CONDENSATION REACTION OF α-AROYL-α-ACETYL KETENE CYCLIC DITHIOACETALS WITH AROMATIC ALDEHYDES

As a versatile three-carbon syntho,α-oxoketene cyclic acetals 1 have been applied in many fields. In order to study the structure and application of 1, we performed that α-aroyl-α-acetyl ketene cyclic dithioacetals 2 or 3 condensed with aromatic aldehydes catalyzed by sodium ethoxide and fifteen new condensation products 4 and 5 were obtained.     

α－OXOKETENE CYCLIC DITHIOACETALS CHEMISTRY ──REACTION OF α，α－DIOXO（ESTER）KETENE CYCLIC DITHIOACETALS WITH BUTANONE

α－ＯＸＯＫＥＴＥＮＥＣＹＣＬＩＣＤＩＴＨＩＯＡＣＥＴＡＬＳＣＨＥＭＩＳＴＲＹ──ＲＥＡＣＴＩＯＮＯＦα，α－ＤＩＯＸＯ（ＥＳＴＥＲ）ＫＥＴＥＮＥＣＹＣＬＩＣＤＩＴＨＩＯＡＣＥＴＡＬＳＷＩＴＨＢＵＴＡＮＯＮＥ￥ＺａｉＭｉｎｇＺＨＵ；ＹｏｎｇＴｉｎｇＸ...     

STUDIES ON THE REACTIVITY OF CYCLOAROMATIZATION REACTION VIA a－OXO KETENE DITHIOACETALS

ＳＴＵＤＩＥＳＯＮＴＨＥＲＥＡＣＴＩＶＩＴＹＯＦＣＹＣＬＯＡＲＯＭＡＴＩＺＡＴＩＯＮＲＥＡＣＴＩＯＮＶＩＡａ－ＯＸＯＫＥＴＥＮＥＤＩＴＨＩＯＡＣＥＴＡＬＳ￥ＱｕｎＬＩＵ；ＺｈｉＬｉｎｇＷＡＮＧ；ＳｈｕＪｉａＺＨＡＮＧ；ＺｈｉＹｕｎＹＡＮＧ（Ｄｅｐａｒ...     

ON THE POLYCONDENSATION REACTION WITH MONOMER OF A_aB_b TYPE (Ⅲ)——THE SCALING STUDY

For the polycondensation reaction with monomer of A_aB_b type, the scaling problem asso-ciated with sol-gel transition is investigated to obtain an asymptotic form of the equilibriumnumber fraction distribution of n-mer near the gel point. As a direct result, a generalizedscaling law is obtained.     

STUDIES ON THE REACTION OF d-ACETAMIDCCINNAMAMIDE WITH TRIS(DIETHYLAMINO)PHOSPHINE

d-Acetamidocinnamamide do not react with P(OMe)_3, with P(NEt_2)_3 they give rise to 2-methyl-4-hydroxy-5-d-[bis(diethylamino)phosphoryl] benzyl imidazole.The pathway is studied for the formation of Ⅰ. The two intermediates(Ⅱ) are isolated.The structures of Ⅰ and Ⅱ are confirmed by IR, ~1H NMR, ~(31)P NMR, Ms.     

APPLICATION OF NOETHER'S THEOREM IN CHEMISTRY (Ⅲ)——THE SKILL IN REACTION OPERATOR

IN the previous papers of the author's,the elementary reactionoperator concerning point group was discussed.In thispaper,more complex reaction operators will be analysed.Byusing the skillin reaction operator,the electrocyclic and cy-cloaddition reactions are illustrated.     

ON THE POLYCONDENSATION REACTION WITH MONOMER OF A_aB_b TYPE (Ⅱ)——THE POLYMER MOMENTS

With monomer of A_aB_b type, the polymer moments of polycondensation reaction is inves-tigated in detail by means of direct differentiation technique to obtain a recursion formula.This formula is suitable for both pre-gel and post-gel in evaluating the polymer momentsexplicitly.     

KINETIC STUDIES ON THE ACID-CATALYZED PUMMERER REACTION OF α-(METHYLSULFINY)ACETOPHENONES

Abstract

The kinetic behavior of the acid-catalyzed Pummerer reaction of α-(methylsulfinyl)acetophenones in dilute hydrochloric acid has been studied in detail. The kinetic data were analyzed in the light of correlations between the reaction rates and acidity functions, activation parameters, solvent isotope effects, polar effects of substituents, etc. Moreover, ¹⁸O-tracer experiments were also carried out using acid media containing H₂ ¹⁸O. Based on these observations, a plausible mechanism for this reaction has been discussed.     

ON THE POLYCONDENSATION REACTION OF A_a<(B_b C_c) TYPE

For the polycondensation reaction of A_a相似文献   

STUDIES ON POLYHALOALKANES Ⅳ. THE REACTION OF POLYFLUOROALKYL IODIDES WITH SILVER(I) SALTS

The conversion of polyfluoroalkyl iodides into the corresponding carboxylic acids by the reaction with silver (I) salts is described.     

THE CONDENSATION REACTION OF BIS(PERFLUOROALKANESULFONYL)METHANES WITH AROMATIC ALDEHYDES

The ccndensation reactions occurred when heating bis(perfluoroalkane-sulfonyl)methanes with aromatic aldehydes in acetic acid anhydrideand gave high yields of 1-aryl-2,2-di(perfluoroalkanesulfonyl)ethylenesThe perfluoroalkanesulfonyl groups R_FSO_2 are known as the strongestelectron-attracting substituents~(1-2).This property is often used in theactivation of C-C multiple and 2,2'-C-H bonds.The synthesis and reactionsof perfluoroalkanesulfonyl substituted alkenes and alkynes are of greatinterest in synthetic organic chemistry~(3-6).Recently,Hanack~7 reported the preparation of 2-aryl-l-(perfluoroalkane-sulfonyl)acrylonitrile R_FSO_2C(CN)=CHAr.However,he failed to obtainthe 1,1-di(perfluoroalkanesulfonyl)alkenes by the Knoevenagel reactionof bis(perfluoroalkanesulfonyl)methane with aldehydes.     

STUDIES ON CYCLOPENT-2-ENONE: (Ⅲ) THE STUDY ON DECONJUGATION OF CYCLOPENT -2-ENONE ALDOL ADDUCTS

Deconjugation of cyclopent-2-enone aldols were attempted under various conditions, and the desired deconjugated product was achieved via dianion approach. Various results obtained in this study are explained by structure and transition state analysis.     

STUDIES ON THE ADDITION REACTION OF GRIGNARD REAGENTS TO α－CINNAMOYLKETENE（1，3－PROPYLENE）DITHIOACETALS

ＳＴＵＤＩＥＳＯＮＴＨＥＡＤＤＩＴＩＯＮＲＥＡＣＴＩＯＮＯＦＧＲＩＧＮＡＲＤＲＥＡＧＥＮＴＳＴＯα－ＣＩＮＮＡＭＯＹＬＫＥＴＥＮＥ（１，３－ＰＲＯＰＹＬＥＮＥ）ＤＩＴＨＩＯＡＣＥＴＡＬＳＱｕｎＸｉｎｇＦＡＮＧ；ＣｈｕｎＬＩＮ；ＳｈｕＪｉａＺＨＡＮＧ；...     

KINETIC AND APPLICATION: STUDIES ON THE REACTION SYSTEM OF OSMIUM(Ⅳ)-ARSENIC(Ⅲ)-CHLORATE

The experiments have proved that Os(Ⅳ) has very strong catalytic effect on the chlorate oxidation of As(Ⅲ) in perchloric acid media, and As(Ⅲ) exhibits a sensitive single-sweep oscillopolarographic wave at-0.75 V vs. SCE. The kinetics of this catalytic reaction has been investigated by the initial rate procedure. The mechanism has been proposed. A new and highly sensitive catalytic reaction-oscillopolarographic method for the determination of ultratrace amounts of osmium has been described, based on the Os(Ⅳ) catalytic effect on the reaction. The linear range of 5.0×10~(-11)-4.4×10~(-9) mol/L and 6.0×10~(-9)-1.3×10~(-7) mol/L Os was obtained using the fixed-time procedure and the initial rate procedure, respectively. Osmium in refined ore was analysed by this method.     

ON THE POLYCONDENSATION REACTION WITH MONOMER OF A_aB_b TYPE (Ⅰ)——SOL FRACTION AND GELATION CONDITION

With monomer of A_aB_b type, the sol fraction of polycondensation for post-gel, in whichnot only the functional groups of A to react with those of B, but also the functional groupsof A with those of A and the functional groups of B with those of B are involved, is discuss-ed in detail. As a direct result, the gelation condition is obtained explicitly.     

STUDIES ON THE WITTIG REACTION(XIII): KINETICS OF THE PTC-WITTIG REACTIONS OF 2-BUTENYL METHYL-DIPHENYLPHOSPHONIUM SALT WITH SUBSTITUTED BEN2ALDEHYDES

The kinetics of PTC-Wittig reaction between substitutedaromatic aldehydes and 2-butenyl methyldiphenylphosphonium salthas been studied. The low reaction constant (ρ=0. 30) impliesthat these PTC-Wittig reactions take place through low polarintermediate.     

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS Ⅲ TRANSMETALLATION REACTION OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS WITH METALLIC TIN

The transmetallation reaction of 4 Schiff base type arylmercury compoundswith metallic tin has been carried out in refluxing xylene.It was found that thereaction proceeds in the same manner as that of chloro[2-(phenylazo)phenyl]mercury(Ⅱ)to give dichlorobisaryltin(Ⅳ).The ~1H NMR spectra of the products provide evidence forthe presence of N→Sn intramolecular coordination.The formation ofdichlorobisaryltin(Ⅳ)as a unique product probably arises from the N→Sn intramolecularcoordination which results in the increasing of the stability of the molecule.     

ENE REACTION WITH PUMMERER-TYPE REACTION INTERMEDIATE OF α-(METHYLTHIO)ACETIC ACID PYRROLIDIDE:SYNTHESIS OF ACHILLEA AMIDE AND TRICHONINE

The dienamide group is an important structural feature of a number of natural products, which have been reported to be biologically active, especially as insecticides. Several methods for their synthesis have appeared involving Wittig reaction, elimination reaction, and amidation of corresponding dienoic acids or esters. Achillea amide [(E,E)-2,4-tetradecadienoic acid pyrrolidide] and Trichonine [(E,E)-2,4-eicosadienoic acid pyrrolidide)] which are naturally occurring insecticides isolated from Achillea nana and P. trichostachyon leaves, respectively. Severál methods have reported successful syntheses of unsaturated pyrrolidine amides. In this work we wish to report that the Pummerer-type reaction intermediate 2 derived from α-(methylthio)acetic acid pyrrolidide (1) and phenyliodine(Ⅲ) bis(trifluoroacetate) (PIFA) undergoes an ene reaction with 1-alkenes to give the ene adducts 3. Also reported is its application to the synthesis of Achillea amide (4) and Trichonine (5).     

A RAPID FLUORIMETRIC DETERMINATION OF TYROSINE IN SERUM BY THE REACTION WITH CERIUM (Ⅳ)

A fluorimetric method for the determination of tyrosine in serum was proposed. The fluoriscence intensity is a linear function of tyrosine content in the range 0-1. 44ug/ml. The percentage of recovery was satisfactory.     

HIGHER VIBRATIONAL EXCITATION OF OH(Х~зП,v)FROM THE REACTION OF O(D)WITH TETRAMETHYLSILANE

The vibrational excited OH(X~ Ⅱ,v=1—4)was observed by time-resolvedFTIR emission spectroscopy.The nascent species were produced by a reaction ofO(~1D) and Si(CH_3).The effect of beery Si atom blocking the energy migration wasidentified.