- A Convenient Synthesis of Fluorobenzaldehydes by KF/Ph4PBr/18-Crown-6 Reagent System
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4-Fluorobenzaldehyde was easily synthesized from 4-chlorobenzaldehyde by potassium fluoride in the presence of tetraphenylphosphonium halide plus 18-crown-6 or poly(ethylene glycol) dimethyl ether.Several fluorobenzaldehyde derivatives were similarly prepared from the corresponding chloro-derivatives in good yields.
- Yoshida, Yasuo,Kimura, Yoshikazu
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Read Online
- Method for efficiently synthesizing fluorine-containing compound
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The invention discloses a method for efficiently synthesizing a fluorine-containing compound, and relates to the field of fluorine-containing compound synthesis. The method is a method for generating a corresponding fluorine atom substituted fluorine-containing compound by reacting aromatic chloride or activated chloride serving as a raw material with potassium fluoride under the action of a novel catalyst. The method disclosed by the invention has the advantages of good product selectivity, high efficiency, mild reaction conditions, simplicity and convenience in operation, convenience in application and the like.
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Paragraph 0061-0063
(2021/06/26)
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- Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
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The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 645 - 656
(2020/05/14)
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- Direct formylation of fluorine-containing aromatics with dichloromethyl alkyl ethers
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Formylations of fluorine-containing aromatic compounds with dichloromethyl alkyl ethers have been investigated. Dichloromethyl propyl ether and dichloromethyl butyl ether have been applied for the formylation of fluorine-containing anisoles to give the corresponding aldehydes in good yields. Application of these ethers is preferable to that of methyl ether, which is prepared from volatile methyl formate. Reaction of fluorine-containing phenols with these dichloromethyl alkyl ethers did not give salicylaldehyde derivatives, leading instead to corresponding aryl formates in high yields. A plausible mechanism is discussed.
- Warashina, Takuya,Matsuura, Daisuke,Kimura, Yoshikazu
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p. 587 - 593
(2019/07/22)
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- Novel method for synthesizing dolutegravir key intermediate 2,4-difluorobenzylamine
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The invention discloses a novel production method which is concise and green in route, low in cost and easy to industrialize to prepare 2,4-difluorobenzylamine. The method comprises the following twosteps: a) at certain pressure, carrying out a carbonylation reaction on m-difluorobenzene and CO in the presence of a catalyst so as to generate 2,4-difluorobenzaldehyde, or carrying out a formylationreaction on m-difluorobenzene, namely carrying out chlorocarbene substitution on m-difluorobenzene in a chloroform strong base system, and further carrying out hydrolysis so as to prepare a product 2,4-difluorobenzaldehyde (Reimer-Tiemann reactions); b) putting the product 2,4-difluorobenzaldehyde of the step a) into an alcohol solvent, at certain pressure, in the presence of the catalyst, carrying out a reduction ammonolysis reaction on the component with an ammonia gas and hydrogen directly in the presence of a catalyst, or enabling the component to react with ammonium formate, thereby obtaining the 2,4-difluorobenzylamine. The preparation method disclosed by the invention is simple and easy in raw material obtaining, concise in route, green and environmentally friendly, low in cost andeasy in industrial production.
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Paragraph 0029; 0031; 0032; 0035
(2018/11/22)
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- Method for preparing 2,4-difluorobenzaldehyde through continuous oxidation of 2,4-difluorotoluene
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The invention relates to a method for preparing 2,4-difluorobenzaldehyde through continuous oxidation of 2,4-difluorotoluene, and belongs to the technical field of organic synthesis processes. According to the method, a 2,4-difluorotoluene compound is adopted as a raw material, one or a plurality of metal ion complexes of cobalt, molybdenum and bromine are adopted as a catalyst, hydrogen peroxide is adopted as an oxidant, acetic acid is adopted as a solvent, and 2,4-difluorotoluene is continuously oxidized in a tubular reactor to prepare 2,4-difluorobenzaldehyde. According to the present invention, the method has advantages of mild condition, short reaction time, high raw material utilization rate, safety, stability, continuous operation and high production efficiency, and can achieve the effective control during the reaction process.
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Paragraph 0040-0066
(2017/08/28)
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- Aldehyde and Ketone Synthesis by P450-Catalyzed Oxidative Deamination of Alkyl Azides
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Heme-containing proteins have recently attracted increasing attention for their ability to promote synthetically valuable transformations not found in nature. Following the recent discovery that engineered variants of myoglobin can catalyze the direct conversion of organic azides into aldehydes, we investigated the azide oxidative deamination reactivity of a variety of hemoproteins featuring different heme coordination environments. Our studies show that although several heme-containing enzymes possess basal activity in this reaction, an engineered variant of the bacterial cytochrome P450 CYP102A1 constitutes a particularly efficient biocatalyst for promoting this transformation, and it exhibits a broad substrate scope along with high catalytic activity (up to 11 300 turnovers), excellent chemoselectivity, and enhanced reactivity toward secondary alkyl azides to yield ketones. Mechanistic studies and Michaelis–Menten analyses provided insight into the mechanism of the reaction and the impact of active-site mutations on the catalytic properties of the P450. Altogether, these studies demonstrate that engineered P450 variants represent promising biocatalysts for the synthesis of aryl aldehydes and ketones through the oxidative deamination of alkyl azides under mild reaction conditions.
- Giovani, Simone,Alwaseem, Hanan,Fasan, Rudi
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p. 2609 - 2613
(2016/08/30)
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- TRICYCLIC PIPERIDINE COMPOUNDS
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The present invention relates to compounds of the formula (I), wherein R, R1a, R1b, R2, R3, and X are as described in the description, to their preparation, to pharmaceutically acceptable salts thereof, and to their use as pharmaceuticals, to pharmaceutical compositions containing one or more compounds of formula (I), to methods for the preparation of such compounds of formula (I), and especially to their use as TPH modulators.
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Page/Page column 111-112; 122
(2015/06/08)
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- Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin
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The oxidation of primary azides to aldehydes constitutes a convenient but underdeveloped transformation for which no efficient methods are available. Here, we demonstrate that engineered variants of the hemoprotein myoglobin can catalyze this transformation with high efficiency (up to 8500 turnovers) and selectivity across a range of structurally diverse aryl-substituted primary azides. Mutagenesis of the 'distal' histidine residue was particularly effective in enhancing the azide oxidation reactivity of myoglobin, enabling these reactions to proceed in good to excellent yields (37-89%) and to be carried out at a synthetically useful scale. Kinetic isotope effect, isotope labeling, and substrate binding experiments support a mechanism involving heme-catalyzed decomposition of the organic azide followed by alpha hydrogen deprotonation to generate an aldimine which, upon hydrolysis, releases the aldehyde product. This work provides the first example of a biocatalytic azide-to-aldehyde conversion and expands the range of non-native chemical transformations accessible through hemoprotein-mediated catalysis.
- Giovani, Simone,Singh, Ritesh,Fasan, Rudi
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p. 234 - 239
(2015/12/30)
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- Practical Cu(OAc)2/TEMPO-catalyzed selective aerobic alcohol oxidation under ambient conditions in aqueous acetonitrile
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We reported a ligand-and additive-free Cu(OAc)2/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary and secondary benzylic alcohols, primary and secondary 1-heteroaryl alcohols, cinnamyl alcohols, and aliphatic alcohols to the corresponding aldehydes and ketones. This ambient temperature oxidation protocol is of practical features like aqueous acetonitrile as solvent, ambient air as the terminal oxidant, and low catalyst loading, presenting a potential value in terms of both economical and environmental considerations. Based on the experimental observations, a plausible reaction mechanism was proposed.
- Jiang, Jian-An,Du, Jia-Lei,Wang, Zhan-Guo,Zhang, Zhong-Nan,Xu, Xi,Zheng, Gan-Lin,Ji, Ya-Fei
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supporting information
p. 1677 - 1681
(2014/03/21)
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- (Oxime)carbamoyl fatty acid amide hydrolase inhibitors
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The present invention relates to novel oxime carbamyl derivatives and pharmaceutical compositions comprising said derivatives which inhibit fatty acid amide hydrolase. These pharmaceutical compositions are useful for the treatment of conditions which can be effected by inhibiting fatty acid amide hydrolase including, but not limited to, neuropathic pain, emesis, anxiety, altering feeding behaviors, movement disorders, glaucoma, brain injury, and cardiovascular disease.
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- Method for treating patient having precancerous lesions with a combination of pyrimidopyrimidine derivatives and esters and amides of substituted indenyl acetic acides
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Combinations of substituted indenyl acetic acids and pyrimido-pyrimidine derivatives are useful in the treatment of colonic polyps and inhibiting the growth of neoplastic cells.
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- Substituted methoxy benzylidene indenyl-acetic and propionic acids for treating patients with precancerous lesions
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Substituted methoxy benzylidene indenyl compounds are useful in the treatment of precancerous lesions and neoplasms.
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- Ytterbium(III) triflate as a recyclable catalyst for the selective atom economic oxidation of benzyl alcohols to benzaldehydes
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Ytterbium(III) triflate (10mol%) was found to catalyse the selective oxidation of a range of simple benzyl alcohols to benzaldehydes in good to excellent yield using a stoichiometric quantity of 69% nitric acid as the oxidant, and where the only by-products were water and oxides of nitrogen. The catalyst can be readily recovered and recycled by a simple evaporative process.
- Barrett, Anthony G. M.,Braddock, D. Christopher,McKinnell, R. Murray,Waller, Francis J.
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p. 1489 - 1490
(2007/10/03)
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- Synthetic applications of fluorinated phenyllithiums: Preparation of fluorinated α-methylstyrenes, benzhydrols, benzophenones and aryltrimethylsilanes
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Regioselective preparations of a number of fluorinated phenyllithiums have recently been reported, which in some cases also contain one or more bromine substituents. These have now been applied to the synthesis of the corresponding halogenated 2-arylpropenes (α-methyl-styrenes), benzhydrols, trifluoromethylbenzhydrols, benzophenones and aryltrimethylsilanes.
- Yarwood, Thomas David,Waring, Anthony John,Coe, Paul Leslie
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p. 113 - 119
(2007/10/03)
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- Method for treating patients with precancerous lesions by administering substituted sulfonyl idenyl acetic and propionic acids and esters to patients with lesions sensitive to such compounds
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Substituted indenyl sulfonyl acetic acids are useful in the treatment of precancerous lesions sensitive to treatment with those sulfonyl compounds.
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- Esters and amides of substituted indenyl acetic acids
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Esters and amides of substituted indenyl acetic acids of the formula: n is an integer of at least 2;, Q is a deprotonated residue of polymer or macromolecular structure having a molecular weight of at least about 1000 containing at least two primary and/or secondary amino groups and/or hydroxy groups;, R1 is selected from hydrogen, lower alkyl, or haloalkyl;, R2 is selected from hydrogen or alkyl;, R3 and R4 are one or more members each independently chosen from hydrogen, alkyl, acyloxy, alkoxy, nitro, amino, acylamino, alkylamino, diakylamino, dialkylaminoalkyl, sulfamyl, alkythio, mercapto, hydroxy, hydroxyalkyl, alkylsulfonyl, halogen, cyano, carboxyl, carbalkoxy, carbamido, haloalkyl or cycloalkoxy; and, R5 is selected from alkylsulfenyl, alkylsulfinyl or alkylsulfonyl. are useful in the treatment of colonic polyps.
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- 'HALEX' FLUORINATION OF CHLORINATED BENZALDEHYDES AND BENZOYL CHLORIDES
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Spray-dried potassium fluoride, suspended in sulpholane at 220 degC, converted 2,4- and 2,6-dichlorobenzaldehyde into the corresponding difluoroaldehydes (yields ca. 65percent).Small amounts of the mono-substituted products (2-chloro-4-fluoro- + 4-chloro-2-fluorobenzaldehyde, and 2-chloro-6-fluoro-benzaldehyde, respectively) were also produced.Similar treatment of the 3,4-dichloro-analogue gave 3-chloro-4-fluorobenzaldehyde (yield 98percent, conversion 68percent), but 2- and 4-chlorobenzaldehyde gave very poor yields (ca. 5percent) of the 2- and 4-fluoro-derivatives. 2-Fluoro-, 4-fluoro- and 3-chloro-4-fluorobenzoyl fluoride were obtained (yields 60-65percent) by heating the corresponding chlorobenzoyl chlorides with potassium fluoride in sulpholane.
- Banks, R. Eric,Mothersdale, Kevin N.,Tipping, Anthony E.,Tsiliopoulos, Efthimios,Cozens, Barry J.,et al.
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p. 529 - 537
(2007/10/02)
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- Process for the preparation of difluorobenzenes
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Difluorobenzene is prepared by a multistep process involving fluorination of dichlorobenzoyl chloride to provide difluorobenzoyl fluoride, conversion thereof to difluorobenzoyl chloride, hydrogenation of this to difluorobenzaldehyde and decarbonylation of the aldehyde to difluorobenzene.
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- OBSERVATIONS ON THE VILSMEIER REACTION Part 2. THE ANOMALOUS REACTION OF N-BENZYL N-CYANOETHYL-4-METHYLANILINE DERIVATIVES
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The reaction of a series of the title anilines (1) with variously substituted benzyl groups under Vilsmeier conditions was invesigated.Only perfluorobenzyl derivatives showed normal formylation while other fluoro derivatives gave mixed results and other substituents gave solely the anomalous amine (5) together with the aldehyde (6) derived from the benzyl group.
- Shawcross, Andrew P.,Stanforth, Stephen P.
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p. 7063 - 7076
(2007/10/02)
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- Antifungal 2-aryl-1,1-difluoro-3-(1H-1,2,4-triazol-1-yl)2-propanols
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Compounds of the formula STR1 a pharmaceutically or agriculturally acceptable acid addition salt thereof wherein R is 5-chloro-2-pyridyl, phenyl or phenyl substituted by from 1 to 3 substituents, each independently selected from F, Cl, Br, I, CF3, (C1 -C4)alkyl and (C1 -C4)alkoxy; and R1 is H, Cl, phenyl, phenyl substituted by from 1 to 3 substituents each independently selected from F, Cl, Br, I and CF3 or a heterocyclic group linked to the adjacent CF2 group by a ring carbon atom; method for their use in combatting fungal infections in plants, seeds and animals, including humans, and pharmaceutical and agricultural compositions containing them.
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- Fluorine containing 2,4,5-triphenylimidazoles
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Fluorosubstituted benzaldehydes are condensed with anisil and ammonium acetate to yield the corresponding 2-(fluorosubstituted phenyl)-4,5-bis(4-methoxyphenyl)imidazoles. Alternatively fluorosubstituted benzaldehydes are condensed with anisil monoxime and ammonium acetate to yield the corresponding 2-(fluorosubstituted phenyl)-4,5-bis(4-methoxyphenyl)-imidazole-3-oxides which can subsequently be reduced to yield the corresponding 2-(fluorosubstituted phenyl)-4,5-bis(4-methoxyphenyl)imidazoles. These imidazoles have interesting pharmacological properties.
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- Substituted imidazo thiazoles thiazines, thiazepines and thiazocines
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Disclosed herein are novel tetrahydro imidazo thiazoles, tetrahydro imidazo thiazines, hexahydro imidazo thiazepines and hexahydro imidazo thiazocines, intermediates for the preparation thereof, methods of using the compounds as anti-inflammatory agents and methods of using an intermediate thereof as anti-secretory agents to relieve the symptoms of gastric distress.
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