- Method for preparing aldehyde/ketone by breaking C-C key
-
The invention discloses a method for preparing aldehyde/ketone by breaking C-C bonds, and the method comprises the following steps of anaerobic condition. In an organic solvent system, an alcohol is used as a reaction raw material, and the C-C bond is selectively broken under the common action of an iron catalyst, an organic base and an additive to obtain aldehyde/ketone. The method is low in cost, easy to obtain, wide in substrate range, simple and product in post-treatment and high in purity, a new synthetic route and a method are developed for an aldehyde ketone compound, and the method has good application potential and research value.
- -
-
Paragraph 0077-0082
(2021/11/19)
-
- METHOD FOR CONVERTING HYDROXYL GROUP OF ALCOHOL
-
The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.
- -
-
Paragraph 0366-0368
(2021/02/19)
-
- Photochemical oxidation of benzylic primary and secondary alcohols utilizing air as the oxidant
-
A mild and green photochemical protocol for the oxidation of alcohols to aldehydes and ketones was developed. Utilizing thioxanthenone as the photocatalyst, molecular oxygen from air as the oxidant and cheap household lamps or sunlight as the light source, a variety of primary and secondary alcohols were converted into the corresponding aldehydes or ketones in low to excellent yields. The reaction mechanism was extensively studied.
- Nikitas, Nikolaos F.,Tzaras, Dimitrios Ioannis,Triandafillidi, Ierasia,Kokotos, Christoforos G.
-
supporting information
p. 471 - 477
(2020/02/13)
-
- Solvent-free direct α-alkylation of ketones by alcohols catalyzed by nickel supported on silica-alumina
-
The α-alkylation of acetophenone with benzyl alcohol through borrowing hydrogen has been studied using nickel catalysis. Ni/SiO2-Al2O3 was found to be the best catalyst for this transformation and the corresponding alkylated acetophenone was obtained with 93% isolated yield. Following the objectives of clean and sustainable chemistry, the reaction occurs under solvent-free conditions and requires only a catalytic amount of base. This protocol was next applied to a wide range of ketones and alcohols and the desired products were isolated with 18-86% yields (26 examples). The recovery and recyclability of the nickel catalyst was also investigated and it was found to be active over 5 runs without significant loss of activity. Surprisingly, the active catalyst appears to include an amorphous nickel hydroxide layer.
- Charvieux, Aubin,Giorgi, Javier B.,Duguet, Nicolas,Métay, Estelle
-
supporting information
p. 4210 - 4216
(2018/10/02)
-
- Visible-Light-Driven Epoxyacylation and Hydroacylation of Olefins Using Methylene Blue/Persulfate System in Water
-
A visible-light-driven strategy for hydroacylation and epoxyacylation of olefins in water using methylene blue as photoredox catalyst and persulfate as oxidant is reported. In this unprecedented unified approach, two different transformations are accomplished using only one set of reagents. The method has a broad scope spanning a range of aromatic and aliphatic aldehydes as well as conjugated and nonconjugated olefins to deliver ketones and epoxyketones from abundant and inexpensive chemical feedstocks.
- De Souza, Gabriela F. P.,Bonacin, Juliano A.,Salles, Airton G.
-
p. 8331 - 8340
(2018/07/21)
-
- Method for directly oxidizing benzyl-position C-H bond into ketone
-
The invention discloses a method for directly oxidizing a benzyl-position C-H bond into ketone, wherein aryl ethyl compounds are catalyzed and oxidized by nitrite ester; a synergistic catalytic system of free radical initiator and nitrite ester is adopted, and a catalytic system of non-metallic catalyst and oxygen is adopted, the oxidization of the C-H bond of a free radical-activated aryl side chain is simple in operation; after completing the reaction, petroleum ether/ethyl acetate at a volume ratio of (50-1):1 is used as an eluent; column chromatography separation is performed to obtain a target product. The catalytic system in the invention uses oxygen as an oxygen source and has high atomic economy; the invention is a non-metallic catalytic system and provides a novel method for avoid metal residues in synthetic drugs; for diethyl aromatic hydrocarbon, the method provided by the invention can be adopted to selectively oxidize diethyl aromatic hydrocarbon into monoketone and diketone; the method of the invention can be adopted to efficiently synthesize tranquillizer lenperone, so that a novel method for synthesizing lenperone is provided.
- -
-
Paragraph 0043-0045
(2017/08/29)
-
- Iron-Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides
-
An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C?C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.
- Zhu, Xiaotao,Ye, Changqing,Li, Yajun,Bao, Hongli
-
p. 10254 - 10258
(2017/08/07)
-
- Synthesis of new chiral and racemic 1,3-dioxolanes
-
A series of chiral 1,3-dioxolanes, 3-12, with >99% ee values, have been synthesized. This is the first study of chiral ketalization reaction starting from ketones with aryl, monosubstituted aryl, and long alkyl chains (C 11-AC13). Their ee values were determined by chiral high-performance liquid chromatography (HPLC) on Chiralcel OD column, using their racemic 1,3-dioxolanes rac-3-12, which were also synthesized for the first time. These chiral and racemic 1,3-dioxolanes were characterizated by infrared, NMR (1H, 13C), mass spectrometry, elemental analysis, optical rotation, and chiral HPLC.
- Kuecuek, Hatice Baspinar,Yusufoglu, Ayse
-
p. 1066 - 1070,5
(2012/12/12)
-
- Synthesis of new chiral and racemic 1,3-dioxolanes
-
A series of chiral 1,3-dioxolanes, 3-12, with >99% ee values, have been synthesized. This is the first study of chiral ketalization reaction starting from ketones with aryl, monosubstituted aryl, and long alkyl chains (C 11-AC13). Their ee values were determined by chiral high-performance liquid chromatography (HPLC) on Chiralcel OD column, using their racemic 1,3-dioxolanes rac-3-12, which were also synthesized for the first time. These chiral and racemic 1,3-dioxolanes were characterizated by infrared, NMR (1H, 13C), mass spectrometry, elemental analysis, optical rotation, and chiral HPLC.
- Kuecuek, Hatice Baspinar,Yusufoglu, Ayse
-
p. 1066 - 1070
(2013/01/15)
-
- Synthesis, insecticidal evaluation of novel 1,3,4-thiadiazole chrysanthemamide derivatives formed by an EDCI/HOBt condensation
-
A series of novel pesticides with two components derived from a 1,3,4-thiadiazole and chrysanthemic acid were synthesised via an EDCI/HOBt condensation. These 1,3,4-thiadiazole chrysanthemamides were identified by IR, 1H NMR and elemental analyses. Their insecticidal activity was also evaluated.
- Yu, Peng,Hu, Jun,Zhou, Tao-Yu,Wang, Peng,Xu, Yan-Hua
-
experimental part
p. 703 - 706
(2012/03/10)
-
- Double hydroacylation reactions of acyclic and cyclic α,β- unsaturated aldehydes
-
Double or quits? double hydroacylation reactions of acyclic and cyclic α,β-unsaturated aldehydes with olefins afford ketone and diketone products, respectively. Enantiomers are formed whose absolute configurations are controlled by the order of alkene addition.
- Cha, Kyung-Mi,Lee, Hyejeong,Park, Jung-Woo,Lee, Yura,Jo, Eun-Ae,Jun, Chul-Ho
-
supporting information; experimental part
p. 1926 - 1930
(2011/10/17)
-
- Nucleophilic benzoylation using a mandelic acid dioxolanone as a synthetic equivalent of the benzoyl carbanion. Oxidative decarboxylation of α-hydroxyacids
-
The synthesis of alkyl aryl ketones using a mandelic acid dioxolanone as a synthetic equivalent (Umpolung) of the benzoyl carbanion is reported. The methodology involves alkylation of the mandelic acid dioxolanone, hydrolysis of the dioxolanone moiety in the alkylated products and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co (III) complex in the presence of pivalaldehyde under very mild conditions.
- Blay, Gonzalo,Fernandez, Isabel,Monje, Belen,Pedro, Jose R.
-
p. 365 - 372
(2007/10/03)
-
- Novel Diradical-Mediated Ring Opening Reactions
-
Thermo-isomerization of medium- and large-ring 1-phenylcycloalkanols 1e-i at around 650 deg C in a flow reactor system delivers the open-chain phenones 4e-i. A reaction mechanism via an open-chain diradical intermediate, followed by an intramolecular hydrogen transfer is proposed. Thermo-isomerization of α-substituted 1-phenylcyclododecanols 6 proceeds regioselectively under the formation of ω-substituted phenones 7. Furthermore, this novel hydrogen transfer reaction provides a new access to ω-substituted fatty acids.
- Rueedi, Georg,Nagel, Matthias,Hansen, Hans-Juergen
-
p. 1210 - 1212
(2007/10/03)
-
- Nucleophilic benzoylation using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion. Oxidative decarboxylation of α-hydroxyacids
-
The synthesis of alkyl aryl ketones using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion is reported (Umpolung). The methodology involves alkylation of methyl mandelate, hydrolysis of the ester group and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co(III) complex in the presence of pivalaldehyde under very mild and advantageous conditions. The procedure is also applied to methyl mandelates substituted on the aromatic ring.
- Blay, Gonzalo,Fernández, Isabel,Formentin, Pilar,Monje, Belén,Pedro, José R,Ruiz, Rafael
-
p. 1075 - 1081
(2007/10/03)
-
- Catalytic aerobic oxidative decarboxylation of α-hydroxy-acids. Methyl mandelate as a benzoyl anion equivalent
-
The monomeric square-planar cobalt(III) complex of bis-N,N'- disubstituted oxamides catalyses the oxidative decarboxylation of α-hydroxy acids with molecular oxygen/pivalaldehyde with very good yields. This reaction offers an interesting alternative in the use of methyl mandelate as a convenient benzoyl anion equivalent.
- Blay, Gonzalo,Fernandez, Isabel,Formentin, Pilar,Pedro, Jose R.,Rosello, Antonio L.,Ruiz, Rafael,Journaux, Yves
-
p. 3327 - 3330
(2007/10/03)
-
- Direct formation of organomanganese bromides using Rieke manganese
-
The direct formation of organomanganese bromides can be accomplished under mild conditions from the direct oxidative addition to Rieke manganese to alkyl and thienyl bromides.
- Kim, Seung-Hoi,Hanson, Mark V.,Rieke, Reuben D.
-
p. 2197 - 2200
(2007/10/03)
-
- A Convenient and Efficient Unsymmetrical Ketone Synthesis from Acid Chlorides and Alkyl Iodides Catalyzed by Palladium
-
Unsymmetrical ketones are prepared in good or excellent yields by a palladium catalyzed coupling reaction of acid chlorides and alkyl iodides meditated by Zn-Cu couple.
- Tamaru, Yoshinao,Ochiai, Hirofumi,Sanda, Fumio,Yoshida, Zen-ichi
-
p. 5529 - 5532
(2007/10/02)
-
- THE PREPARATION OF PHENYL KETONES USING (PHENYLTHIO)PHENYL(TRIMETHYLSILYL)METHYL-LITHIUM
-
Phenyl ketones are prepared by alkylation of (phenylthio)phenyl(trimethylsilyl)methyl-lithium followed by oxidation and rearrangement.
- Ager, David J.
-
p. 4759 - 4762
(2007/10/02)
-