
2-Alkyloxaziridine-3, 3-dicarboxylic acid esters have been obtained by oxidizing alkylaminomalonic acid esters by monoperphthalic acid. The activation parameters for the inversion of the nitrogen atom have been obtained for a number of alkyliminomalonic acid and 2-alkyloxaziridine-3, 3-dicarboxylic acid ester.Report 46 from a series entitled Asymmetric Nonbridging Nitrogen. For report 45 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 525–532, April, 1986.  相似文献   

14.
Treatment of an alcoholic suspension of amino acids with trimethylchlorosilane yielded phenylglycine, valine, β-phenylalanine, and homovaline ester hydrochlorides. Their saccharin-catalyzed silylation with hexamethyldisilazane proceeds quantitatively and involves only one proton of the amino group. The best conversion of the amino acid esters to the corresponding isocyanates was achieved by phosgene treatment of their monosilyl urethanes, rather than of the silylated amino esters. Monosilyl urethanes are formed quantitatively by treatment of the amino acid ester hydrochlorides with the hexamethyldisilazane-CO2 system. The 1H NMR spectra show that monosilyl urethanes derived from α-and β-amino acid esters are characterized by intramolecular interaction of the silicon atom and the oxygen atom of the carboxy group.  相似文献   

15.
Conclusion The reduction of esters of chloro- and bromonitroacetic acids by sodium dithionite leads to the replacement of the halogen atoms by hydrogen, while the catalytic hydrogenation of chloronitroacetate esters proceeds with the formation of hydrochloride salts of alkyl esters of glycine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1162–1164, May, 1987.The authors express their gratitude to K. K. Babievskii for providing samples of the nitroacetate esters.  相似文献   

16.
The reaction of singlet oxygen with α,β-unsaturated esters shows a general preference for hydrogen abstraction on the alkyl group geminal to the ester.  相似文献   

17.
A series of stilbeneboronate pinacol cyclic esters, containing none to three nitro groups, have been synthesized by various olefination reactions and characterized by X-ray single-crystal structure analysis. A stilbeneboronate ester bearing electron-acceptor groups experiences transition to a push-pull pi-electron system upon complexation with one fluoride ion at the boron atom. The UV-vis absorption maxima of the presented nitro-substituted stilbeneboronate esters are red-shifted upon addition of fluoride ions, indicating this binding event. The enhancement of the polarity of the investigated compounds and the changes in the electronic system were investigated by UV-vis absorption spectroscopy and solvatochromism. Additionally, studies were performed by natural bond orbital (NBO) analysis and RI-CC2 calculations of the vertical excitation energies. The synergism of fluoride ion complexation and solvation upon the UV-vis band shift is interpreted in terms of linear solvation energy relationships (LSERs) using the Kamlet-Taft solvent parameter set. It is found that the UV-vis absorption of the fluoro-boronates is strongly dependent on the solvents hydrogen-bond donating ability.  相似文献   

18.
Acid, aldehyde and carbon dioxide were the major products of the vacuum photodegradations of poly(vinyl acetate) (PVAC), poly(vinyl propanoate) (PVPR) and poly(ethylene-co-vinyl acetate) (PEVAC). Aldehydes have not previously been reported as formed from the acid portions of esters undergoing photolysis. The generality of aldehyde formation has been demonstrated by the detection of the respective aldehydes in the liquid-phase photolysis of butane-1,3-diol diacetate (BDAC) and butane-1,3-diol dipropanoate (BDPR) in this study, which is the first to report the quantum yields for acid and aldehyde formation in low molecular mass esters. Two mechanisms, one involving hydrogen abstraction by the acyl radical formed in a Norrish Type I cleavage process and the other involving an intramolecular hydrogen abstraction by an excited carbonyl group followed by fragmentation, have been proposed to account for aldehyde formation. The absence of propanal from the product distribution in the photo-oxidation of PVPR could be explained by both mechanisms.  相似文献   

19.
The concerned diols (general abbreviation, H(2)L) are catechol (H(2)L(1)) and its 3,5-Bu(t)(2) derivative (H(2)L(2)). Esters of the type VO(xsal)(HL), 2, are obtained by reacting H(2)L with VO(xsal)(H(2)O) or VO(xsal)(OMe)(HOMe), where xsal(2-) is the diionized salicylaldimine of glycine (x = g), L-alanine (x = a), or L-valine (x = v). The reaction of VO(acac)(2) with H(2)L and the salicylaldimine (Hpsal) of 2-picolylamine has furnished VO(psal)(L), 3. In the structures of VO(gsal)(HL(1)), 2a, and VO(vsal)(HL(2)), 2f, the HL(-) ligand is O,O-chelated, the phenolic oxygen lying trans to the oxo oxygen atom. The xsal(2-) coligand has a folded structure and the conformation of 2f is exclusively endo. In both 2a and 2f the phenolic oxygen atom is strongly hydrogen bonded (O...O, 2.60 A) to a carboxylic oxygen atom of a neighboring molecule. In VO(psal)(L(2)).H(2)O, 3b, the diionized diol is O,O-chelated to the metal and the water molecule is hydrogen bonded to a phenoxidic oxygen atom (O.O, 2.84 A). The C-O and C-C distances in the V(diol) fragment reveal that 2 is a pure catecholate and 3 is a catecholate-semiquinonate hybrid. In solution each ester gives rise to a single (51)V NMR signal (no diastereoisomers), which generally shifts downfield with a decrease in the ester LMCT band energy. The V(V)/V(IV) and catecholate-semiquinonate reduction potentials lie near -0.75 and 0.35, and 1.10 and 0.70 V vs SCE for 2 and 3, respectively. Molecular oxygen reacts smoothly with 2 quantitatively furnishing the corresponding o-quinone, and in the presence of H(2)L the reaction becomes catalytic. In contrast, type 3 esters are inert to oxygen. The initial binding of O(2) to 2 is proposed to occur via hydrogen bonding with chelated HL(-).  相似文献   

20.
Conclusions The decomposition of the 2-hydroxyalkylthiol esters of phosphorus acids at atmospheric pressure leads to alkylene sulfides and the corresponding phosphorus acids. The direction of the reaction for the thermal decomposition of these esters in vacuo depends on the structure of the substituents on the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2625–2627, November, 1976.  相似文献   

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