- Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
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Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
- Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
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supporting information
p. 5251 - 5255
(2019/03/07)
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- Method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate
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The invention discloses a method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate. According to the method, an acidic poly(ionic liquid) that can swell in formic acid is synthesized at first; 1-vinyl-3-alkyl imidazolium bromine salt ionic liquid and sodium acrylate are taken as the copolymerization monomers, and throughfree radical polymerization and acidification that uses an acid with an equal molar weight, the poly(ionic liquid) is prepared. The poly(ionic liquid) is taken as a catalyst to catalyze the esterification reactions between formic acid and alkenes; the catalytic activity of the poly(ionic liquid) is equal to that of a homogeneous catalyst and the selectivity is higher than that of a homogeneous catalyst or a heterogeneous catalyst. The swelling-able acidic poly(ionic liquid) is used to catalyze the esterification reactions between formic acid and alkenes, the characteristic that the poly(ionicliquid) can swell in formic acid is utilized, the poly(ionic liquid) is fully dispersed in the substrate, at the same time, the active centers of the acid are immobilized on the poly(ionic liquid), thus the active centers can fully contact with the substrate, and the catalytic efficiency is largely improved.
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Paragraph 0029; 0030; 0031; 0033; 0034; 0042; 0043-0046
(2018/11/04)
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- Alkyl Formate Ester Synthesis by a Fungal Baeyer–Villiger Monooxygenase
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We investigated Baeyer–Villiger monooxygenase (BVMO)-mediated synthesis of alkyl formate esters, which are important flavor and fragrance products. A recombinant fungal BVMO from Aspergillus flavus was found to transform a selection of aliphatic aldehydes into alkyl formates with high regioselectivity. Near complete conversion of 10 mm octanal was achieved within 8 h with a regiomeric excess of ~80 %. Substrate concentration was found to affect specific activity and regioselectivity of the BVMO, as well as the rate of product autohydrolysis to the primary alcohol. More than 80 % conversion of 50 mm octanal was reached after 72 h (TTN nearly 20 000). Biotransformation on a 200 mL scale under unoptimized conditions gave a space-time yield (STY) of 4.2 g L?1 d?1 (3.4 g L?1 d?1 extracted product).
- Ferroni, Felix Martin,Tolmie, Carmien,Smit, Martha Sophia,Opperman, Diederik Johannes
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p. 515 - 517
(2017/03/22)
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- TiCl4/Et3N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates
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A methodology to build (E)-β-alkoxy- and (E)-β-aryloxyacrylate moieties from acetate and formate esters promoted by the TiCl4/Et3N system is presented. The reaction is compatible with a broad range of structural skeletons and elapses through an unusual condensation pathway. Taking into account the obtained results, we propose a plausible mechanism involving a bimetallic titanium intermediate for this type of transformation.
- álvarez-Calero, José María,Jorge, Zacarías D.,Massanet, Guillermo M.
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supporting information
p. 6344 - 6347
(2016/12/23)
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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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- Polyvinylpolypyrrolidoniume tribromide as new and metal-free catalyst for the formylation and trimethylsilylation of hydroxyl group
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Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3- hexamethyldisilazane (HMDS) as silylating agent, in the presence of polyvinylpolypyrrolidoniume tribromide in acetonitrile at room temperature. Also a variety of alcohols were converted into alkyl formates by ethyl formate and a catalytic amount of polyvinylpolypyrrolidoniume tribromide under solvent free conditions at room temperature.
- Ghorbani-Choghamarani, Arash,Goudarziafshar, Hamid,Zamani, Parisa
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scheme or table
p. 1207 - 1210
(2012/01/05)
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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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- Highly efficient formylation of alcohols, thiols and aniline derivatives by a heterogeneous (HCOOH/SiO2) system under microwave irradiation and solvent-free conditions
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A simple, rapid and efficient microwave-assisted procedure for the formylation of aniline derivatives and alcohols, using a heterogeneous (HCOOH/SiO2) system under solvent-free conditions is reported. The method is applied to a set of amines, alcohols and thiols and short reaction times (10 min) with high yields are reported. This protocol introduces a practical and viable green technology of solvent-free and catalyst-free reactions.
- Ghorbani-Vaghei, Ramin,Veisi, Hojat,Amiri, Mostafa,Chegini, Mohammad,Karimi, Mehdi,Dadamahaleh, Somayeh Akbari,Sedrpoushan, Alireza
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experimental part
p. 39 - 43
(2010/09/03)
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- Efficient one-step conversion of tetrahydropyranyl ethers into acetates and formates in the presence of potassium dodecatungstocobaltate K 5CoW12O40·3H2O
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Tetrahydropyranyl ethers derived from primary alcohols were directly and efficiently converted into the corresponding acetates and formates by the action of ethyl acetate, acetic acid, acetic anhydride, and ethyl formate in the presence of a catalytic amount of potassium dodecatungstocobaltate K 5CoW12O40 ? 3H2O. Tetrahydropyranyl ethers derived from secondary alcohols and phenols can also be transformed into the corresponding acetates with the use of acetic anhydride, but K5CoW12O40 ? 3H2O was ineffective for esterification with ethyl acetate, acetic acid, and ethyl formate.
- Rafiee,Tangestaninejad,Habibi,Mohammadpoor-Baltork,Mirkhani
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p. 393 - 395
(2007/10/03)
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- Cerium polyoxometalate as a reusable catalyst for acetylation and formylation of alcohols
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Efficient esterification of primary and sterically-hindered secondary or tertiary alcohols with acetic anhydride was achieved in the presence of ammonium decatungestocerate(IV) icosahydrate, (NH4)8[CeW 10O36]·OH2O, as catalyst in high yields. Primary and secondary alcohols were also converted to their corresponding acetates and formates with acetic acid and ethyl formate in the presence of this catalyst. Easy work-up, non-toxicity, reusability, and stability of the catalyst are noteworthy advantages of this method. Springer-Verlag 2004.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Moghadam, Majid,Yadollahi, Bahram,Alipanah, Ladan
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p. 1257 - 1263
(2007/10/03)
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- A convenient and chemoselective acetylation and formylation of alcohols and phenols using acetic acid and ethyl formate in the presence of Bi(III) salts
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A variety of alcohols are acetylated and formylated efficiently with acetic acid and ethyl formate in the presence of catalytic amounts of Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3. BiCl3 and Bi(OTf)3 are also effective catalysts for acetylation of phenols. All of these catalysts are ineffective in formylation of phenols. Selective acetylation and formylation of alcohols in the presence of phenols is an additional advantage of this procedure.
- Mohammadpoor-Baltork,Khosropour,Aliyan
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p. 280 - 282
(2007/10/03)
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- Novel catalytic acetylation and formylation of alcohols with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O)
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Acetylation and formylation reactions of alcohols with ethyl acetate, acetic acid and ethyl formate were catalyzed with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O) in a mild, efficient and convenient method with high to excellent yields.
- Habibi, Mohammad H,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yadollahi, Bahram
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p. 8333 - 8337
(2007/10/03)
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