Reactions of dimethyl acetylenedicarboxylate—X: Reaction with salicylaldehyde,ortho hydroxyacetophenone, 2-hydroxychalcones and 2,2′-dihydroxychalcones

Salicylaldehyde reacts with dimethyl acetylenedicarboxylate in benzene solution to give a mixture of dimethyl o-formylphenoxymaleate, dimethyl o-formylphenoxyfumarate, 2,3-dicarbomethoxychrom - 2 - en - 4 - ol, 2,3 - dicarbomethoxychrom - 3 - en - 2 - ol, dimethyl (2,3 - dicarbomethoxychrom - 2 - en - 4 - yl) - oxalacetate and dimethyl fumarate. 2,3 - Dicarbomethoxychrom - 3 - en - 2 - ol in this reaction is formed from 2,3 - dicarbomethoxychrom - 2 - en - 4 - ol through a benzopyrylium intermediate. The reaction of salicylaldehyde with excess of dimethyl acetylenedicarboxylate, however, gives a mixture of 2,3 - dicarbomethoxychrom - 3 - en - 2 - ol and dimethyl (2,3 - dicarbomethoxychrom - 3 - en) - 2 - oxyfumarate. 2,3 - Dicarbomethoxychrom - 3 - en - 2 - ol itself reacts further with dimethyl acetylenedicarboxylate to give 2,3,12 - tricarbomethoxychrom - 3,4 - eno[2,3 - b] pyrone. Similarly, the reaction of o-hydroxyacetophenone with dimethyl acetylendicarboxylate gives a mixture of dimethyl o-acetylphenoxymaleate, dimethyl o-acetylphenoxyfumarate, 2,3 - dicarbomethoxy - 4 - methylchrom - 2 - en - 4 - ol and 2,3 - dicarbomethoxy - 4 - methylchrom - 3 - en - 2 - ol. Both 2-hydroxychalcone and 2 - hydroxy - 4′ - methoxychalcone give mixtures of chalcone - 2 - oxymaleate and chalcone - 2 - oxyfumarate. The reaction of 2,2t?-dihydroxychalcone, however, gives 2′-hydroxyflavone, in addition to the expected maleate and fumarate. Similar reactions of 5 - chloro - 2,2′ - dihydroxychalcone and of 3,5 - dibromo - 2,2′ - dihydroxychalcone, on the other hand, give 2,3 - dicarbomethoxy - 4 - (o - hydroxyphenacyl) - 6 - chlorochrom - 2 - ene and 2,3 - dicarbomethoxy - 4 - (o - hydroxyphenacyl) 6,8 - dibromochrom - 2 - ene, respectively, together with the corresponding maleates and fumarates.     

2-芳基吲哚的敏化光氧化偶合反应

本文研究了十七种2-芳基吲哚(1a-1q)在甲醇-乙酸介质中的亚甲基蓝(MB)敏化光氧化反应, 发现有十五种吲哚(1a-1o)以85%-95%的产率给出2,2'-二芳基-[2,3'-联-1H-吲哚]-3(2H)-酮(2a-2o), 而2-(4-硝基苯基]吲哚(1p)和2-联苯基吲哚(1q)则分别生成2-甲氧基-2-(4-硝基苯基)-1,2-二氢-3H-吲哚-3-酮(7p)和2-联苯基-4H-3,1-苯并恶嗪-4-酮(11q), 其中7p在分离过程中失去甲醇分子给出2-(4-硝基苯基)-3H-吲哚-3-酮(10p)。     

Isolation and synthesis of glutamine and glutarimide derivatives fromCroton humilis

Extract ofCroton humilis L. were shown to contain N - [N - (2 - methylpropanoyl) -l - glutaminoyl] - 2 - phenylethylamine, N - [N - 2R - methylbutanoyl) -l - glutaminoyl] - 2 - phenylethylamine, 2 - [N- (2 - methylpropanoyl)] - N - phenylethylglutarimide and 2 - [N- (2R - methylbutanoyl)] - N - phenylethylglutarimide. Structural proof was based on acid degradation, spectral studies as well as the synthesis of N - [N- (2- methylpropanoyl) -l - glutaminoyl] - 2 - phenylethylamine and 2 - [N - (2 - methylpropanoyl] - N - phenylethylglutarimide.     

Diisophorone and related compounds—IV: 2,7-Epoxydiisophoranes: synthesis and reactions of 3,4-diketo-2,7-epoxydiisophoran-1-OL

Selenium dioxide oxidises 2,7 - epoxydiisophoran - 1 - ol - 3 - one to the corresponding yellow 3,4-diketone. This is reduced to diisophor - 2(7) - en - 1 - ol - 3 - one (“diisophorone”) by Zn in acetic acid or on catalytic hydrogenation, or to 2,7 - epoxydiisophorane - 1,3,4 - triol by LAH or NaBH₄. Alkaline H₂O₂ cleaves ring A of the 3,4-diketone, providing a degradation of the diisophorane- to the bicyclo[3.3.1]nonane-system. The resulting 3 - (2' - carboxy - 2',2' - dimethyl)ethyl -2, 3 - epoxy -1 - hydroxy - 5,7,7 - trimethylbicyclo(3.3.1]nonane - 2- carboxylic acid is convertible into its dimethyl ester by the action of diazomethane.     

Synthesis,optical, and spectroscopic characterisation of substituted 3-phenyl-2-arylacrylonitriles

The Knoevenagel condensation between aldehydes and substrates with active methylene groups was applied to synthesise a series of 3-(4-substituted phenyl)-2-arylacrylonitriles (aryl = phenyl or pyridyl). Chloro-, fluoro-, or dimethylamino-substituted aryls and a cyano group attached to the double bond of acrylonitrile were studied. Previous studies showed that the condensation products were E isomers. The compounds synthesised were: 3-(4-chlorophenyl)-2-phenylacrylonitrile, 3-(4-chlorophenyl)-2-(pyridin-2-yl)acrylonitrile, 3-(4-chlorophenyl)-2-(pyridin-3-yl)acrylonitrile, 3-(4-chlorophenyl)-2-(pyridin-4-yl)acrylonitrile, 3-(4-fluorophenyl)-2-phenylacrylonitrile, 3-(4-fluorophenyl)-2-(pyridin-2-yl)acrylonitrile, 3-(4-fluorophenyl)-2-(pyridin-3-yl)acrylonitrile, 3-(4-fluorophenyl)-2-(pyridin-4-yl)acrylonitrile, 3-(4-dimethylaminophenyl)-2-phenylacrylonitrile, 3-(4-dimethylaminophenyl)-2-(pyridin-2-yl)acrylonitrile, 3-(4-dimethylaminophenyl)-2-(pyridin-3-yl)acrylonitrile, and 3-(4-dimethylaminophenyl)-2-(pyridin-4-yl)acrylonitrile. Structures were confirmed by IR, MS, and NMR spectral data. Molar absorption coefficient, absorbance, and fluorescence emission spectra were compared in order to evaluate the effects of substituents on phenyl and the position of nitrogen in pyridine moiety on the electronic properties of acrylonitrile derivatives prepared.     

3-取代胺甲基-5-连三唑基-1,3,4-噁二唑-2-硫酮的合成

2-苯基-1,2,3-三唑-4-甲酰肼(1)在CS_2/KOH作用下环化得到5-(2-本基-1,2,3-连三唑-4-基)-1,3,4-噁二唑-2-硫酮(2),2经Mannich反应合成得到标题化合物3-取代胺甲基-5-(2-本基-1,2,3-连三唑-4-基)-1,3,4-噁二唑-2-硫酮(3)。     

Generation of simple methylenecyclopropenes as reactive intermediates

The dehydrochlorination of either 1,2 - dichloro - 1 - methylcyclopropane or 1 - bromo - 2 - chloro - 2 - methylcyclopropane with potassium t-butoxide yields 2 - t - butoxy - 1 - methylenecyclopropane. These results are interpreted in terms of methylenecyclopropene as a reactive intermediate which is trapped by addition of nucleophile (t-butoxide) to the cyclopropenyl double bond. The introduction of methanethiol to the reaction medium yields 2 - thiomethyl - 1 - methylenecyclopropene 2,2 - Dichloro - 1 - methylenecyclopropane reacts with potassium t-butoxide in tetrahydrofuran to yield trans- and cis - t - butoxybut - 1 - ene - 3 - yne. The addition of thiomethide ion results in the formation of 2,2 - bis(thiomethyl) - 1 - methylenecyclopropane and 2 - t - butoxy - 2 - thiomethyl - 1 - methylenecyclopropane. Other evidence for simple methylenecyclopropenes as reactive intermediates comes from the observation that nucleophiles add nonregiospecifically to the reactive intermediate produced by the dehydrohalogenation of 2 - halo - 1 - alkylidenecyclopropanes. Novel methylenecyclopropane→ cyclopropene transformations were found in the reaction of 2 - halomethylenecyclopropanes with thiomethide ion.     

载体对担载Ni催化剂甲烷与二氧化碳重整反应活性的影响

制备了 Zr O2 、Mg O改性的 Al2 O3、Ti O2 复合载体 ,并应用 X-射线粉末衍射 (XRD)、比表面积测定、扫描电镜 (SEM)等手段进行了表征 .结果表明 ,这些氧化物在 Al2 O3上的晶粒尺寸小、比表面积大 ,分散较好 ,而在Ti O2 上的分散性较差 .对经 10 73K焙烧的 Mg O/ Ti O2 ,还发现部分 Ti O2 载体由锐钛矿变为金红石 ,同时生成Mg Ti O3 新相 .考察了载体对 Ni催化剂的 CH4与 CO2 重整反应活性的影响 ,其次序为 :Mg O/ Al2 O3>Zr O2 /Al2 O3>Al2 O3>Mg O >Zr O2 >Ti O2 >Mg O/ Ti O2 . Ti O2 及 Mg O/ Ti O2 担载 Ni催化剂的低活性可能与 Ti O2 本身的还原性有关     

The reducive amination of phthalaldehyde by tetracarbonylhydridoferrate : Synthesis of 2-arylisoindoles

Phthalaldehyde reacted with primary amines in the presence of tetracarbonylhydridoferrate under mild conditions to give 2-substituted isoindoles and/or isoindolines in good to excellent yields. Aliphatic amines gave selectively the isoindolines but aromatic amines had a great tendency to the isoindoles. 2-(2-Tolyl)-, 2-(4-tolyl)-, 2-(4-methoxyphenyl)-, 2-(3-chlorophenyl)-, 2-(4-chlorophenyl)- and 2-(3,4-dichlorophenyl)-isoindole were prepared by this method.     

新型P,N配体及基1,4-共轭加成反应

以2-萘酚为起始原料,经过氧化偶联,消旋体的拆分得到手性骨架2-氨基-2'-羟基-1,1'-联萘(NOBIN),并以S-NOBIN为原料,经过六步反应合成了两个新型配体S-(+)-2-(2-吡啶酰胺基)-2'-二苯基膦基-1,1'-联萘(1a)和S-(+)-2-(6-甲基-2-吡啶酰胺基)-2'-二苯基膦基-1,1'-联萘(1b)。并进行了铜配合物催化的二乙基锌对2-环己烯酮的1,4-共轭加成反应的研究。反应产物3-乙基环己酮(13)的e.e.值高达92%。     

Synthesis of 1-alkoxy-3-(2-hydroxyethyl)-1-triazene 2-oxides

Synthetic procedure to access the first representatives of a new series of 3-monosubstitued functional derivatives of 1-alkoxy-1-triazene 2-oxides, i.e., 1-alkoxy-3-(2-hydroxyethyl)- and 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides, were elaborated. 1-Alkoxy-3,3-bis(2-hydroxyethyl)-1-triazene 2-oxides were used to derive 3-(2-acetoxyethyl)-, 3-(2-bromoethyl)- and 3-(2-cyanoethyl)substituted 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides.     

A Raman and infrared spectroscopic study of the uranyl silicates--weeksite, soddyite and haiweeite: part 2

Raman spectroscopy has been used to study the molecular structure of a series of selected uranyl silicate minerals including weeksite K2[(UO2)2(Si5O13)].H2O, soddyite [(UO2)2SiO4.2H2O] and haiweeite Ca[(UO2)2(Si5O12(OH)2](H2O)3 with UO2(2+)/SiO2 molar ratio 2:1 or 2:5. Raman spectra clearly show well resolved bands in the 750-800 cm(-1) region and in the 950-1000 cm(-1) region assigned to the nu1 modes of the (UO2)2+ units and to the (SiO4)4- tetrahedra. Soddyite is characterized by Raman bands at 828.0, 808.6 and 801.8 cm(-1), 909.6 and 898.0 cm(-1), and 268.2, 257.8 and 246.9 cm(-1), attributed to the nu1, nu3, and nu2 (delta) (UO2)2+, respectively. Coincidences of the nu1 (UO2)2+ and the nu1 (SiO4)4- is expected. Bands at 1082.2, 1071.2, 1036.3, 995.1 and 966.3 cm(-1) are attributed to the nu3 (SiO4)4-. Sets of Raman bands in the 200-300 cm(-1) region are assigned to nu2 (delta) (UO2)2+ and UO ligand vibrations. Multiple bands indicate the non-equivalence of the UO bonds and the lifting of the degeneracy of nu2 (delta) (UO2)2+ vibrations. The (SiO4)4- tetrahedral are characterized by bands in the 470-550 cm(-1) and in the 390-420 cm(-1) region. These bands are attributed to the nu4 and nu2 (SiO4)4- bending modes. The minerals show characteristic OH stretching bands in the 2900-3500 and 3600-3700 cm(-1).     

Reactivity of TCNE or TCNQ derivatives of quinonoid zwitterions: platinum-induced HCN elimination vs oxidative-addition

The reaction of the functional, zwitterionic quinonoid molecule (6E)-4-(butylamino)-6-(butyliminio)-3-oxo-2-(1,1,2,2-tetracyanoethyl)cyclohexa-1,4-dien-1-olate, [C(6)H-2-{C(CN)(2)C(CN)(2)H}]-4,6-(···NH n-Bu)(2)-1,3(···O)(2) (2), which has been previously prepared by regioselective insertion of TCNE into the C-H bond adjacent to the C···O bonds of the zwitterionic benzoquinone monoimine (6E)-4-(butylamino)-6-(butyliminio)-3-oxocyclohexa-1,4-dien-1-olate, C(6)H(2)-4,6-(···NHn-Bu)(2)-1,3-(···O)(2) (1), with 2 equiv of [Pt(C(2)H(4))(PPh(3))(2)], afforded the Pt(0) complex [Pt(PPh(3))(2)(4)] (6) (4 = 2-HCN; (6E)-4-(butylamino)-6-(butyliminio)-3-oxo-2-(1,2,2-tricyanoethenyl)cyclohexa-1,4-dien-1-olate), in which a tricyanoethenyl moiety is π-bonded to the metal. A metal-induced HCN elimination reaction has thus taken place. The same complex was obtained directly by the reaction of 1 equiv of the Pt(0) complex [Pt(C(2)H(4))(PPh(3))(2)] with the olefinic ligand [C(6)H-2-{C(CN)═C(CN)(2)}]-4,6-(···NHn-Bu)(2)-1,3-(···O)(2)) (4), previously obtained by the reaction of 2 with NEt(3) in THF. A similar reactivity pattern was observed between 2 and 2 equiv of the Pd(0) precursor [Pd(dba)(2)] in the presence of dppe, which led to [Pd(dppe)(4)] (7), which was also directly obtained from 4 and 1 equiv [Pd(dba)(2)]/dppe. In contrast to the behavior of the TCNE derivative 2, the reaction of the TCNQ derivative (6E)-4-(butylamino)-6-(butyliminio)-2-(dicyano(4-(dicyanomethyl)phenyl)methyl)-3-oxocyclohexa-1,4-dien-1-olate, [C(6)H-2-{C(CN)(2)p-C(6)H(4)C(CN)(2)H}]-4,6-(···NHn-Bu)(2)-1,3-(···O)(2)) (3), with 2 equiv of [Pt(C(2)H(4))(PPh(3))(2)] led to formal oxidative-addition of the C-H bond of the C(CN)(2)H moiety to give the Pt(II) hydride complex trans-[PtH(PPh(3))(2){N═C═C(CN)p-C(6)H(4)C(CN)(2)-2-[C(6)H-4,6-(···NHn-Bu)(2)-1,3-(···O)(2))}] (8). The molecular structures of 3, 4, 6·0.5(H(2)O), and 8·3(CH(2)Cl(2)) have been determined by single-crystal X-ray diffraction.     

Synthesis of 1,3-dithianes and 1,3-dithiolanes. Baker's yeast reduction and lipase-catalyzed resolution for synthesis of enantiopure derivatives.

Three 1,3-dithiolanes and four 1,3-dithianes have been synthesised from 1-(1,3-dithiolan-2-yl)-2-propanone and 1-(1,3-dithian-2-yl)-2-propanone, respectively. Asymmetric reductions of these ketones using baker's yeast gave the corresponding enantiopure (S)-alcohols. Baker's yeast also reduced the double bond in 3-(1,3-dithian-2-yl)-3-buten-2-one enantioselectively to give (S)-3-(1,3-dithian-2-yl)-2-butanone. 3-(1,3-Dithian-2-yl)-3-buten-2-one was also reduced chemo-selectively and the resulting 3-(1,3-dithian-2-yl)-3-buten-2-ol was resolved by transesterification in organic solvent using lipase B from Candida antarctica to yield the (S)-alcohol and the (R)-acetate with very high enantiomeric ratio, E. Racemic 1-(1,3-dithiolan-2-yl)-2-propanol and 1-(1,3-dithian-2-yl)-2-propanol were also resolved under similar conditions to give the (S)-alcohols and the corresponding (R)-acetates.     

Cyanoacetylene and Its Derivatives: XXVIII. Reactions of 2-Mercaptobenzothiazole with Nitriles of αα,ββ-Acetylene γγ-Hydroxyacids and with 3-Phenyl-2-propynonitrile

Nucleophilic addition of 2-mercaptobenzothiazole to 4-alkyl-4-hydroxy-2-alkynonitriles at 1:1 ratio in the presence of 4-6 wt% of Et₃N occurs regio- and stereospecifically to afford (Z)-4-alkyl-3-(benzothiazolyl-2-thio)-4-hydroxy-2-alkenonitriles (yield 40-51%). In the presence of 1.3 wt% of Dabco the thiazole and 4-hydroxy-4-methyl-2-pentynonitrile (1:1) give rise to a mixture of 2-alkenonitrile and 2-(3,3,6,6-tetramethyl-2-cyanomethyl-5-cyanomethylene-1,4-oxathian-2-yl)thiobenzothiazole. At the use of 4-6 wt% of LiOH arises an intractable mixture containing 1,4-oxathiane, benzothiazol-2-one, 2-[1-(5,5-dimethyl-2-cyanomethyl)-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl]thiobenzothiazole, bis(2,2,5,5-tetramethyl-6-cyanomethyl-3-cyanomethylene-1,4-oxathian-6-yl) disulfide, bis[1-(5,5-dimethyl-2-cyanomethyl-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl] disulfide, and 3-[1-(5,5-dimethyl-2-cyanomethyl-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl]benzothiazol-2-one (according to ¹H and ¹³C NMR data). 2-mercaptobenzothiazole adds to 3-phenyl-2-propynonitrile in the presence of 7 wt% of KOH with regio- and stereospecific formation of (Z)-3-(benzothiazolyl-2-thio)-3-phenyl-2-propenonitrile (88%).     

The autoxidation of 2-(2-aminophenyl)-3- methylindole

Fischer indolisation of 2-aminophenyl ethyl ketone phenylhydrazone using glacial acetic acid saturated with hydrogen chloride as catalyst affords 3-methylindolo(l′:2′-3:4)2-methylquinazoline and 2-(2-aminophenyl)-3-methylindole. The latter compound is autoxidised to 2-(2-amino-phenyl)-3-hydroxy-3-methyl-3H-indole, a reaction which is shown to be dependent upon the presence of the primary amino group at the 2-position of the 2-phenyl substituent and which is much slower than the corresponding autoxidation of 2-(2-hydroxyphenyl)-3-methylindole to 3-hydroxy-2-(2-hydroxyphenyl)-3-methyl-3H-indole previously reported.Nitration of isopropyl phenyl ketone occurs preferentially at the ortho- rather than the meta- positions of the benzene nucleus.     

Substitution, cage functionalization, and oxidation of the charge-compensated triruthenium monocarbollide cluster complex [1-SMe2-2,2-(CO)2-7,11-(mu-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8

The compound [1-SMe2-2,2-(CO)2-7,11-(mu-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8] 1a reacts with PMe3 or PCy3(Cy = cyclo-C6H11) to give the structurally different species [1-SMe2-2,2-(CO)2-7,11-(mu-H)2-2,7,11-{Ru2(CO)5(PMe3)}-closo-2,1-RuCB10H8] 4 and [1-SMe2-2,2-(CO)2-11-(mu-H)-2,7,11-{Ru2(mu-H)(CO)5(PCy3)}-closo-2,1-RuCB10H8]5, respectively. A symmetrically disubstituted product [1-SMe2-2,2-(CO)2-7,11-(mu-H)2-2,7,11-{Ru2(CO)4(PMe3)2}-closo-2,1-RuCB10H8] 6 is obtained using an excess of PMe3. In contrast, the chelating diphosphines 1,1'-(PPh2)2-Fe(eta-C5H4)2 and 1,2-(PPh2)2-closo-1,2-C2B10H10 react with 1a to yield oxidative-insertion species [1-SMe2-2,2-(CO)2-11-(mu-H)-2,7,11-{Ru2(mu-H)(micro-[1',1'-(PPh2)2-Fe(eta-C5H4)2])(CO)4}-closo-2,1-RuCB10H8] 7 and [1-SMe2-2,2-(CO)2-11-(mu-H)-2,7,11-{Ru2(mu-H)(CO)4(1',2'-(PPh2)2-closo-1',2'-C2B10H10)}-closo-2,1-RuCB10H8] 8, respectively. In toluene at reflux temperatures, 1a with Bu(t)SSBu(t) gives [1-SMe2-2,2-(CO)2-7-(mu-SBu(t))-11-(mu-H)-2,7,11-{Ru2(mu-H)(mu-SBu(t))(CO)4}-closo-2,1-RuCB10H8] 9, and with Bu(t)C [triple bond] CH gives [1-SMe2-2,2-(CO)2-7-{mu:eta2-(E)-CH=C(H)Bu(t)}-11-{mu:eta2-(E)-CH=C(H)Bu(t)}-2,7,11-{Ru2(CO)5}-closo-2,1-RuCB10H8] 10. In the latter, two alkyne groups have inserted into cage B-H groups, with one of the resulting B-vinyl moieties involved in a C-H...Ru agostic bond. Oxidation of 1a with I2 or HgCl2 affords the mononuclear ruthenium complex [1-SMe2-2,2,2-(CO)3-closo-2,1-RuCB10H10] 11.     

Disproportionation pathways of aqueous hyponitrite radicals (HN2O2(*)/N2O2(*-))

Pulse radiolysis and flash photolysis are used to generate the hyponitrite radicals (HN2O2(*)/N2O2(*-)) by one-electron oxidation of the hyponitrite in aqueous solution. Although the radical decay conforms to simple second-order kinetics, its mechanism is complex, comprising a short chain of NO release-consumption steps. In the first, rate-determining step, two N2O2(*-) radicals disproportionate with the rate constant 2k = (8.2 +/- 0.5) x 10(7) M(-1) s(-1) (at zero ionic strength) effectively in a redox reaction regenerating N2O2(2-) and releasing two NO. This occurs either by electron transfer or, more likely, through radical recombination-dissociation. Each NO so-produced rapidly adds to another N2O2(*-), yielding the N3O3(-) ion, which slowly decomposes at 300 s(-1) to the final N2O + NO2(-) products. The N2O2(*-) radical protonates with pKa = 5.6 +/- 0.3. The neutral HN2O2(*) radical decays by an analogous mechanism but much more rapidly with the apparent second-order rate constant 2k = (1.1 +/- 0.1) x 10(9) M(-1) s(-1). The N2O2(*-) radical shows surprisingly low reactivity toward O2 and O2(*-), with the corresponding rate constants below 1 x 10(6) and 5 x 10(7) M(-1) s(-1). The previously reported rapid dissociation of N2O2(*-) into N2O and O(*-) does not occur. The thermochemistry of HN2O2(*)/N2O2(*-) is discussed in the context of these new kinetic and mechanistic results.     

2-氯-2-氧代(硫代)-1, 3, 2-二氧磷杂环己烷的甲醇解及其开环 异构化反应

报道了trans-2-氧代-2-氯-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷以及cis-2-硫代-2-氯-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷甲醇解反应的立体化学。结果表明,反应体系的酸碱性对前者甲醇解反应的立体化学有着重要影响。而硫代环磷酰氯在碱性条件下的甲醇解反应存在一个开环异构化过程。     

Synthesis of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles

The reaction of azolylacetonitriles with γ-chlorobutyryl chlorides gave the corresponding 2-(1-R-1,3-di- hydro-2H-benzimidazol-2-ylidene)-, 2-(1,3-benzothiazol-2-ylidene)-, and 6-chloro-2-(4-methylthiazol-2-ylidene)-3-oxohexanenitriles. A study of the intramolecular cyclization of 2-(quinazolin-2-ylidene)-3-oxo-6-hexanenitriles and -heptanenitriles has led to the development of an efficient method for the preparation of 2-(quinazolin-2-yl)-2-(tetrahydrofuran-2-ylidene)acetonitriles. The (Z,E)-isomerism of the synthesized 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles was studied.