A NEW CONVENIENT SYNTHESIS OF S-ALKYL N,N-DIALKYL THIOPHOSPHORAMIDIC ACID DERIVATIVES

The chlorination of O,O-dialkyl N,N-dialkyl thiophosphoramidateswith phosphorus oxychloride proceeds with isomerization to give S-alkylN,N-dialkyl thiophosphoramidochloridates,which react further with variousnucleophiles in the presence of base to give the title compounds.     

A CONVENIENT SYNTHESIS OF β-CYCLODEXTRIN 2-AND 3-O-MONOBENZOATE

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A CONVENIENT PREPARATION OF 1,2,3,4,5,6,7,8-OCTAHYDRO-NAPHTHALENE SKELETON. SYNTHESIS OF (±)-ISOCARIDIENE

ABSTRACT

Synthesis of isocaridiene, an isomeric compound of natural sesquiterpene caridiene, is described starting from myrcene. Dehydration of tertiary alcohol leading exclusively to isocaridiene was in agreement with the semiempirical and ab initio quantum mechanical calculations.     

A CONVENIENT SYNTHESIS OF S-ALKYL PHENYLTHIOPHOSPHONIC ACID DERIVATIVES

The chlorination of O,O-dialkyl phenylthiophosphonates withphosphorus oxychloride proceeds with isomerization to give S-alkyl phenyl-thiophosphonochloridates,which react further with various nucleophilesin the presence of base to obtain the title compounds.     

STUDY OF THE REACTION MECHANISM OF CYCLOHEXENE HYDROGENATION CATALYZED BY RhCl(PPh_3)_3

The hydrogenation rate of styrene in benzene using RhCI(PPh_3)_3 as catalyst increases with the concentration of styrene. But the hydrogenation rate of cyclohexene is rather different, It shows a maximum. So we inquire into the reaction mechanism of cyclohexene hydrogenation catalyzed by RhCI(PPh_3)_3. The rate of hydrogenation was measured at 25±0.15℃, as a function. of catalyst concentration, olefin concentration, triphenylphosphine concentration and hydrogen pressure. The maximum of the reaction rate is interpreted by the formation of RhClL_2S_2. The rate determining step is considered to be the reaction of olefin insertion into one of the Rh-H bonds formed by hydrogenation of RhClL3 to H_2RhClL_3. The hydrogenation rate of the substrate can be described by a third order equation in terms of concentration of H_2RhClL_3. Average error between the results evaluated by this equation and experimental results is about 4.9％. The quantum chemistry calculation gives support to the present mechanism.     

PALLADIUM CATALYZED REACTION OF 3-TRIMETHYLSILYLPROPARGYLIC CARBONATES WITH DINUCLEOPHILES

Methyl 3-trimethylsilylpropargyl carbonate reacted with dinucleophiles under the catalysis of palladium(0) complex to give the corresponding desilylated annulation products.     

A CONVENIENT SYNTHESIS OF 8-ALKYL S''''-ALKYL (ARYL) DITHIOPHOSPHORIC ACID DERIVATIVES**

The chlorination of S-alkyl(aryl) 0,0-dialkyl dithiophosphates with phosphorus oxychloride proceeds with isomerization to give S-alkyl S'-alkyl(aryl) dithiophosphorochtoridates, which react further with various nucleophiles in the presence of base to give the title compounds     

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.     

IRON(III)-ETHYLENEDIAMINETETRA-ACETIC ACID MEDIATED AEROBIC OXIDATION OF α-HYDROXYKETONES: A SIMPLE AND CONVENIENT SYNTHESIS OF α-DIKETONES

ABSTRACT

Iron(III)-ethylenediaminetetraacetic acid in aqueous methanol offers a simple, environmentally acceptable synthetic tool to oxidize α-hydroxyketones α-diketones with molecular oxygen, in excellent yields and under mild conditions and without any side reactions.     

SYNTHESIS OF 1 - (N - BENZYLOXYCARBONYLAMINO)ALKANEPHOSPHATES AND - PHOSPHINIC ACIDS CATALYZED BY A CATION EXCHANGE RESIN

An improved method is developed by using strongly acidic cation exchange resin(001×1, H+ form) as a catalyst for the synthesis of diphenyl 1 - (N - benzyloxycarbonyl - amino) alka-nephosphonates and 1 - (N - benzyloxycarbonylamino) alkanephenyl phosphinic acids in high yields.     

A CONVENIENT STEREOSELECTIVE SYNTHESIS OF CONJUGATED 1E,3E-DIENYL-DIENYL-DIETHYL PHOSPHONATE AND 1E,3E-DIENYLDIPHENYL PHOSPHINE OXIDE

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STUDIES ON THE REACTION OF SULFUR,SELENIUM AND TELLURIUM WITH SODIUM HYDROXIDE UNDER PHASE TRANSFER CATALYSIS(Ⅱ).A CONVENIENT METHOD FOR THE SYNTHESIS OF BI(ACYL)DISULFIDES

A simple and general method for the synthesis of bi(acyl)disulfides isreported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfideat 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides ingood to excellent isolated yields.The effects of solvents and phase transfercatalysts are discussed.     

SYNTHESIS AND CHARACTERIZATION OF A NEW POLYSILOXANE CONTAINING N,N’-BIS(DIPHENYLSILYL)TETRAPHENYLCYCLODISILAZANE

A new kind of polysiloxane containing N,N'-bis(diphenylsilyl)tetraphenylcyclodisilazane was prepared by anionicnon-equilibrium polymerization with a "seed solution" as initiator. The monomer, N,N'-bis(hydroxydiphenylsilyl)-tetraphenyl-cyclodisilazane (BHPTPC), was synthesized via the hydrolysis of N,N'-bis(chlorodiphenylsilyl)tetraphenyl-cyclodisilazane (BCPTPC). A new method for the preparation of BCPTPC is also reported here with high yield and simplermanipulation. The synthesized polysiloxane containing N,N'-bis(diphenylsilyl)tetraphenylcyclodisilazane was characterized by ~1H-NMR, ~(29)Si-NMR, gel permeation chromatography (GPC) and intrinsic viscosity.     

SYNTHESIS OF FUNCTIONAL MACROMOLECULE INTERMEDIATE THROUGH COUPLING REACTION CATALYZED BY [bmim]Cl/FeCl_3 IONIC LIQUID

1. INTRODUCTION The coupling reactions of aromatic compounds have important application in both laboratory work and industry processes such as in organic synthesis, dye preparation and pesticide produce, especially in special medicament exploiture. Since the cross-coupling reaction between Grignard agent and arylic halide catalyzed by complex compound of nickel and phosphorus was reported by Corriu and Kumada in 1972, various coupling reactions have been developed [1~4]. These coupling r…     

A NEW POLYFUNCTIONAL BIPYRIDINE ANALOGUE: MILD AND CONVENIENT SYNTHESIS OF 3,3′-BIS(5,6-DIBROMOMETHYL-1,2,4-TRIAZINE)

3,3′-Bis(5,6-dibromomethyl-1,2,4-triazine), a new polyfunctional bipyridine analogue for constructing supramolecular structures, has been synthesized from 2,3-butanedione and oxylhydrazidine by two routes in moderate to high yields.     

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 NOVEL SYNTHESIS OF α－ARYLSELENO－α－ACYL PHOSPHORANES AND ITS INTRAMOLECULAR WITTIG REACTION

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SYNTHESIS OF MESO-TETRA (4-METHOXYPHENYL-3-SULFONATE) PORPHINE AND SPECTROPHOTOMETRIC STUDY OF COLOUR REACTION WITH COPPER

In this paper meso-tetra (4-methoxyphenyl-3-sulpho) Porphine (TMPPS_4) was synthesized and its colour reaction with copper was studied. It was found to be a highly sensitive and highly selective reagent for the direct spectrophotometric determination of ultramicro amount of copper. The apparent molar absorptivity of the complex is 3.72×10~5L/mol·cm. Beer's law is obeyed for Cu(Ⅱ)of 0～1.4μg/10ml. The interference of 21 different ions and 6 kinds of salts were examined and found to be minimal. The complex formation of Cu(Ⅱ) with TMPPS_4 is generally slow at room temperature<<25℃>, but the reaction can be accelerated in the presence of NH_2OH·>HCl and completed within 5min. At PH 5.2 the Soret band of TMPPS_4 overlaps almost completetely with that of the complex. Therefore, the complex formation is taken to completion at this PH. Then the Soret band of TMPPS_4 shifted away from that of the complex by acidification.This simple and rapid method has been successfully applied to the direct determination of Cu in Al-alloys, industrial water, foods and human hair.     

A FACILE SYNTHESIS OF(±)-MURICATAIN

(±)-Muricatain has been synthesized employing ringopening of allylic alcohol epoxide with lithium acetonitrileand lactonization.     

SYNTHESIS OF 3-PER(POLY)FLUOROALKYLPYRAZOLES

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