• Title/Summary/Keyword: N, N-dimethylacetamide

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Synthesis of N,N-Dimethylacetamide from Carbonylation of Trimethylamine by Rhodium(I) Complex Under Anhydrous Condition

  • Hong, Jang-Hwan
    • Journal of Integrative Natural Science
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    • v.8 no.4
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    • pp.235-243
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    • 2015
  • Rhodium(I)-complex of $[Rh(CO)_2I_2{^-}]$ catalyzed carbonylation of anhydrous-trimethylamine in the presence of methyl iodide to give DMAC (N,N-dimethylacetamide) in no solvent. The catalyst had been reused 20 times, the analyses and distillation of collected products showed that the yields of DMAC, MAA (N-methylacetamide), and DMF (N,N-dimethylformamide) were 82.3%, 12.6%, and 4.4%. The conversion rate of trimethylamine was 99 % and the selectivity of DMAC was 82.3% with TON (Turnover Number) of 700. Stepwise procedure of inner-sphere reductive elimination for the formation of DMAC was suggested instead of acyl iodide intermediate.

Effect of Some Amides on the Hindered Rotation of N-C(S) Bond of Thioacetamide in $CCl_4$ ($CCl_4$속에서 Thioacetamide의 N-C(S) 부자유회전에 미치는 몇가지 Amide의 영향)

  • Seong-Gu Ro;Young-Sang Choi;Chang-Ju Yoon
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.486-490
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    • 1987
  • The effect of the hydrogen-bonding between thioacetamide (TA) and amides (N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA) and N,N-dimethylpropionamide (DMP)) on the hindered rotation of N-C(S) bond of TA was investigated by the nmr spectroscopy. The $^1H$-nmr spectrum of $NH_2$ group in TA was distinctly separated into two peaks with increasing the amount of $CCl_4$ and the effect of amides on the peak separation was in the order of DMF < DMA < DMP. Those phenomena were interpreted in terms of hydrogen-bonding between TA and amide.

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Syntheses of Amide Bonds and Activations of N-C(sp3) Bonds

  • Hong, Jang-Hwan
    • Journal of Integrative Natural Science
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    • v.10 no.4
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    • pp.175-191
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    • 2017
  • In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

Near-IR Spectroscopic Studies of the Hydrogen Bonding between Thioacetamide and N,N-Dimethylacetamide in $CCl_4$ ($CCl_4$중에서 Thioacetamide와 N,N-Dimethylacetamide사이의 수소 결합에 관한 분광학적인 연구)

  • Kang Bong Lee;Byung-Chul Kim;Chang-ju Yun;O. D. Bonner;Young-Sang Choi
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.510-515
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    • 1986
  • Spectra for the $v_3$+ Amide II combination band of thioacetamide(TA) were obtained in carbon tetrachloride solutions and in very dilute solutions of TA-N,N-dimethlylacetamide (DMA) in carbon tetrachloride in the range of 5~55$^{\circ}$C. The combination band in the three component system can be resolved into components due to monomeric TA, 1 : 1 TA-DMA complex and 1 : 2 TA-DMA complex. In the dilute solutions the experimental spectrum was resolved by using the computer into its two Lorentzian-Gaussian product components which have been identified with the monomeric TA and the 1 : 1 complex. The equilibrium constants and thermodynamic parameters of 1 : 1 complex were determined by analysis of concentration and temperature dependent spectra. The ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ for the 1 : 1 complex were -14.4 KJ mol$^{-1}$ and -15.6 J mol$^{-1}deg^{-1}$, respectively.

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Microwave Assisted Rapid Synthesis of Novel Optically Active Poly(amide-imide)s Based on N-Trimellitylimido-L-Leucine Diacid Chloride and Hydantoin Derivatives

  • Faghihi, Khalil
    • Macromolecular Research
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    • v.12 no.3
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    • pp.258-262
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    • 2004
  • We have developed facile and rapid polycondensation reactions of N-trimellitylimido-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h, in the presence of a small amount of a polar organic medium, such as Ο-cresol, by using a domestic microwave oven. The polycondensation reactions proceeded rapidly-they were complete within 7-9 min-to produce a series of novel optically active poly(amide-imide)s (3a-h) in high yield with inherent viscosities of 0.33-0.51 dL/g. We characterized the resulting poly(amide-imide)s by elemental analysis, thermal gravimetric analysis (DSC, TGA, and DTG), and FTIR spectroscopy, and by measuring their viscosities, specific rotations, and solubilities. All of the polymers were soluble at room temperature in polar solvents such as N ,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and N-methyl-2-pyrrolidone.

Static Dielectric Constant and Relaxation Time for the Binary Mixture of Water, Ethanol, N. N-Dimethylformamide, Dimethylsulphoxide, and N, M-Dimethylacetamide with 20Hethoxyethanol

  • Ajay Chaudgari;N. M. More;S. C. Mehrotra
    • Bulletin of the Korean Chemical Society
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    • v.22 no.4
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    • pp.357-361
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    • 2001
  • Frequency spectra of the complex permittivity of 2-methoxyethanol (2-ME) with water, ethanol, dimethylsulphoxide (DMSO), N,N-dimethylformamide (DMF) and N,N-dimethylacatamide (DMA) have been determined over the frequency range of 10 MHz to 20 GHz at 25 $^{\circ}C$, using the Time domain reflectometry method, for 11 concentrations for each system. The static dielectric constant, dielectric constant at microwave frequency, relaxation time, excess dielectric parameters, and Kirkwood correlation factor have been determined. The relaxation in these systems within the frequency range can be described by a single relaxation time constant, using the Debye model. The parameters show a systematic change with the concentration.

Using Microwave Irradiation to Prepare New Poly(amide-imide)s Containing Tetrahydropyrimidinone, Tetrahydro-2-thioxopyrimidine, and Trimellitic Rings in Their Main Chains: Synthesis and Characterization

  • Faghihi Khalil;Hagibeygi Mohsen
    • Macromolecular Research
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    • v.13 no.1
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    • pp.14-18
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    • 2005
  • Under irradiation in a microwave oven, six novel poly(amide-imide)s containing tetrahydropyrimidinone, tetrahydro-2-thioxopyrimidine moieties and trimellitic rings in their main chains were synthesized through the polycondensation reaction of N,N'-(4,4'-diphenylether)bis(trimellitimide) diacid chloride with six different derivatives of tetrahydropyrimidinone and tetrahydro-2-thioxopyrimidine in the presence of a small amount of a polar organic medium, such as o-cresol. The polycondensation proceeded rapidly and completed within 7-9 min, producing a series of new poly(amide-imide)s in high yield that showed inherent viscosities in the range 0.33-0.52 dL/g. These poly(amide-imide)s were characterized by elemental analysis, viscosity measurement, thermal gravimetric analysis, solubility test, and FT-IR spectroscopy. All of the polymers were soluble at room temperature in polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and N-methyl-2-pyrrolidone.

MO Studies on the Conformational Stabilities and the Rotational Barriers about C-N Bond in Amides (Amide류에서 형태안정화와 C-N결합의 회전장벽에 관한 분자궤도론적 연구)

  • Wang Ki Kim;Chang Kook Sohn;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.163-170
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    • 1988
  • The MNDO calculations were performed on the various rotamers of N-methyl formamide, N,N-dimethyl formamide, N-methyl acetamide, and N,N-dimethylacetamide in order to investigate the contribution of the one-electron and the steric effect on their rotational barriers about the C-N bond. Results show that while the conformational stabilities of formamides depend mainly on the one-electron factor, those of acetamides depend mainly on the steric factor. According to results obtained by calculations on the rotational barriers about C-N bond, for N-monosubstituted amides the steric effect is larger in the rotational ground state than in the transition state and for N,N-disubstituted amides the steric effect is larger in the rotational transition state.

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Preparation of Poly(imide)-based Carbon Fiber web from PMDA-ODA Poly(amic acid) solution (PMDA-ODA poly(amic acid) 용액의 전기방사에 의한 폴리이미드계 탄소섬유 웹의 제조)

  • 최영옥;임대영;변성원;양갑승
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10b
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    • pp.130-133
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    • 2003
  • 폴리이미드(poly(imide), PI)는 반복 단위 내에 이미드 그룹을 함유하고 있는 고분자로 매우 강한 물리적인 특성을 지니며 열적 및 화학적 안정성이 매우 큰 고분자이다[1-4]. 그러나 이는 대부분이 불용ㆍ불융하기 때문에 프리커서인 poly(amic acid) (PAA) 용액 상태에서 어느 특정한 형태로 가공한 후 열적 혹은 화학적 방법에 의해 이미드 구조로 전환시켜준다. PAA 용액에 사용되는 용매로는 N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N-dimethyl-formamide(DMF) 등과 같이 비등점이 높은 극성 용매들이 사용되어진다. (중략)

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