STUDIES ON ORGANOPHOSPHORUS COMPOUNDS. PART VI.† THE REACTION OF ALKOXIDES WITH 2,4-BIS(4-METHOXYPHENYL)-1,3,2,4-DITHIADIPHOSPHETANE 2,4-DISULFIDE (LR). A NEW APPROACH FOR THIO-INEZIN

Abstract

Sodium alkoxide, a hard nucleophile, reacts with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (LR) on phosphorus to give O-alkyl S-sodium-(4-methoxyphenyl) phosphonothiolothionate 5 as an intermediate. Compound 5 reacts with benzyl (or benzoyl) chloride to give good yields of O-alkyl S-benzyl (benzoyl) (4-methoxy-phenyl)phosphonothiolothionate (6a–e).     

REACTION OF ORGANODILITHIUM REAGENT WITH α,α''''-DIHALO-o-XYLENE

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LOW-VALENT TITANIUM INDUCED REDUCTIVE CROSS-COUPLING REACTION OF ESTERS WITH DIARYL KETONES

The intermotecular coupling reaction of esters with diarvl ketones induced by titanium tetrachtoride and zinc powder was studied.     

STUDY ON THE CHAIN-EXTENDING REACTION OF POLY (ETHYLENE TEREPHTHALATE) WITH 2, 2′-BIS (4H-3, 1-BENZOXAZIN-4-ONE)

2,2'-Bis (4H-3, 1-benzoxazin-4-one) (BBON) has been proved to be an effective chainextender for poly (ethylene terephthalate) (PET). In order to study the reaction mechanismand kinetics of chain-extending reaction, β-bishydroxyethylene terephthalate (BHET) wasselected as model compound. The NMR data, IR spectra and number average molecularweight (M_n) of the products obtained from the reaction of BBON and BHET verify thatBBON is a hydroxyl-reactive extender. The mechanism was discussed. Kinetics dataindicate that extending reaction is a second order reaction, and BBON has high reactivity.The activation energy (E_a) was measured.     

SOLVENT EFFECT ON CONFORMATIONS OF α,ω-BIS(4-NITROPHENOXY)-ALKANES

Solvent effect on the conformations of-bis(4-nitrophenoxy)-alkanesw th different chain Lengths(Nn)was studied by UV spectra.In poor solvents such asEG-H_2O and THF-H_2O,with the water content higher than 50%,the K-bands of N_4.N,N_6 and N_(10)in the UV absorption spectra shifted to longer wavelengths as comparedwth 4-nitrophenoxyethane(N_0).It is suggested that in poor solvents the two aromaticgrps are close to each other in parallel,forming ground state complexes.The K-bead of N_4 showed a blue shift from that of N_0 when the water content was around5%,probably attributable to a conformation with the nitro group of one benzene ringsiting on the plane of the other benzene ring.     

THE BAYLIS—HILLMAN REACTION: TiCl4 MEDIATED COUPLING OF ALKYL VINYL KETONES WITH α-KETO ESTERS AND ALDEHYDES

TiCl₄ mediated coupling of alkyl vinyl ketones with α-keto esters and aldehydes provides respectively 2-aryl-2-hydroxy-3-methylene-4-oxoalkanoates and (Z)-keto allyl chlorides in 1 h time at room temperature. Similar coupling of trifluoromethyl phenyl ketone with methyl vinyl ketone produces 1,1,1-trifluoro-2-hydroxy-2-phenyl-3-methylenepentan-4-one.     

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).     

UNUSUAL REACTION OF α,α-DIHALOGEN ETHERS WITH SULFINATE ANIONS

Abstract

Unsymmetrical dihalogen ethers halogenate arene sulfinate anions yielding the corresponding arene sulfonyl halides in addition to other products. A reaction mechanism is proposed.     

REACTION OF α-(1H-1,2,4-TRIAZOL-1-YL)ACETOPHENONE WITH PHENYL ISOTHIOCYANATE

Reaction of α-(1H-1,2,4-triazol-1-yl)acetophenonewith phenyl isothiocyanate in the presence of a base and subse-quent alkylation leads to the ketene S,N-acetal(2),(4),(7),(8);thiazolidone(3),thiazolidine(5)and 1,3-thiazine(6),     

SYNTHESIS AND CHARACTERIZATION OF COPOLYMER OF 2,5-BIS[（4-METHOXYPHENYL）OXYCARBONYL]STYRENE AND STYRENE WITH HIGH MOLECULAR WEIGHT

The random copolymers of styrene and 2,5-bis[(4-methoxyphenyloxycarbonyl)styrene] (MPCS) with different copolymerization ratio were synthesized by conventional free radical polymerization. The copolymer having high molecular weight was experimentally elucidated using a combination of proton nuclear magnetic resonance spectroscopy and gel permeation chromatography. The liquid crystalline behavior of the copolymer was studied using differential scanning calorimetry, X-ray diffractometry and polarized optical microscopy. It was found that the liquid crystalline behavior was dependent on the content of styrene. Experimental results show that the copolymer could turn into a liquid crystalline phase at about 180℃ when the content of styrene was less than 20%. The mechanical properties of the copolymer were also studied. Preliminary results indicate that the tensile strength decreases while the tensile modulus increases as the content of MPCS is increased.     

REACTION OF α-CHLOROTOLUENE WITH ELEMENTAL SULFUR IN LIQUID AMMONIA

Abstract

α-Chlorotoluene (1) reacts with elemental sulfur in liquid ammonia affording dibenzyl disulfide (2), dibenzyl trisulfide (3), dibenzyl tetrasulfide (4), dibenzyl pentasulfide (5) and benzylidene benzylimide (6) at a low temperature such as 20°C. This reaction is presumed to be initiated by the nucleophilic attack of ammonium thioaminohydroxylate, “H₂NS^-NH₄ ⁺,” or dithioaminohydroxylate, “H₂NSS^-NH₄,” formed upon treating elemental sulfur in liquid ammonia, on α-chlorotoluene (1). Benzylidene benzylimide (6) is presumed to be formed from benzylamine, which can be formed by treatment of α-chlorotoluene (1) with ammonia.     

1-(4-ANTIPYRINYL)-3-(2, 4-DINITROPHENYL)-TRIAZENE AND ITS COLOUR REACTION WITH CADMIUM

A new reagent,1(4 antipyriny1) 3(2,4-dinitropheny1)triazene(APDNBT), was synthesized in this lab and its analytical properties and its colour reaction with cadmium were studied.     

THE COLOUR REACTION OF CADMIUM WITH 1-(2-BENZOTIIIAZOLYL)-3-(4-PHENYLAZOPHENYL)-TRIAZENE AND ITS APPLICATION

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SYNTHESIS OF 1-(ACETYLSALICYLYL)-BENZOTRIAZOLE AND ITS REACTION WITH POLYVINYL ALCOHOL

l-(Acetylsalicylyl)-benzotriazole, a new active amide of acetylsalicylic acid has been synthesized either from acetylsalicylic acid and benzotriazole using DCCI as condensation agent or via acetylsalicylyl chloride and benzotriazole in the presence of triethylamine. The obtained active amide reacted readily with the hydroxyl group of PVA to produce the acetylsalicylyl ester of PVA.     

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.     

POLYMERIZATION OF ETHYLENE WITH UNSYMMETRIC 2,6-BIS(IMINO)PYRIDINE IRON(Ⅱ)COMPLEX

An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol~(-1)·Fe·h~(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.     

REACTIONS WITH PHOSPHACUMULENES: SYNTHESIS OF PYRAN DERIVATIVES FROM THE REACTION OF N-PHENYLIMINOKETENYLIDENE TRIPHENYL-PHOSPHORANE WITH α,β-UNSATURATED CARBONYL COMPOUNDS

Abstract

2-Benzylidene-1,3-indanedione (2), 4-benzylidene-1,2-diphenyl-3,5-pyrazolidenedione (4) and/or 5-benzylidenebarbituric acid (6) can be converted by reaction with N-phenyliminoketenylidene triphenylphosphorane (1) into pyransubstituted phosphoranes 3, 5 and 7. The structure of the new cyclic imino-phosphoranes 3, 5 and 7 was confirmed on the basis of elemental analysis and spectral studies. Moreover, when Wittig reaction was carried out on the pyran compound 7, using p-nitrobenzaldehyde, the new olefin 8 was isolated.     

SYNTHESIS AND STRUCTURE OF THE COMPLEX OF N, N''''-(4, 6-DINITRO-1, 3-PHENYLENE)-BIS(4''''-BENZO-15-CROWN-5-AMINE) WITH POTASSIUM THIOCYANATE

Crystals of the title compound were prepared, whose structure has been determined by X-ray diffraction as a biscrown complex. The crystal is monoclinic with a=22.512 (11), b=22.649(9), c=18.113(8), β=104.84(4)°, V=8926(7)~3, Z=8, space group C2/c. Least square retinement has been performed on 2807 unique observed reflections to a final R of 0.91. It is noted from the structure that K+ is coordinated with ten oxygen atoms, forming an intramolecutar sandwiched complex. The bond distance of K+—O ranges from 2.780 to 3.102 with a mean value of 2.906. Local disorder is observed for SCN-group which distributes on three positions with site occupation factors 0.4, 0.3 and 0.3, respectively.     

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.     

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.