• Title/Summary/Keyword: nitrile

Search Result 177, Processing Time 0.024 seconds

A Facile Reduction of Acid Anhydrides with Borane in the Presence of Lithium Chloride in Tetrahydrofuran

  • Yoon, Nung-Min;Lee, Whee-Seong
    • Bulletin of the Korean Chemical Society
    • /
    • v.7 no.4
    • /
    • pp.296-298
    • /
    • 1986
  • Carboxylic acid anhydrides are rapidly reduced with borane-lithium chloride (1:0.1) system to give corresponding alcohols (diols in the case of cyclic anhydride) quantitatively in tetrahydrofuran at room temperature. This reagent tolerates aromatic acid ester, nitro, and halide functional groups, however competitively reduces aliphatic ester and nitrile groups.

Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N in MeCN. Effects of β-Aryl Group and Base-Solvent on the Nitrile-Forming Transition-State

  • Cho, Bong-Rae;Ryu, Eun-Mi;Pyun, Sang-Yong
    • Bulletin of the Korean Chemical Society
    • /
    • v.33 no.9
    • /
    • pp.2976-2980
    • /
    • 2012
  • Nitrile-forming eliminations from (E)-2,4-$(NO_2)_2C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1a-e) promoted by $R_3N$ in MeCN have been studied kinetically. The reactions are second-order and exhibit Br$\ddot{o}$nsted ${\beta}$ = 0.83-1.0 and ${\mid}{\beta}_{lg}{\mid}$ = 0.41-0.46. The results have been interpreted in terms of highly E1cb-like transition state with extensive $C_{\beta}$-H bond cleavage and limited $N_{\alpha}$-OAr bond cleavage. Comparison with existing data reveals that the structure of the transition state changes from E2-central to highly E1cb-like either by the change of the ${\beta}$-aryl group from Ph to 2,4-dinitrophenyl under the same condition or by the base-solvent system variation from $EtO^-$-EtOH to $Et_3N$-MeCN for a given substrate (1a-e).

The Mechanism in the Photolysis of 5-Phenyl-tetrazole Derivatives (5-Phenyl-tetrazole의 光分解反應과 그 메카니즘에 관한 硏究)

  • Chae, Young-Bok;Chang, Kyung-Soo;Kim, Sung-Soo
    • Journal of the Korean Chemical Society
    • /
    • v.11 no.3
    • /
    • pp.85-88
    • /
    • 1967
  • The main object of this experiment is to provide a systematic approach to the reaction mechanism in the photolysis of 5-phenyl-1,2,3,4-tetrazole during which the formation of C-phenyl-nitrile-imine of 1.3-dipole was expected. So the occurrence of 1,3-dipole-addition was examined but not observed despite the formation of nitrile-imine. 3,6-diphenyl-1,2,4,5-tetrazine (IV); 3,6-diphenyl-1,4-dihydro-1,2,4,5-tetrazine (III); 3,5-diphenyl-1,2,4-triazole; 4-amino-3,5-diphenyl-1,2,4-triazole; benzonitrile; ammonia and nitrogen were isolated as final products of this reaction.

  • PDF

Environmentally Friendly Synthesis of Amide by Metal-catalyzed Nitrile Hydration in Aqueous Medium (수중에서 금속 촉매의 니트릴 수화 반응에 의한 환경친화적 아미드 합성)

  • Hussain, Muhammad Asif;Kim, Jung Won
    • Applied Chemistry for Engineering
    • /
    • v.26 no.2
    • /
    • pp.128-131
    • /
    • 2015
  • Hydration of nitriles in the environmentally benign neutral conditions is the most economical and attractive way to produce amides. Substantial research works have been carried out to apply the solid metal oxides and transition metal supported catalytic systems to promote the hydration of nitriles. The most significant feature of these catalysts is the applicability to a wide range of substrates including aromatic, alicyclic, hetero-atomic, and aliphatic nitriles. These catalysts are also characterized by the easy isolation from the reaction mixture and the reusability while maintaining the high catalytic activity. This review accounts over the detailed survey of the metal oxide and solid supported metal catalysts for preparing amides from the hydration of nitriles.

Preparation and Mechanical Properties of NBR/Clay Nanocomposite (NBR/Clay 나노복합체의 제조와 특성에 관한 연구)

  • Li, Dun;Park, Se-Hyeong;Sur, Gil-Soo
    • Polymer(Korea)
    • /
    • v.34 no.3
    • /
    • pp.215-219
    • /
    • 2010
  • Nitrile rubber (NBR) composites were prepared using the commercially avaliable rubber compounding process with Cloisite$^{(R)}$ 10A or carbon black as fillers. When Cloisite$^{(R)}$ 10A was used as a filler in the NBR composites, the mechanical properties, oil resistant, and oxygen barrier were better than those for carbon black composites. In cure characteristics of NBR/clay composites, scorch time and curing time were reduced. It was found that alkyl ammonium ion inserted in Cloisite$^{(R)}$ 10A was considered as an accelerator of vulcanization for NBR composites.

Elimination Reactions of (E)-2,4,6-Trinitrobenzaldehyde O-Aryloximes Promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effect of β-Aryl Group the Nitrile-Forming Transition-State

  • Pyun, Sang-Yong;Byun, Woong-Sub;Cho, Bong-Rae
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.6
    • /
    • pp.1921-1924
    • /
    • 2011
  • Nitrile-forming eliminations from $(E)-2,4,6-(NO_2)_3C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1) promoted by $R_3NH/R_3NH^+$ in 70 mol % MeCN(aq) have been studied kinetically. When X = $NO_2$, the reactions exhibited second-order kinetics as well as Br$\"{o}$nsted ${\beta}$ = 0.63 and ${\mid}{\beta}_{lg}{\mid}$ = 0.34-0.46, and an E2 mechanism is evident. As the leaving group was made poorer (X = H, Cl, and $CF_3$), Br$\"{o}$nsted ${\beta}$ value increased from 0.63 to 0.85-0.89 without much change in the ${\mid}{\beta}_{lg}{\mid}$ value E2, indicating that structure of the transition state changed to an E1cb-like with extensive $C_{\beta}-H$ bond cleavage, significant negative charge development at the ${\beta}$-carbon, and limited $C_{\alpha}$-OAr bond cleavage.

Enhancement of Compatibility between Ultrahigh-Molecular-Weight Polyethylene Particles and Butadiene-Nitrile Rubber Matrix with Nanoscale Ceramic Particles and Characterization of Evolving Layer

  • Shadrinov, Nikolay V.;Sokolova, Marina D.;Okhlopkova, A.A.;Lee, Jungkeun;Jeong, Dae-Yong;Shim, Ee Le;Cho, Jin-Ho
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.12
    • /
    • pp.3762-3766
    • /
    • 2013
  • This article examines the modification of surface properties of ultrahigh-molecular-weight polyethylene (UHMWPE) with nanoscale ceramic particles to fabricate an improved composite with butadiene-nitrile rubber (BNR). Adhesion force data showed that ceramic zeolite particles on the surface of UHMWPE modulated the surface state of the polymer and increased its compatibility with BNR. Atomic force microscopy phase images showed that UHMWPE made up the microphase around the zeolite particles and formed the evolving layer with a complex interface. The complex interface resulted in improvements in the mechanical properties of the composite, especially its low-temperature resistance coefficients, thereby improving its performance in low-temperature applications.

Structural evolution and kinetic study of high isotacticity poly(acrylonitrile) during isothermal pre-oxidation

  • Zhang, Li;Dai, Yongqiang;Kai, Yi;Jin, Ri-Guang
    • Carbon letters
    • /
    • v.12 no.4
    • /
    • pp.229-235
    • /
    • 2011
  • Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by $^{13}C$ NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and $280^{\circ}C$. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter $CNF={I_{2240cm}}^{-1}/ ({I_{1595cm}}^{-1}+f^*{I_{1595cm}}^{-1})$ was defined to evaluate residual nitrile groups. Crystallinity and crystal size were calculated with X-ray diffraction dates. The results indicated that the nitrile groups had partly converted into a ladder structure as stabilization proceeded. The rate of reaction increased with treatment temperature; crystallinity and crystal size decreased proportionally to pyrolysis temperature. The iso-conversional method coupled with the Kissinger and Flynn-Wall-Ozawa methods were used to determine kinetic parameters via differential scanning calorimetry analysis with different heating rates. The active energy of the reaction was 171.1 and 169.1 kJ/mol, calculated with the two methods respectively and implied the sensitivity of the reaction with temperature.

Effects of Commercial Nitrilase Hydrolysis on Acrylic Fabrics

  • Kim, Hye Rim;Seo, Hye Young
    • Fashion & Textile Research Journal
    • /
    • v.18 no.6
    • /
    • pp.889-896
    • /
    • 2016
  • This study aims to evaluate the hydrolytic activity of a commercial nitrilase and optimize nitrilase treatment conditions to apply eco-friendly finishing on acrylic fabrics. To assess the possibility of hydrolyzing nitrile bonds in acrylic fabric using a commercial nitrilase, the amounts of hydrolysis products, ammonia and carboxylate ions, were measured. The treatment conditions were optimized via the amount of ammonia. The formation of carboxylate ions on the fabric surface was detected by X-ray photoelectron spectroscopy and wettability measurements. After nitrilase treatment, ammonia was detected in the treatment liquid; thus, nitrilase hydrolyzed the nitrile bonds in acrylic woven fabric. The largest amount of ammonia was released into the treatment liquid under the following conditions: pH 8.0, $40^{\circ}C$, and a treatment time of 5 h. The formation of carboxylate ions on the acrylic woven fabric surface by nitrilase hydrolysis was proven by the increased O1s content measuring of XPS analysis. From comparison of the results of nitrilase and alkaline hydrolysis, the white index and strength of the alkali-hydrolyzed acrylic fabric decreased, whereas those of the nitrilase-hydrolyzed samples were maintained. The nitrilase hydrolysis improved the sensitivity of acrylic fabrics to basic dye similarly to alkaline hydrolysis without the drawbacks of yellowing and decreased strength caused by alkaline hydrolysis.