149-73-5Relevant articles and documents
A PRIMARY KINETIC ISOTOPE EFFECT FOR THE O-H INSERTION OF DIMETHOXYCARBENE
Moss, Robert A.,Shen, Shilan,Wlostowski, Marek
, p. 6417 - 6420 (1988)
The primary kinetic isotope effect for the insertion of dimethoxycarbene into MeOH(D) is 3.3 +/- o.5.
Unexpected formation of acylformamidines by reaction of primary carboxamides with MeONa in DMF in the presence of CHCl3
Anelli, Pier Lucio,Brocchetta, Marino,Copez, Debora,Palano, Daniela,Visigalli, Massimo,Paoli, Paola
, p. 15827 - 15832 (1997)
Dichlorocarbene, which is generated by reaction of CHCl3 with MeONa, is likely to chlorinate DMF to produce tile Vilsmeier-Haack-Arnold salt that in the presence of excess MeONa, gives DMF dimethylacetal (2). This latter reacts with primary amides to yield the corresponding N,N-dimethyl-N'-acylformamidines. Solid state structure of N-[(dimethylamino)methylene]phenoxyacetamide (4) obtained by X-ray crystallography is also reported.
Selective production of difluoromethyl methyl ether from chlorodifluoromethane using alkali metal carbonates
Lee,Hoon Sik Kim,Sang Deuk Lee,Won Koo Lee,Kim
, p. 133 - 136 (2001)
CHF2OCH3 (HFE-152a), an important starting material for synthesizing various C2 hydrofluoroethers and a prospective alternative to CH3CF2Cl (HCFC-142b), has been found to be effectively produced from the reaction of CHF2Cl (HCFC-22) with alkali metal carbonates in methanol. Some alkali metal carbonates induce selective production of CHF2OCH3 with a small amount of CH(OCH3)3, a major side product. Activities of alkali metal carbonates for producing CHF2OCH3 are in the order of K2CO3 > Na2CO3 > Li2CO3, suggesting that the solubility and ionization tendency of alkali metal carbonate in methanol play important roles in the reaction.
Reactions of dimethoxycarbene and fluoromethoxycarbene with hydroxyl compounds. Absolute rate constants and the heat of formation of dimethoxycarbene
Du,Fan,Goodman,Kesselmayer,Krogh-Jespersen,LaVilla,Moss,Shen,Sheridan
, p. 1920 - 1926 (1990)
Dimethoxycarbene [(MeO)2C] and fluoromethoxycarbene (FCOMe) were photochemically generated from the appropriate diazirines (2a and 2b) and characterized by UV and IR spectroscopy in cold matrices and by UV in solution at 20-25°C. Laser flash photolytic studies determined rate constants for the reactions of the carbenes with ethanol, methanol, chloroethanol, fluoroethanol, trifluoroethanol, hexafluoroisopropyl alcohol, and acetic acid. The reactivity of (MeO)2C with the alcohols spanned 4 orders of magnitude, with kψ for carbene decay in 1 M ROH/CH3CN ranging from 3.2 X 104 S-1 (ethanol) to 6.7 X 108 S-1 (hexafluoroisopropyl alcohol). A Bronsted correlation (α = 0.66) was obtained between log kψ for the decay of (MeO)2C in 1 M ROH/CH3CN and the pK(a) of ROH (in water). FCOMe was much less reactive toward ROH than (MeO)2C; only with hexafluoroisopropyl alcohol (kψ ~9 X 103 s-1 for carbene decay in 1 M ROH/CH3CN) could quenching be observed. Products of some of the carbene/alcohol reactions were characterized. A photoacoustic calorimetry study of the (MeO)2/MeOH reaction afforded ΔH(f) ~ -61 kcal/mol for (MeO)2C;ΔH(f) for FCOMe was estimated at ~ -53 to -56 kcal/mol. The mechanism(s) of the carbene/O-H insertion reactions are discussed. The results of ab initio and semiempirical molecular orbital calculations on FCOMe are presented.
Synthesis method of crude carboxylic ester (by machine translation)
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Paragraph 0021; 0022, (2020/08/09)
The method is characterized in that the carboxylic ester and the ether are prepared by reacting a carboxylic ester with an ether at a certain temperature under the catalysis of a catalyst at a certain pressure for a certain time. (by machine translation)
Trimethyl orthoformate and a preparation method thereof
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Paragraph 0032; 0035-0036; 0039-0040; 0043-0044; 0047-0048, (2020/03/17)
The invention provides trimethyl orthoformate and a preparation method thereof. The method comprises the following steps: 1) salt forming: taking methyl alcohol and solvent oil, mixing, adding hydrogen chloride and hydrocyanic acid, and carrying out a salt forming reaction, wherein the temperature of the salt forming reaction is controlled at 5-30 DEG C; and 2) alcoholysis: after the salt formingreaction is finished, adding methanol again, and carrying out an alcoholysis reaction to obtain trimethyl orthoformate. According to the invention, solvent oil is used as a solvent, so that the salt forming temperature is increased, the raw materials and the energy consumption cost are effectively reduced, and the yield is increased so as to effectively improve the market competitiveness of the product.
Method for producing high purity orthoformate simple and convenient method of
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Paragraph 0014-0017; 0029-0031, (2017/12/04)
The invention provides a simple and convenient method for producing high-purity ortho-formate by using acrylonitrile byproduct hydrocyanic acid. The method comprises the following steps: firstly producing amine salt from the acrylonitrile byproduct hydrocyanic acid, fatty alcohol and hydrogen chloride, subsequently performing alcoholysis reaction on the presence of corresponding fatty alcohol so as to obtain an ortho-formate reaction liquid, adding a proper amount of an alkali substance in the generated ortho-formate reaction liquid, decomposing nitrogenous impurity compounds such as byproduct 1,3,5-s-triazine at certain temperature, wherein the decomposed product is nitrogen and solid formate with low boiling point, performing aftertreatment on the reaction liquid so as to obtain the high-purity ortho-formate through normal distillation. Therefore, the purpose of producing the high-purity ortho-formate with high yield is achieved.
Green preparing orthoformate cleaning process
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Paragraph 0038; 0040; 0041, (2016/10/07)
The invention provides a green process for preparing orthoformate. A hydrogen chloride alcohol solution is prepared from a byproduct hydrogen chloride tail gas of the chlorine-related synthesis industry and then is slowly added into a reaction system, so that loss caused by escape of hydrocyanic acid is reduced, the yield is increased, great equipment corrosion caused by the byproduct hydrochloric acid prepared by the companies is avoided, the economic additional value of the byproduct hydrogen chloride is greatly increased, three wastes are avoided, the byproduct only comprises ammonium chloride, resources are reasonably utilized, and the green process for preparing the orthoformate is an environment-friendly production process and has a good social benefit.
Orthoester exchange: A tripodal tool for dynamic covalent and systems chemistry
Brachvogel, Ren-Chris,Von Delius, Max
, p. 1399 - 1403 (2015/02/05)
Reversible covalent reactions have become an important tool in supramolecular chemistry and materials science. Here we introduce the acid-catalyzed exchange of O,O,O-orthoesters to the toolbox of dynamic covalent chemistry. We demonstrate that orthoesters readily exchange with a wide range of alcohols under mild conditions and we disclose the first report of an orthoester metathesis reaction. We also show that dynamic orthoester systems give rise to pronounced metal template effects, which can best be understood by agonistic relationships in a three-dimensional network analysis. Due to the tripodal architecture of orthoesters, the exchange process described herein could find unique applications in dynamic polymers, porous materials and host-guest architectures.
Alcoholysis of fluoroform
Miloserdov, Fedor M.,Grushin, Vladimir V.
, p. 105 - 109 (2015/03/03)
Fluoroform (CHF3) reacts with alkali metal alkoxides MOR (M = Na, K) in the corresponding alcohols ROH (R = Me, Et, i-Pr, t-Bu, and Allyl) at 80-120°C to give orthoformate esters HC(OR)3 in 55-90% yield. Particularly notable is the f
