- PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
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Paragraph 00177; 00178
(2019/02/15)
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- Method for preparing formate-type compound
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The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
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Paragraph 0039; 0047; 0048
(2018/07/30)
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- METHOD OF CONVERTING ALCOHOL TO HALIDE
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The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
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Page/Page column 53; 132; 139; 140
(2017/01/02)
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- MONOMER, POLYMER, RESIST COMPOSITION, AND PATTERNING PROCESS
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A polymer comprising recurring units derived from a (meth)acrylate monomer of tertiary ester type having branched alkyl on alicycle is used to form a resist composition. When subjected to exposure, PEB and organic solvent development, the resist composition is improved in dissolution contrast.
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- Nickel-catalyzed hydrosilylation of CO2 in the Presence of Et3B for the synthesis of formic acid and related formates
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The reaction of CO2 with Et3SiH catalyzed by the nickel complex [(dippe)Ni(μ-H)]2 (1) afforded the reduction products Et3SiOCH2OSiEt3 (12%), Et 3SiOCH3 (3%), and CO, which were characterized by standard spectroscopic methods. Part of the generated CO was found as the complex [(dippe)Ni(CO)]2 (2), which was characterized by single-crystal X-ray diffraction. When the same reaction was carried out in the presence of a Lewis acid, such as Et3B, the hydrosilylation of CO2 efficiently proceeded to give the silyl formate (Et3SiOC(O)H) in high yields (85-89%), at 80 C for 1 h. Further reactivity of the silyl formate to yield formic acid, formamides, and alkyl formates was also investigated.
- Gonzalez-Sebastian, Lucero,Flores-Alamo, Marcos,Garcia, Juventino J.
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p. 7186 - 7194
(2014/01/06)
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- Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation: Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation
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A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.
- Ochiai, Masahito,Yoshimura, Akira,Miyamoto, Kazunori,Hayashi, Satoko,Nakanishi, Waro
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supporting information; experimental part
p. 9236 - 9239
(2010/11/02)
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- Oxidative C-C bond cleavage of primary alcohols and vicinal diols catalyzed by H5PV2Mo10O40 by an electron transfer and oxygen transfer reaction mechanism
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Primary alcohols such as 1-butanol were oxidized by the H5PV2Mo10O40 polyoxometalate in an atypical manner. Instead of C-H bond activation leading to the formation of butanal and butanoic acid, C-C bond cleavage took place leading to the formation of propanal and formaldehyde as initial products. The latter reacted with the excess 1-butanol present to yield butylformate and butylpropanate in additional oxidative transformations. Kinetic studies including measurement of kinetic isotope effects, labeling studies with 18O labeled H5PV2Mo10O40, and observation of a prerate determining step intermediate by 13C NMR leads to the formulation of a reaction mechanism based on electron transfer from the substrate to the polyoxometalate and oxygen transfer from the reduced polyoxometalate to the organic substrate. It was also shown that vicinal diols such as 1,2-ethanediol apparently react by a similar reaction mechanism. Copyright
- Khenkin, Alexander M.,Neumann, Ronny
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supporting information; scheme or table
p. 14474 - 14476
(2009/02/08)
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- PROCESS FOR PREPARATION OF FORMATE ESTERS OR METHANOL AND CATALYST THEREFOR
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A production process and a catalyst are provided, which can be less decreased in activity of the catalyst even when CO2, water and the like are present in the starting material and/or the reaction system, and which can produce a formic ester or a methanol at a low temperature and a low pressure. The present invention relates to a process for producing methanol, comprising reacting carbon monoxide with an alcohol in the presence of an alkali metal-type catalyst, and/or an alkaline earth metal-type catalyst to produce a formic ester, wherein a hydrogenolysis catalyst of formic ester and hydrogen are allowed to be present together in the reaction system to hydrogenate the produced formic ester and thereby obtain a methanol.
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Page column 7
(2008/06/13)
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- Preparation of optically active 2-halopropionic acids
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The present invention relates to a process for the preparation of optically active 2--halopropionic acids, in which the corresponding optically active alkyl 2--halopropionates are caused to react with a carboxylic acid at elevated temperature in a transacylation reaction with the formation of the optically active 2--halopropionic acid and the alkyl carboxylate, and the optically active 2--halopropionic acid obtained is separated from the reaction mixture. The optically active products produced are important intermediates for the preparation of plant protectants and pharmaceuticals.
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- Reaction of Carbonyl Oxides and Thioketones. Cycloaddition vs. Oxygen Atom Transfer
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The ozonolysis of vinyl ethers (1a, b) in the presence of thioadamantan-2-one (4a) gave in each case the corresponding thio-ozonide (5a, b) in around 70percent yield, whilst ozonolysis of a mixture of vinyl ethers (1a-c) and thiobenzophenone derivatives (4b-d) gave the corresponding thione-S-oxides (8b-d) in 15-30percent yields, together with the benzophenones (6b-d).
- Tabuchi, Toshihiko,Nojima, Masatomo,Kusabayashi, Shigekazu
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p. 625 - 627
(2007/10/02)
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- Synthesis of 1,2,4-Dioxazolidines by the Ozonolysis of Vinyl Ethers in the Presence of Imines. The First Cycloaddition of Carbonyl Oxide to the Carbon-Nitrogen
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Carbonyl oxides, derived from the ozonolysis of vinyl ethers, readily undergo cycloaddition reactions with imines affording 1,2,4-dioxazolidines in good yield.
- Mori, Mitsuyuki,Nojima, Masatomo,Kusabayashi, Shigekazu,McCullough, Kevin J.
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p. 1550 - 1552
(2007/10/02)
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- FREE-RADICAL LIQUID-PHASE FRAGMENTATION OF MIXED FORMALS
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The homolytic liquid-phase reactions of methoxyalkoxymethanes, initiated by the decomposition of tert-butyl peroxide, in the range of 120-150 deg C were investigated.The fragmentation of the formals occurs as an unbranched chain process, and the main products are the corresponding alkyl and methyl formates.A scheme is proposed which describes the formation of all the observed products from fragmentation of mixed formals.A comparison was made of tha ease of β- elimination of various primary alkyl radicals during the fragmentation of the methoxyalkoxymethyl radicals which form.The physicochemical constants were determined, and the 1H and 13C NMR spectra of the mixed formals were recorded.
- Kalashnikov, S. M.,Zlotskii, S. S.,Imashev, U. B.,Rakhmankulov, D. L.
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p. 1379 - 1382
(2007/10/02)
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