- An improved preparation of 3,5-bis(trifluoromethyl)acetophenone and safety considerations in the preparation of 3,5-bis(trifluoromethyl)phenyl Grignard reagent
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An improved and efficient bromination of 3,5-bis(trifluoromethyl)benzene was developed. A safe and reliable preparation of the potentially explosive 3,5-bis(trifluoromethyl)phenyl Grignard and 3-trifluoromethylphenyl Grignard reagents, from the precursor bromides, is described. Reaction System Screening Tool (RSST) and Differential Thermal Analysis (DTA) studies suggest these trifluoromethylphenyl Grignard reagents can detonate on loss of solvent contact or upon moderate heating. When prepared and handled according to the methods described herein, these Grignard reagents can be safely prepared and carried on to advanced intermediates.
- Leazer Jr., Johnnie L.,Cvetovich, Raymond,Tsay, Fuh-Rong,Dolling, Ulf,Vickery, Thomas,Bachert, Donald
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- V2O5@TiO2 Catalyzed Green and Selective Oxidation of Alcohols, Alkylbenzenes and Styrenes to Carbonyls
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The versatile application of different functional groups such as alcohols (1° and 2°), alkyl arenes, and (aryl)olefins to construct carbon-oxygen bond via oxidation is an area of intense research. Here, we report a reusable heterogeneous V2O5@TiO2 catalyzed selective oxidation of various functionalities utilizing different mild and eco-compatible oxidants under greener reaction conditions. The method was successfully applied for the alcohol oxidation, oxidative scission of styrenes, and benzylic C?H oxidation to their corresponding aldehydes and ketones. The utilization of mild and eco-friendly oxidizing reagents such as K2S2O8, H2O2 (30 % aq.), TBHP (70 % aq.), broad substrate scope, gram-scale synthesis, and catalyst recyclability are notable features of the developed protocol.
- Upadhyay, Rahul,Kumar, Shashi,Maurya, Sushil K.
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p. 3594 - 3600
(2021/07/02)
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- Preparation method of 3, 5-bis (trifluoromethyl) acetophenone
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The invention provides a preparation method of 3, 5-bis (trifluoromethyl) acetophenone. 3, 5-bis (trifluoromethyl) acetophenone is synthesized by using 3, 5-bis (trifluoromethyl) bromobenzene as a rawmaterial. The preparation method comprises the following steps: under a reaction temperature, selectively mixing either N-methoxy-N-methylacetamide or N-methoxy-N-methylformamide with 3, 5-bis (trifluoromethyl) bromobenzene and n-butyl lithium, and carrying out a stirring reaction under a reaction solvent condition at a reaction temperature of -70 to -90 DEG C; and executing a post-processing step, namely, heating to room temperature, extraction and washing, drying and evaporating to remove the residual solvent, and performing column chromatography separation to obtain 3, 5-bis (trifluoromethyl) acetophenone. According to the invention, cheap 3, 5-bis (trifluoromethyl) bromobenzene as a raw material directly reacts with N-methoxy-N-methylacetamide to obtain the high-yield 3, 5-bis (trifluoromethyl) acetophenone, the method is simple in reaction steps, easy to control and suitable for industrial production, so that a more valuable synthesis route is provided for preparation of aprepitant, good social benefits and economic benefits can be brought, and the economic value potential is relatively large.
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Paragraph 0029; 0034-0035
(2020/07/13)
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- Asymmetric aerobic oxidation of secondary alcohols catalyzed by poly(: N-vinyl-2-pyrrolidone)-stabilized gold clusters modified with cyclodextrin derivatives
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Surface modification of poly(N-vinyl-2-pyrrolidone)-stabilized gold clusters (1.8 ± 0.6 nm) with aminated cyclodextrins induced aerobic oxidative kinetic resolution of racemic secondary alcohols (krel = 1.2).
- Hirano, Koto,Takano, Shinjiro,Tsukuda, Tatsuya
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supporting information
p. 15033 - 15036
(2020/01/03)
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- A Straightforward Deracemization of sec-Alcohols Combining Organocatalytic Oxidation and Biocatalytic Reduction
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An efficient organocatalytic oxidation of racemic secondary alcohols, mediated by sodium hypochlorite (NaOCl) and 2-azaadamantane N-oxyl (AZADO), has been conveniently coupled with a highly stereoselective bioreduction of the intermediate ketone, catalyzed by ketoreductases, in aqueous medium. The potential of this one-pot two-step deracemization process has been proven by a large set of structurally different secondary alcohols. Reactions were carried out up to 100 mm final concentration enabling the preparation of enantiopure alcohols with very high isolated yields (up to 98 %). When the protocol was applied to the stereoisomeric rac/meso mixture of diols, these were obtained with very high enantiomeric excesses and diastereomeric ratios (95 % yield, >99 % ee, >99: 1 dr).
- Liardo, Elisa,Ríos-Lombardía, Nicolás,Morís, Francisco,González-Sabín, Javier,Rebolledo, Francisca
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supporting information
p. 3031 - 3035
(2018/06/27)
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- Conversion of Olefins into Ketones by an Iron-Catalyzed Wacker-type Oxidation Using Oxygen as the Sole Oxidant
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We describe a mild and operationally simple procedure for the oxidation of olefins into ketones. The reaction is catalyzed by the hexadecafluorinated iron–phthalocyanine complex FePcF16 with stoichiometric amounts of triethylsilane as an additive under oxygen atmosphere to give ketones in good to high yields with excellent chemoselectivity and functional group tolerance. Ketone formation proceeds in up to 95 % yield and with 100 % regioselectivity while the corresponding alcohols were observed as side products.
- Puls, Florian,Kn?lker, Hans-Joachim
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supporting information
p. 1222 - 1226
(2018/01/01)
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- Efficient and mild swern oxidation using a new sulfoxide and bis(trichloromethyl)carbonate
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A new type of sulfoxide, 4-(2-(2-(methylsulfinyl) ethyl)-4-nitrophenyl)-morpholine (I), was designed and prepared in good yield. Upon the combination of I and bis(trichloromethyl)carbonate, the Swern oxidation of primary and secondary alcohols was significantly promoted under mild conditions, which afforded the corresponding aldehydes or ketones in good yields. It is noteworthy that the reoxidation of the isolated by-product sulfide V could be further recycled in Swern oxidation.
- Ye, Xiaojing,Fu, Hongliang,Ma, Jiahao,Zhong, Weihui
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supporting information
p. 885 - 892
(2017/01/28)
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- HIGH-PURITY (FLUOROALKYL)BENZENE DERIVATIVE AND PROCESS FOR PRODUCING THE SAME
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The process for producing a (fluoroalkyl)benzene derivative according to the present invention comprises a step of reducing the total content of group 3 to group 12 transition metals in an alkylbenzene derivative to 500 ppm or less in terms of metal atoms; a step of halogenating the branched alkyl group of the purified alkylbenzene derivative by a photohalogenation to obtain a (haloalkyl)benzene derivative; and a step of subjecting the (haloalkyl)benzene derivative to a halogen-fluorine exchange using HF in an amount of 10 mol or higher per one mole of the (haloalkyl)benzene derivative. The (fluoroalkyl)benzene derivative produced by the process is reduced in the content of impurities such as residual halogens and residual metals, and is useful as intermediates for functional chemical products for use in applications such as medicines and electronic materials.
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- PROCESS FOR THE MANUFACTURE OF 3,5-BIS(TRIFLUOROMETHYL)ACETOPHENONE
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The present invention relates to a process for the manufacture of 3,5-bis(trifluoromethyl)acetophenone by oxidation of 3,5-bis(trifluoromethyl)phenyl-1-hydroxyethane by means of hydrogen peroxide in an inert solvent in the presence of an oxidation catalyst.
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- 1,3-Bis(trifluoromethyl)benzene derivatives
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A method of manufacture of 3,5-bis(trifluoromethyl)bromobenzene, comprising the addition of a brominating reagent to a mixture of 3,5-bis(trifluoromethyl)benzene together with at least one of sulphuric acid or oleum in the absence of acetic acid. A method of production of 3,5-bis(trifluoromethyl)acetophenone comprising the reaction of 3,5-bis(trifluoromethyl)phenyl magnesium bromide with acetyl chloride in the presence of cuprous chloride. A method of production of 3,5-bis(trifluoromethyl)acetophenone comprising the steps of reacting 3,5-bis(trifluoromethyl)phenyl magnesium bromide with acetic anhydride, adding water, and recovering the product by azeotropic distillation. A method of removal of impurities including 3,5-bis(trifluoromethyl)acetate, 4-bromobutyl acetate and 4-chlorobutyl acetate from a preparation of 3,5-bis(trifluoromethyl)acetophenone, the method comprising heating the 3,5-bis(trifluoromethyl)acetophenone with a dilute solution of alkali. A method of production of 3,5-bis(trifluoromethyl)phenyl magnesium bromide comprising the reaction of 3,5-bis(trifluoromethyl)bromobenzene with magnesium in a solvent whilst maintaining the temperature of the reactants above 20° C. and below the reflux temperature of the solvent.
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- SUBSTITUTED 4-PHENYLTETRAHYDROISOQUINOLINES, METHOD FOR THE PRODUCTION THEREOF, THE USE OF THE SAME AS MEDICAMENTS, AND MEDICAMENT CONTAINING SUCH COMPOUNDS
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The invention relates to compounds of formula I wherein R1 to R9 have the designations cited in the patent claims. Medicaments containing this type of compound can be used in the prevention or treatment of various illnesses. Said compounds can be used, inter alia, for renal diseases such as acute or chronic kidney failure, for disturbances of the biliary function, for respiratory disturbances such as snoring or sleep apnoea, or for apoplexy.
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Page/Page column 70
(2008/06/13)
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- Process for the synthesis of (R)-1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-ol by asymmetric transfer hydrogenation
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The present invention is concerned with novel processes for the preparation of (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol. This compound is useful as an intermediate in the synthesis of compounds which possess pharmacological activity.
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- Method of treating cancer
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The present invention relates to methods of treating cancer using a combination of a compound which is a PSA conjugate and a tachykinin receptor antagonist, which methods comprise administering to said mammal, either sequentially in any order or simultaneously, amounts of at least two therapeutic agents selected from a group consisting of a compound which is a PSA conjugate and a tachykinin receptor antagonist. The invention also relates to methods of preparing such compositions.
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- Scope of enantioselective Palladium(II)-catalyzed aerobic alcohol oxidations with (-)-sparteine
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Evaluation of the substrate scope for Pd(II)/ (-)-sparteine catalyzed aerobic oxidative kinetic resolution of secondary alcohols is disclosed. An improved system is found with use of tert-butyl alcohol solvent in which benzylic and aliphatic alcohols as well as alcohols containing olefins are effectively oxidatively resolved. For substrates that successfully undergo oxidative kinetic resolution, krel values are generally between 10 and 20. Successful scale-up of various substrates to 10-mmol scale is described. Extension to oxidative desymmetrization of 1,3-meso-diols is successful with enantiomeric excesses ranging from 78 to 85%.
- Mandal, Sunil K.,Jensen, David R.,Pugsley, Jacob S.,Sigman, Matthew S.
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p. 4600 - 4603
(2007/10/03)
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- Process for the synthesis of 1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-one
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The present invention is concerned with a novel process for the preparation of 1-(3,5-bis(trifluromethyl)phenyl)ethan-1-one (CAS 30071-93-3). This compound is useful as an intermediate in the synthesis of therapeutic agents.
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- Trans-glycosidation process for the synthesis of (2R, 2-alpha-R, 3a) -2-(1- (3,5-bis(trifluoromethyl) phenyl) ethoxy ) -3- (4-fluorophenyl) -1, 4-oxazine
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The present invention is concerned with novel processes for the preparation of (2R, 2-alpha-R, 3a)-2-[1-[3,5-bis(trifluoromethyl)phenyl]ethoxy-3-(4-fluorophenyl)-1,4-oxazine. This compound is useful as an intermediate in the synthesis of compounds which possess pharmacological activity.
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- Process for the syntehesis of (2R, 2-alpha-R, 3A) - 2- [1- (3, 5-bis(trifluoromethyl) phenyl) ethoxy] -3- (4-fluorophenyl) -1, 4-oxazine
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The present invention is concerned with novel processes for the preparation of (2R, 2-alpha-R, 3a)-2-[1-[3,5-bis(trifluoromethyl)phenyl]ethoxy-3-(4-fluorophenyl)-1,4-oxazine. This compound is useful as an intermediate in the synthesis of compounds which possess pharmacological activity.
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- Process for the synthesis of (2R, 2-alpha-R) -4-benzyl-2-[1- (3,5-bis (trifluoromethyl) phenyl) ethoxy] -1,4-oxazine-3-one
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The present invention is concerned with novel processes for the preparation of (2R, 2-alpha-R)-4-benzyl-2-[1-[3,5-bis(trifluoromethyl)phenyl]ethoxy-1,4-oxazin-3-one. This compound is useful as an intermediate in the synthesis of compounds which possess pharmacological activity.
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- Polymorphic form of a tachykinin receptor antagonist
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This invention is concerned with a novel polymorphic forms of the compound 2-(R)-(1-(R)-(3,5-bis(trifluoromethyl)phenyl)ethoxy)4-( 5-(dimethyl-amino)methyl-1,2,3-triazol-4-yl)methyl-3-(S)-(4-fluorophenyl)morpholine hydrochloride which is a tachykinin receptor antagonist useful in the treatment or prevention of disorders of the central nervous system, inflammatory diseases, pain or migraine, asthma, and emesis. The instant polymorphic forms have advantages over the other known forms of 2-(R)-(1-(R)-(3,5-bis(trifluoromethyl)phenyl)ethoxy)4-( 5-(dimethylamino)methyl-1,2,3-triazol-4-yl)methyl-3-(S)-(4-fluorophenyl)morpholine hydrochloride in terms of thermodynamic stability and suitability for inclusion in pharmaceutical formulations.
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- OPTICALLY ACTIVE METHOXYIMINOACETAMIDE DERIVATIVES, PROCESS FOR THE PREPARATION OF THEM, INTERMEDIATES THEREFOR, AND PESTICIDES CONTAINING THEM AS THE ACTIVE INGREDIENT
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An optically active methoxyiminoacetamide derivative represented by the following general formula (I) (in the above general formula, Ar represents an aryl group or a heteroaryl group, Y represents a hydrogen atom, a halogen atom, a C1-C4alkyl group, a C1-C4haloalkyl group, a C1-C4alkoxy group, a C1-C4haloalkoxy group, a C1-C4alkylthio group, a C2-C6alkynyloxy group, a cyano group, a nitro group or an aryl group and n is an integer of 1 to 3), wherein its angle of rotation shows a negative value in chloroform has markedly excellent activities as agricultural chemicals.
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