STUDY OF THE REACTION BETWEEN α-KETOTHIOANILIDE AND PHENYLENE DIAMINE

When α-ketothioanilide reacts with o-phenylenediamine,there aretwo competing reactions.One is condensation which forms substituted quinoxalineand the other is substitution which forms substituted quinoxaline-2-thione·Bycontrolling the reaction condition,we can obtain either quinoxaline orquinoxaline-2-thione as the main product.     

INVESTIGATION OF THE INTERACTIONS BETWEEN WATER AND MODIFIED SILICA GEL BY IGC AND TPD

1. INTRODUCTIONSilica gel is an amorphous inorganic polymer composed of siloxane (Si-O-Si) groups in the inner region and silanol (Si-OH) groups distributed on the surface [1]. Silanol groups can be easily functionalized by different chemical procedures. …     

KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

α,α-dimethoxy-α-Phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator. Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyi benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and k_p/k_1~(1/2) value were found to be 0.5 and 0.066 mol(-1/2)l~(1/2)s~(-1/2), respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.     

THE REACTION BETWEEN π-CYCLOPENTADIENYLDI-CARBONYLCOBALT AND PHENYLETHYNYLSILANE,AND AN X-RAY CRYSTALLOGRAPHIC INVESTIGATION OF ONE OF THE PRODUCTS, (π-CYCLOPENTADIENYL)-[trans-DIPHENYL-DI(TRIMETHYLSILYL)-CYCLOBUTADIENE]-COBALT

Abstract

This is a report of the broad range of reactions and products that occur in refluxing xylene when π-cyclopentadienylcobalt or (π-cyclopentadienyl)-dicarbonylcobalt react with either symmetric or unsymmetrical acetylenes, specially when one of the substituents of the acetylene is an aromatic moeity. Since these reactions produce a variety of products, several of which are cis- and trans- tetrasubstituted cyclobutadiene-cobalt isomers, mnr and mass spectral methods were used to distinguish between them. In order to obtain an independent and indisputable structure assignment for the structural isomers investigated by spectral techniques, the crystal structure of the title compound was investigated by x-ray crystallographic techniques. The compound crystallizes in space group Pbca with the following cell dimensions: a = 29.622(7), b = 9.967(2) and c = 17.140(3) Å; V = 5060.46 ų; D(exp) = 1.23(2) gm-cm^?3, D(calc) = 1.24 gm-cm^?3 for Z = 8 molecules/unit cell. The intensity data were collected with MoKα radiation (Λ = 0.71069 Å) using a computer-controlled diffractometer equipped with a graphite monochromator. In all 6331 reflections were collected of which 3173 were independent and had F ₀ ² ± 3[sgrave] (F ₀ ²). The data were corrected for absorption and the transmission coefficients ranged from 0.72 to 0.79. The (π-cyclopentadienyl) ring is planar and has normal Co–C and C–C distances which average 2.049(7) and 1.389(17) Å, respectively. The Co–(Cp ring centroid) distance is 1.67 Å and the ring librates about this axis to a small degree which is not, however, large enough to affect the C–C distances. The average value of the C–C–C angle in the π-cyclopentadienyl ring is 108° indicating that it is planar and, in fact, the largest deviation of any carbon from the least-squares plane is 0.006 Å. In the Co-cyclobutadiene moiety, the Co–C and C–C distances are 1.982(15) and 1.467(3) Å and the Co–(cyclobutadiene ring centroid) distance is 1.69 Å. The angle between the normals of the five- and four-membered rings is 1.6°. The phenyl rings and trimethylsilyl fragments have normal distances and angles and the phenyl rings are planar. The two silicon and two carbon atoms of the phenyl rings linked to the π-cyclobutadiene moeity are out of the mean plane of the ring and bend away from the Co atom.

Finally, and most important, the four-membered ring is planar (the largest deviation from planarity is 0.003 Å) and the four C–C distances are the same length; however, the internal angles are not 90.0°. Instead, the two angles at carbons bonded to phenyl rings have values of 88.1(2)° and 88.4(2)° while those at carbon atoms bonded by silicons have values of 91.6(2)° and 91.8(2)°. The final discrepancy indices for this structural analysis were R ₁ = 0.038 and R ₂(F) = 0.044.     

THERMAL AND PHOTOCHEMICAL REACTIONS BETWEEN α, α′-DIBROMOKETONES AND FIVE-MEMBERED HETEROCYCLES IN THE PRESENCE OF IRON NONACARBONYL

Abstract

[3 + 4] Cycloaddition reactions of 2-oxyallilic cations to furan¹ to form seven-membered oxobicyclic compounds have been known for some time. The purpose of this paper has been to try to extend the reaction to five-membered heterocycles with more aromatic character than furan. An analogy has been found between the behavior of thiophene, selenophene and tellurophene in these reactions and in oxetane-forming reactions. The higher the aromaticity of the heterocycle, the more difficult it is to achieve the formation of the seven-membered ring. Contrary to what is observed in oxetane-forming reactions, where it is not possible to isolate a stable tellurium compound, the tellurabicyclic compound was isolated and identified by spectroscopic methods in the present investigation.     

MHEORETICAL STUDIES ON THE REACTION MECHANISMS OF CYCLOADDITION REACTIONS BETWEEN KETENE OR SUBSTITUTED KETENES AND CYCLOPENTADIENE

The cycloaddition reactions between ketene or substituted ketenes andcyelopentadiene have been studied theoretically by means of the semiempirical AMImethod.Three different substituted ketenes have been selected and tentransition states,corresponding to different approach geometries have beenlocated and characterized,The regioselectivity and stereoselectivity of thereactions are correctly predicted by the calculations and the reaction mechanismsare analyzed in terms of electronic and steric effects of the substitutents onthe reacting ketene and cyc-lopentadiene.     

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).     

INVESTIGATION ON THE RELATIONSHIP BETWEEN INTRINSIC VISCOSITY AND MOLECULAR WEIGHT OF POLY (VINYL CHLORIDE-DIETHYL MALEATE)

A poly (vinyichloride-diethyl maleate) copolymer has been fractionated by repeated precipitation method. All fractions and the unfractionated sample have been characterized by viscometry, dynamic osmometry, Zimm static osmometry, light scattering and gel permeation chromatography. After correction for polydispersity, a [η]～M relationship for monodisperse polymer solutions has been obtained:[η]=1.99×10~(-3)M~(0.87) (ml/g, at 25℃, in cyclohcxanone)For the copolymer solution in THF, the second virial coefficient A_2 decreases as the molecular weight increases. The relationship isA_2=2 slope ((?)_n RT)~(-1/2).     

HIGHLY REGIOSELECTIVE AND STEREOSELECTIVE RADICAL ADDITION OF p-TsBr TO α-ALLENIC ALCOHOLS AND THEIR ELIMINATION REACTION: SYNTHESIS OF β-p-TOSYL-SUBSTITUTED α,β-UNSATURATED KETONES

ABSTRACT

Regio- and stereoselective radical addition of α-allenic alcohols with p-TsBr in the presence of a catalytic amount of AIBN afforded (E)-γ-bromo-β-sulfonyl allylic alcohols in moderate yields. The base-promoted 1,4-elimination followed by isomerization to give β-sulfonyl-α,β-unsaturated ketones is described.     

STUDY OF THE REACTION BETWEEN N,N''''-DI(4-METHYL)PHENYL DITHIOXAMIDE AND TRANS-1,2-CYCLOHEXADIAMINE

The reaction between N,N-di(4-methylphenyl)dithfoxamide andtrans-1,2-cyclohexadiamine was studied in this paper.     

Synthesis, crystal structure and forming mechanism of two novel copper (Ⅱ) α-methacrylate complexes with benzimidazole

Two copper (Ⅱ) a-methacrylate complexes with benzimidazole, Cu [CH_2=C( CH_3)-COO]_2(C_7H_6N_2)_2(1) and Cu_2 [CH_2=C(CH_3)-COO]_4(C_7H_6N_2)_2 (2), have been prepared and characterized by elemental analyses, IR and electronic reflectance spectroscopies. The single crystal X-ray diffraction study of the two complexes shows that complex 1 has a square planar configuration, while complex 2 has a binuclear cage structure. The crystal structural analyses show that both complexes 1 and 2 are monoclinic, with space group P2_1/c, a=0.924 16(8) nm, b=1.233 02(13) nm, c =0.989 1(3) nm, β=91.912(13)°, D_c=1.386 g/cm~3, Z=2, R=0.033 9 for the former; and a=0.905 7(2) nm, b=2.252 1(5) nm, c=1.623 5(4) nm, β=90.11(2)°, D_c =1.411 g/cm~3 , Z=4, R=0.056 8, Cu-Cu=0.266 21 nm for the latter. Different structural types of complexes 1 and 2 were produced simultaneously in the reaction of copper (Ⅱ) α-methacrylate with benzimidazole in methanol solution. The forming mechanism of the complexes has been summarized.     

PREPARATION AND CHARACTERIZATION OF INCLUSION COMPLEXES OF TWO-ARM LINEAR AND FOUR-ARM STAR-SHAPED POLY（ε-CAPROLACTONE）S WITH α-CYCLODEXTRIN

Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of α-CD.     

A FOURIER TRANSFORM INFRARED SPECTROSCOPIC STUDY OF THE REACTION BETWEEN POLY (VINYL PYRIDINE)S AND EPOXY COMPOUNDS

Chemical reactions between poly (vinyl pyridine)s and 1, 4-butanediol diglycidyl ether and other epoxy compounds were studied by Fourier transform infrared spectroscopy and other techniques. The epoxy group was found to react with the pyridine side group of poly (4-vinyl pyridine), forming crosslinked networks which contain cyclic amide structures. The reaction was also observed in the interracial region of poly(vinyl pyridine) and γ-glycidoxy propyl trimethoxysilane hydrolyzate (γ-GPS) coatings on PET fiber substrates. Poly(2-vinyi pyridine) does not show the same reaction.     

Iodine-catalyzed Synthesis of α-Amino Phosphonates

α-Amino phosphonates are structural analogues of the corresponding α-amino acids. They are found to exhibit intriguing biological activities1, for example as enzyme inhibitors, peptidomimetics, antibacterial agents and other pharmacological agents. A va…     

AN INVESTIGATION ON THE LOW TEMPERATURE RELAXATION OF POLYETHERETHERKETONE

The temperature spectra of internal friction of polyetheretherketone (PEEK) are investigated from 130K to 250K with a multi-function torsion pendulum in the frequency range of 0.1 Hz to 5 Hz. A relaxation process, γrelaxation, appears in the temperature range of the measurement. Its relaxation time distribution in terms of a Gaussian distribution, and the relation between molecular motion mechanism and the distribution characteristic are discussed. The element process of γrelaxation is found to be a disordering one.     

SUBSTITUENT CHEMICAL SHIFT (SCS) AND THE SEQUENCE STRUCTURE OF ETHYLENE-VINYL ALCOHOL COPOLYMERS

Three ethylene-vinyl alcohol copolymers were studied by means of the substituent chemical shift (SCS) method. The SCS parameters of hydroxy (-OH) in two different solvents were obtained: in deuterium oxide/phenol (20/80 W/W ) the parameters are S_1 = 42.77±0.08ppm, S_2 = 7.15±0.06 ppm, S_3 (s)= -4.08±0.02ppm, S_3 (t) =-3.09±0.20ppm,S_4 = 0.48±0.03ppm, S_5 = 0.26±0.05ppm. In o-dichloro-benzen-d_4 S_1(s)=44.79±0.61ppm, S_2=7.40±0.00ppm, S_3(s)=-4.51±0.17ppm, S_3(t)=-3.13 ±0.00 ppm, S_4 =0.63±0.04ppm, S_5=0.36±0.00ppm.Simultaneously the ~(13)CNMR spectra of EVA copolymers were assigned by using the SCS parameters obtained.     

Ligand Steric Effects on Naphthyl-α-diimine Nickel Catalyzed α-Olefin Polymerization

Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane(MMAO), were tested in the polymerization of higher α-olefin(1-hexene, 1-decene and 1-hexadecene) under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers(42-88/1000 C) with high molecular weights(M_n:(4.3-15.2) × 10~4 g·mol~(-1)) and narrow molecular weight distribution(M_w/M_n = 1.13-1.29, RT), which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.     

Electrochemical Reduction Characteristics of α-Nitronaphthalene inSulfuric Acid Solution

1-Amino-5-naphtholisanimportantintermediateproductfororganicsynthesis'.Itwastraditionallysynthesizedfroma-nityonaphthalenebychemicalmethod.HO:wever,thechemicalmethodneedstwostepsandproducesalargequantityofwastewater,indicatingthehigherenergyconsumptionandpollution.Inthispaper,theelectrochemicalreductionofa-nitronaphthalenetol-amino-5-naphtholwasfirstputforward,theelectrochemicalreductioncharacteristicsofa-nitronaphthalenetol-amino-5-naphtholwerestudiedandthereactionmechanismwasproposedaswell.…     

REACTIONS BETWEEN BORIC ACID AND POLYHYDROXY COMPOUNDS AND THE DEVELOPMENTS OF BORON—SELECTIVE RESINS

A Review with 56 references on the reaction between boric acid and polyhydroxy compounds,and the developments of boron-selective resins.