- Enthalpic Interaction Coefficient of Formamides Dissolved in N,N-Dimethylformamide
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Enthalpies of dilution of formamide, N-methylformamide, N-ethylformamide, N-propylformamide, N-butylformamide, N-pentylformamide, N,N-diethyl-formamide, N,N-dipropylformamide, N,N-dibutylformamide, and N,N-dipentyl-formamide dissolved in N,N-dimethylformamide as solvent have been measured calorimetrically at 25 deg C.The results are interpreted in terms of the McMillan-Mayer theory.Enthalpic interaction parameters are obtained for pairs, triplets, and in some cases, quadruplets of solute molecules.In general, the enthalpic pair interaction coefficients are negative, whereas the triplet coefficients are positive.The interaction enthalpies are positive only for N-methylformamide and formamide.The magnitudes of the enthalpic pair and triplet interaction coefficients increase with increasing number of C atoms in the N-alkyl groups.The results for the formamides presented in this paper are compared with those for corresponding acetamides published earlier.Although the trends are comparable, distinct differences are observed.The contribution of the α-CH3 group at the CO side of the dialkylacetamides to the enthalpic interaction coefficient appears to be negligible.The same is true for α-CH2 groups at the NH side of a number of amides and related compounds.The enthalpic pair interaction coefficients of the mono-N-alkylsubstituted formamides show a shift of about 100 J-kg-mol-2 as compared with isomeric N-alkylacetamides.This is discussed in terms of the difference in proton donating and accepting ability of several types of amide molecules.It is concluded that substitution effects should be incorporated in additivity models for these type of systems.
- Bloemendal, M.,Sijpkes, A. H.,Somsen, G.
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- A tertiary amine oxidation cracking method of preparing carboxamide
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The invention provides a method for preparing formamide through tertiary amine oxicracking. According to the method, tertiary amine serves as a substrate, air or oxygen serves as an oxygen source, and oxicracking occurs on the tertiary amine under the action of a catalyst to generate the formamide. The method is high in oxidation efficiency and product yield and economical and environmentally friendly by taking the air or oxygen as the oxygen source and has a very good application prospect.
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Paragraph 0014; 0023
(2017/08/26)
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- Visible light induced photocatalytic conversion of enamines into amides
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A series of enamines were photocatalytically cleaved to produce amide products under simple visible-light irradiation from a 45 W household light bulb. Mechanistically, the reactions appear to involve photosensitized formation of a singlet oxygen intermediate and a subsequent [2+2] cycloaddition event. Georg Thieme Verlag Stuttgart, New York.
- Li, Jing,Cai, Shunyou,Chen, Jietao,Zhao, Yaohong,Wang, David Zhigang
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supporting information
p. 1626 - 1628
(2014/07/08)
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- Visible-light photo-catalytic C-C bond cleavages: Preparations of N,N-dialkylformamides from 1,2-vicinal diamines
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A range of 1,2-vicinal diamines were smoothly converted into N,N-dialkylformamides under the synergistic actions of Ru(bpy) 3Cl2 photo-catalyst, 45 W household lighting bulb, and Cs2CO3 basic additive under very mild reaction conditions. The process involves visible light-enabled photo-catalytic cleavage of C-C bond as the strategic event.
- Zhao, Yaohong,Cai, Shunyou,Li, Jing,Wang, David Zhigang
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p. 8129 - 8131
(2013/08/28)
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- PROCESS FOR PREPARING FORMIC ACID
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Process for obtaining formic acid by thermal separation of a stream comprising formic acid and a tertiary amine (I), in which a liquid stream comprising formic acid, tertiary amine (I) and water is produced by combining tertiary amine (I) and a formic acid source in the presence of water, water and organic decomposition products of the tertiary amine (I) are removed and formic acid is removed by distillation from the resulting liquid stream in a distillation apparatus, wherein the stream comprising water and organic decomposition products of the tertiary amine (I) which have been separated off is separated into two liquid phases, the upper liquid phase is removed and the lower, water-comprising liquid phase is recirculated to the formic acid source.
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Paragraph 0218
(2013/07/31)
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- Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
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The reaction of lithium dialkylamides 1 (dialkyl = dibutyl, dipentyl, dicyclohexyl, 3-oxapentamethylene, and isopropyl cyclohexyl) with carbon monoxide was examined under several reaction conditions.It is shown that the corresponding lithium carbamoyl is the first intermediate and its further reactions can lead to dialkylformamides 2, dialkylglyoxylamides 3, or tetraalkylhydroxymalonamides 4.Dialkylamides were previously assumed to come from hydrolysis of lithium carbamoyls, and these represent an unexplained "island of stability" among the area of acyl anions.Evidence is given that casts doubts on this assumption and suggests that 2 comes from the cleavage of lithium tetraalkylurea dianion.The yields of 2, 3, or 4 obtained by this one-step, rapid procedure are much higher than those afforded by the usual several steps methods of preparation, especially for compounds 3 and 4.Tetraalkylureas, tetraalkyloxalamines, or tetraalkylketomalonamides can be obtained in good yield by the same general procedure, followed by treatment ot the reaction mixture with oxygen after the carbon monoxide absorption has ceased and before the regular workup.
- Perez, Daniel G.,Nudelman, N. Sbarbati
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p. 408 - 413
(2007/10/02)
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- Solvent effect in the ruthenium catalyzed carbonylation of amines. Selective synthesis of dialkylformamides
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Formamides are selectively produced in the ruthenium-catalyzed carbonylation of amines in alcoholic solvents.The process is shown to occur sequentially via initial carbonylation of the alcohol to yield the corresponding formate, which then reacts with the amine to yield the formamide.The method is of interest for the carbonylation of unreactive amines (aniline, t-butylamine).
- Bitsi, G.,Jenner, G.
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p. 429 - 436
(2007/10/02)
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