Reaction of mucochloric and mucobromic acid with (ethoxycarbonylmethylene) triphenyl-phosphorane affords the ethyl ester of (2, 4 -4,5-dichloro- and (2, 4) -4, 5-dibromo-2,4-pentadienoic acid respectively; in the latter case ethyl (2 -5-bromo-2-penten-4-ynoate is formed concomittantly. 相似文献
Oxidation of the complexes -[M(CNR)2(dppe)2] (A) (M = Mo or W; R = Me, But or CH3C6H4-; dppe = Ph2PCH2CH2PPh2) with diiodine or silver (I) salts gives the paramagnetic cations -[M(CNR)2(dppe)2]+, (M = Mo, R = CH3C6H4-; M = W, R = But) and -[M(CNR)2(dppe)2]2+ (M = Mo, R = Me or CH3C6H4-; M = W, R = Me or But). Mixtures of products are generally produced when dichlorine or dibromine are the oxidising agents, however pure salts, the seven-coordinate complex cations [MX(CNC6H4CH3-)2(dppe)2]+ (B, X = Cl or Br) have been isolated. A simple molecular orbital scheme is proposed for complexes (A) and used to discuss their electronic spectra and their oxidation. 相似文献
HC(SO2F)3 has been prepared and characterized. It turned out to be a strong acid, comparable to mineral acids. In aqueous solution the salts of the type Cs+C(SO2F)3? are formed. The anion, as found by crystal structure analysis contains planar CS3 configuration.Quite in contrast to these findings HC(OSO2F)3 is not even soluble in water.Derivatives of HC(SO2F)3 have been prepared so far CH3C(SO2F)3 FC(SO2F)3 ClC(SO2F)3 BrC(SO2F)3 JC(SO2F)3The heavier halogen derivatives ( Cl, Br, J ) are oxidizing agents (‘positive halogen’).A mixture of and (HO)2TeF4 is obtained if HOTeF5 and Te(OH)6 are melted together. The mixture of the isomeres have been transfered into the corresponding silylesters - and (R3SiO)2TeF4, which could be separated by fractional crystallisation and distillation.Without conformational change the pure silylesters have been reacted back to pure - (HO)2TeF4 and - (HO)2TeF4 by means of anhydrous HF. Both and (HO)2TeF4 have been reacted with ClF to give - and - (ClO)2TeF4, yellow liquids. The latter react with elemental bromine to the rather unstable and (BrO)TeF4, red liquids.Starting with -(HO)2TeF4 and XeF2 a polimer Xenon compound of the formula All materials have been characterized by melting point and vapour pressure, 19 F - nmv spectroscopy, vibrational spectroscopy, and elemental analysis. 相似文献
Thermolysis of several trans-1-isopropenyl-4-methylene-spiro[2.x]- alkanes (x = 4,5) in xylene solution at 130° causes quantitative rearrangement to 1-methylene-2-(3′-methylbut-2′-enyl)cycloalkanes ( – ). 相似文献
A short, reliable, and practical synthesis of ()-(+)-2-(-tolylsulfinyl)-2-buten-4-olide has been developed, and the utility of this Michael acceptor for highly enantiocontrolled synthesis of 3-substituted 4-butanolides has been demonstrated. 相似文献
A sequence of formylation followed by a carbene insertion reaction has led to the stepwise introduction of additional ethano bridges into 4,5,7,8- tetramethyl [22](1,4)cyclophane (), providing syntheses of 5,7,8-trimethyl- [23](l,2,4)cyclophane (), a mixture of 5,8-dimethyl[24(1,2,4,5)cyclophane () and 5,7-dimethyl[24(1,2,3,5)cyclophane (, and-4-methyl[25](1,2,3,4,5)-cyclophane (). This route to completes a formal eight-step synthesis of [26](1,2,3,4,5,6)cyclophane (, superphane) with an overall yield of 17%. A Birch reduction of readily gave 12,15-dihydro-5,7,8-trimethyl[23](1,2,4)-cyclophane () in 85% yield. 相似文献
A stereoselectivity in an intramolecular cycloaddition of the olefinic -quinodimethanes 13 and 23 generated from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)--4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described. 相似文献
The reactions of -2-methyl-2-pentene (1) with several - difunctional benzenes afforded eight- and nine-membered benzoheterocyclic compounds carrying perfluoroalkyl groups. Salicylic acid, salicylaldehyde, and their methyl or chloro derivatives reacted in triethylamine-acetonitrile system giving perfluoroalkylated 2H,6H-1,5-benzodioxocin-2,6-dione (8) and 4H,6H-1,5-benzodioxocin (9) compounds respectively, while phthalyl alcohol and o-hydroxyphenethyl alcohol in triethylamine-diethyl ether system gave perfluoroalkylated 1H,3H,7H-2,6- and 4H,6H,7H-1,5-benzodioxonin compounds, (10) and (11). o-Aminobenzyl alcohol and (1) in diethyl ether afforded a perfluoroalkylated benzoxazocinobenzoxazocinone compound (15). 相似文献
3-(t-Butoxycarbonyl)-2-(trifluoromethyl)imidazo[1,2-]-pyridine, prepared from trifluoroacetonitrile and pyridinium t-butoxycarbonylmethylide, reacts smoothly with trifluoroacetic acid to provide 2-(trifluoromethyl)imidazo[1,2-]pyridine-3-carboxylic acid, which gives 2-(trifluoromethyl)imidazo[1,2-]-pyridine when heated. 3-Cyano-2-(trifluoromethyl)imidazo[1,2-]pyridine can be obtained treatment of trifluoroacetonitrile with pyridinium cyanomethylide, which is sufficiently reactive to effect nucleophilic displacement of fluorine from pentafluoropyridine under mild conditions [→pyridinium cyano(tetrafluoro-4-pyridyl)methylide]. 相似文献
A synthesis of (2S,3S,7S)-3,7-dimethylpentadecan-2-yl acetate () and propionate () is described. (2S)-2-Methyldecan-1-yl lithium () was reacted with (3S,4S)-3,4-dimethyl-γ-butyrolactone () to yield the ketoalcohol which upon Huang-Minlon reduction furnished (2S,3S,7S)-3,7-dimethylpentadecan-2-ol (). Acylations gave the esters and . The (2S)-2-methyldecan-1-yl lithium was obtained via asymmetric synthesis. The chiral lactone was obtained from (2S,3S)-trans-2,3-epoxybutane and dimethyl malonate. 相似文献
(5)-Prostaglandin E2 methyl ester was synthesized from ()-4--butyldimethylsiloxy-2-cyclopentenone by 2-alkenyloxycarbonylation of the organocopper conjugate-addition adduct followed by intramolecular palladium-catalyzed decarboxylative 2-alkenylation. A ()-2-butenylated cyclopentanone derivative was obtained from either 2-[()- or ()-2-butenyloxy-carbonyl]cyclopentanone derivative under the similar reaction condition. 相似文献
An enzyme preparation from E. coli catalyses the formation of osuccinylbenzoic acid (, OSB, i.e. 4-(2′-carboxyphenyl)-4-oxobutanoic acid) from α-ketoglutaric acid and -chorismic acid () but not from chorismic acid (). 相似文献
The crystal structure of Ca6Eu2Na2(PO4)6F2 has been determined by single crystal X-ray diffraction. The unit cell constants are and the space group is . The structure was refined by normal full matrix least squares techniques. The final value of the refinement indicator is R = 0.065, based on 419 reflections.The structure of Ca6Eu2Na2(PO4)6F2 contains disordered cations in both the triangle and column positions. The occupation of the six triangle sites is and and of the four column sites , and . 相似文献
The relative rates of formation of and [2+2]cycloadducts of benzyne to , - and , -1,5-cyclooctadiene, - and -cyclooctene are discussed and properties of the adducts (e.g., their unusual hydrogenation) are described. 相似文献
Cycloaddition reactions between vinyl ethers 3 and -quinone methides 2, thermally generated from 2-hydroxybenzyl alcohols 1, have been studied. The structure and conformational preferences of the 4-substituted 2-ethoxy-(2,3)-dihydro-2-benzopyrans 4–9 obtained, which show new interesting features, are discussed together with competitive kinetic data. The cycloaddition process is concerted and involves -quinone methides in the -configuration. The OEt- transition state seems to be preferred with ethyl vinyl ether and -1-propenyl ethyl ether, whereas with -1-propenyl ethyl ether the stereoselectivity of the cycloaddition process depends on substituents on the methylene group of the starting alcohol 1. These results are discussed in terms of and preference of the propenyl ether methyl group. 相似文献
2-Hydroxybenzoic acid heated with 2,4 - bis(4 - methoxyphenyl) - 1,3,2,4 - dithiadiphosphetane - 2,4 -disulfide, 1, gave 2 - (p - methoxyphenyl) - 4 - 1,3,2 - benzoxathiaphosphorin - 4 - one 2 - sulfide, 3, and its thio-analogue, 4, while its ethyl or phenyl esters gave 4 as the sole product. 2 - Mercaptobenzoic acid and its ethyl ester when heated with 1 produced 3 - 1,2 - benzodithiole - 3 - one, 8, 3 -1,2 - benzodithiole - 3 - thione, 9, and 2- (p - methoxyphenyl) - 4 - 1,3,2 - benzodithia - phosphorin - 4 - one 2 - sulfide, 10. The reaction of 2 -aminobenzoic acid with 1 gave 1,2 - dihydro - 2 - (p - methoxyphenyl) - 4 - 3,1,2 - benzoxaphosphorin - 4 - one 2 - sulfide, 12. Reactions of 1 with methyl 2 - aminobenzoate and 2 - aminobenzamides are described. Mechanistic considerations for the formation of the heterocyclic phosphorus compounds are presented. 相似文献
2-(Trifluoromethyl)imidazo[4,5-] and -[4,5-]quinoline have been prepared from 5(6),acetamido-2-(trifluoromethyl)benzimidazole and 7,8-diaminoquinoline respectively. These (trifluoromethyl)- quinolines like 2-(trifluoromethyl)imidazoles but unlike 2-(trifluoromethyl) benzimidazoles, undergo hydrolysis in dilute sodium hydroxide to give ultimately the corresponding imidazo[4,5-] and -[4,5-]- quinoline, respectively. 相似文献
The reactions (I) Hg2Cl2(s) + Br2(g) and (II) HgCl2(s) + HgBr2(s) have been investigated by an X-ray method. Both the reactions yield two forms of the mixed halide HgClBr, designated as α-HgClBr and β-HgClBr. The cell parameters of the two are as follows:α-HgClBr: , , , z = 4, ? = 5.91 g/cm3. The powder pattern and cell parameters are similar to that of HgCl2. Therefore it is probable that the chlorine atoms, in the linear halogenHghalogen molecules of HgCl2 structure have been replaced by bromines, and since the radius of the bromine atom is larger than that of chlorine, the lattice is larger in this case.β-HgClBr: , , , z = 4, ? = 5.40. These parameters are the same as those reported in the literature for β-Hg(ClBr)2, and its X-ray powder pattern is similar to HgCl2. Therefore this phase also has linear halogenHghalogen molecules but the distribution of Cl and Br atoms is perhaps random.Heating the products (I) and (II) up to the melting point increases the amount of α phase and decreases the β phase, whereas crystallization increases the β phase. DTA study has supported the X-ray findings. 相似文献
By appropriate choice of reaction conditions, the enantiomerically pure ()-(+)-2-(-tolylsulfinyl)cycloalkenone can be converted into an ()-or an ()-3-substituted cycloalkanone in good to excellent enantiomeric purity. 相似文献
A reinvestigation of the reaction of glyoxal with 2-(N-alkylamino)ethanol failed to yield the products previously reported, but led selectively to a condensed 2,3,5,6-dioxazino-dioxane and to an heterodecalin ; crystal structures have been established by X-ray crystallography. Furthermore, the easily synthesized triheterocycle reacts with nucleophiles to form original heterocycles. 相似文献