- Practical acetalization and transacetalization of carbonyl compounds catalyzed by recyclable PVP-I
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A novel PVP-I catalyzed acetalizations/transacetalizations of carbonyl compounds has been developed processing with a mild and easy handling fashion. Different types of Acyclic and cyclic acetals were prepared from carbonyl compounds or their acetals successfully. Further applications of newly developed catalytic combination were testified. This protocol featured with simplicity of operation, mild reaction condition, short reaction time, recyclable of catalyst and broad substrates scope with excellent yields.
- Cao, Fu-Rong,Lu, Guangying,Ren, Jiangmeng,Wang, Di,Zeng, Bu-Bing
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- Two-way homologation of aliphatic aldehydes: Both one-carbon shortening and lengthening via the same intermediate
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Aliphatic aldehydes can be homologated to both one-carbon shorter and one-carbon longer homologous carbonyl compounds through the 2–4 steps of reactions via the same intermediates, β,γ-unsaturated α-nitrosulfones, prepared from the proline-catalyzed sequential reactions of several aliphatic aldehydes with phenylsulfonylnitromethane. While the oxidative cleavage of the key intermediates gave one-carbon less homologous carbonyl compounds, the reduction of the same key intermediates followed by an oxidation produced one-carbon more homologous carbonyl compounds.
- Yoo, Jae Won,Seo, Youngran,Park, Jong Beom,Kim, Young Gyu
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- Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling
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A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO2 catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.
- Fan, Yonghui,Li, Shenggang,Bao, Jingxian,Shi, Lei,Yang, Yanzhang,Yu, Fei,Gao, Peng,Wang, Hui,Zhong, Liangshu,Sun, Yuhan
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supporting information
p. 3450 - 3456
(2018/08/06)
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- Hydroformylation-hydrogenation and hydroformylation-acetalization reactions catalyzed by ruthenium complexes
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In this work, the catalytic activity of ruthenium II and III complexes containing chloride, pyridine, phosphine and CO ligands was investigated in the hydroformylation – hydrogenation and hydroformylation – acetalization reactions. The complexes mer-[RuCl3(dppb)(H2O)](1), mer-[RuCl3(dppb)(4-Vpy)](2), mer-[RuCl3(dppb)(4-tBupy)](3), mer-[RuCl3(dppb)(py)](4), mer-[RuCl3(dppb)(4-Phpy)](5), mer-[RuCl3(dppb)(4-Mepy)](6), cis-[RuCl2(CO)2(dppb)](7), trans-[RuCl2(CO)2(dppb)](8), RuCl3·xH2O(9), [RuCl2(PPh3)3](10) and [RuCl2(PPh3)2(dppb)](11) were used as supplied or synthesized as previously described in the literature {Where PPh3?=?triphenylphosphine, dppb?=?1,4-bis(diphenylphosphino)butane, py?=?pyridine, 4-Mepy?=?4-methylpyridine, 4-Vpy?=?4-vinylpyridine, 4-tBupy?=?4-tert-butylpyridine and 4-Phpy?=?4-phenylpyridine}. These complexes were used as a pre-catalysts in a hydroformylation catalytic system to produce C[sbnd]C, C[dbnd]O and C[sbnd]O bonds, where 1-decene resulted in a formation of respective alcohol and dimethyl acetals. Several reactions were performed in order to find the best reaction conditions presenting the best conversion (64% after 24?h). The 1-decene was also used as a substrate in two type tandem reactions labeled as: hydroformylation – hydrogenation (HH) and hydroformylation – acetalization (HA) reactions. The relationship between Ru – catalyst/substrate was 1:100, without free ligands or additives, in a controlled temperature and pressure. All the products of catalytic reactions HH and HA were analyzed by CG-FID with good yields.
- Rodrigues, Claudia,Delolo, Fabio G.,Norinder, Jakob,B?rner, Armin,Bogado, André L.,Batista, Alzir A.
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p. 586 - 592
(2016/12/16)
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- Quantification of Nonanal and Oleic Acid Formed during the Ozonolysis of Vegetable Oil Free Fatty Acids or Fatty Acid Methyl Esters
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The ozonolysis of unsaturated lipids is a process that has been used to generate aldehydes, acids, alcohols, and other biobased chemical intermediates. Reported here is a method that can be used to measure the formation of nonanal and oleic acid during the ozonolysis of unsaturated vegetable oil fatty acids or their methyl esters to indicate the extent of the ozonolysis reaction. Derivatization was performed using boron trifluoride in methanol solution to transform nonanal and oleic acid into nonanal dimethyl acetal and oleic acid methyl ester, respectively. Undecanal and 10-heptadecenoic acid were used as internal standards and separation was performed using gas chromatography coupled with a flame ionization detector. The method was validated by performing a standard addition procedure in which nonanal or oleic acid standards were spiked into samples collected during the ozonolysis of oleic acid or canola oil fatty acid methyl ester (FAME). Linear regression results indicated that the measured nonanal and oleic acid are in good agreement with the actual amounts of nonanal and oleic acid added to the sample with at least 98 % recovery. The application of the method was demonstrated by the successful measurement of nonanal and oleic acid formed throughout the ozonolysis process for high oleic canola oil FAME.
- Tavassoli-Kafrani,Foley,Kharraz,Curtis
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p. 303 - 310
(2016/03/08)
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- Highly efficient acetalization of carbonyl compounds catalyzed by anilin-aldehyde resin salts
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A mild procedures for the syntheses of ethylene acetals and dimethyl acetals from the corresponding aldehydes and ketones catalyzed by 1mol% of anilinealdehyde resin salts are described. This method is also useful for the synthesis of dimethyl acetals of diaryl ketones.
- Tanemura, Kiyoshi,Suzuki, Tsuneo
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supporting information
p. 797 - 799
(2015/06/22)
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- A recyclable fluorous hydrazine-1,2-bis(carbothioate) with NCS as efficient catalysts for acetalization of aldehydes
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A fluorous hydrazine-carbothioate organocatalyst was prepared. Together with NCS, the catalyst showed a good activity in acetalization of aldehydes and alcohols. It could be recovered from the reaction mixture by fluorous solid-phase extraction (F-SPE) with excellent purity for direct reuse.
- Zhu, Yi-Wei,Yi, Wen-Bin,Cai, Chun
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supporting information
p. 890 - 892
(2013/07/05)
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- Highly effective tandem hydroformylation-acetalization of olefins using a long-life Bronsted acid-Rh bifunctional catalyst in ionic liquid-alcohol systems
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A robust and highly effective tandem hydroformylation-acetalization of olefins using a Bronsted acid-Rh bifunctional catalyst (ARBC) in ionic liquid-alcohol systems is reported. The key feature of the ARBC is its use of a zwitterionic phosphine ligand bearing an amino acid tag. This novel ARBC shows an excellent catalytic efficiency and a long service life without a significant drop in both the hydroformylation efficiency and the acetalization efficiency or Rh loss for more than seventeen cycles. We believe that the long-term high activity and acetal selectivity mainly benefit from the synergy between the acidic active site and the Rh active site on the ARBC and the highly effective immobilization and recycling of ARBC in ionic liquid-alcohol systems due to the strong affinity of ARBC for the ionic liquid.
- Jin, Xin,Zhao, Kun,Cui, Feifei,Kong, Fangfang,Liu, Qiangqiang
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p. 3236 - 3242
(2013/11/06)
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- NCS with thiourea as highly efficient catalysts for acetalization of aldehydes
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NCS/thiourea-mediated acetalization of aldehydes and alcohols has rapidly provided acetals in almost quantitative yields.
- Mei,Bentley,Du
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supporting information; experimental part
p. 4199 - 4200
(2009/10/04)
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- Oxidation of monohydric and dihydric alcohols with CCl4 catalyzed by molybdenum compounds
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Mo(CO)6 catalyzed oxidation of alcohols and diols with tetrachloromethane. Primary oxidation products in reaction of alcohols with CCl4 are alkyl hypochlorites, and final products depending on the structure of initial alcohol are aldehydes (as acetals), ketones, chloroketones, and esters.
- Khusnutdinov,Shchadneva,Burangulova,Muslimov,Dzhemilev
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p. 1615 - 1621
(2007/10/03)
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- (Benzotriazol-1-yl)methoxymethyl anion: A novel methylal anion equivalent
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The title anion readily reacts with a variety of electrophiles to give adducts which, upon treatment with methanol in the presence of p-toluenesulfonic acid, afford the corresponding α-functionalized dimethyl acetals.
- Katritzky,Yang,Cundy
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p. 3061 - 3071
(2007/10/02)
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- Oxidative Breaking of Long-Chain Acetylenic Enol Ethers of Glycerol of the Marine Sponges Raspailia pumila and R. ramosa and of Model Compounds with Aerial Oxygen
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The raspailynes (novel long-chain enol ethers of glycerol having the enol ether double bond conjugated, in sequence, to an acetylenic and an olefinic bond, isolated from the North-East-Atlantic sponges Raspailia pumila and R. ramosa) are stable under normal hydrolytic conditions for enol ethers.In contrast, when their solutions are evaporated, these lipids such as raspailyne B1 (=(-)-3--1,2-propanediol; (-)-2) rapidly react with aerial O2 under normal laboratory-daylight conditions, with rupture of the C=C enol ether bond to give 1-O-formylglycerol (3) and an aldehyde (such as tridec-4-en-3-ynal(4) from (-)-2).This reaction must be caused by triplet O2, since thermally generated singlet O2 has no effect on (-)-2 in solution.That the mere presence of an enol-ether moiety conjugated to an acetylenic group is responsible for such a behaviour is demonstrated with the model compounds 1-methoxypentadec-1-en-3-yn-5-ol (6a) and its 5-O-acetyl or 5-O-tetrahydropyranyl derivatives 6b and 6c, respectively.Resistance to both hydrolytic conditions and singlet O2 of these compounds is thought to arise from electron depletion at the enol-ether C(β) atom by the acetylenic group.Plausible reaction pathways for enol-ether bond rupture in these compounds by aerial O2 are outlined.
- Guella, Graziano,Mancini, Ines,Pietra, Francesco
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p. 1400 - 1411
(2007/10/02)
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- SYNTHESIS OF DIMETHYL ACETALS, DIETHYL ACETALS, AND CYCLIC ACETALS CATALYZED BY AMINOPROPYLATED SILICA GEL HYDROCHLORIDE (APSG*HCl)
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The aminopropylated Silica-Gel hydrochloride (APSG*HCl) proved to be an efficient catalyst for the rapid conversion of carbonyl compounds in the corresponding acetals with high yields and in mild and selective conditions.In addition to the obvious advantages offered by heterogeneous catalysis, the present method results very useful when the presence of a weakly-acidic function chemically bonded on the catalyst surface (alkyl ammonium salt) is necessary (compounds which contains functions unstable in acidic media).
- Gasparrini, F.,Giovannoli, M.,Misiti, D.,Palmieri, G.
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p. 1491 - 1500
(2007/10/02)
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