- Novel synthesis method of 4, 4, 4-trifluoro-1-butanol and homologue thereof
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The invention discloses a novel synthesis method of 4, 4, 4-trifluoro-1-butanol and a homologue thereof, and relates to the technical field of organic synthesis. The method mainly comprises the following steps of: (1) reacting ethyl trifluoroacetate with a Grignard reagent to prepare benzyloxy substituted alkyl-trifluoromethyl ketone; (2) carrying out reduction reaction on the benzyloxy substituted alkyl-trifluoromethyl ketone to prepare 1-benzyloxy-trifluorosubstituted alkyl; and (3) carrying out hydrolysis on the 1-benzyloxy-trifluorosubstituted alkyl, so as to prepare 4, 4, 4-trifluoro-1-butanol or a homologue thereof disclosed by the invention. Compared with the prior art, Freon raw materials which can pollute air are not used; dangerous lithium aluminum hydride is not used; high-temperature reaction is not needed; and the raw material ethyl trifluoroacetate is cheap and easily available, and the other main raw material Grignard reagent can also be synthesized from cheap raw materials.
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Paragraph 0032; 0039-0050
(2021/05/12)
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- Method for synthesizing 4,4,4-trifluorobutanol
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The invention discloses a method for synthesizing 4,4,4-trifluorobutanol, and belongs to the technical field of organic synthesis. The method comprises the following steps: using 3-halo-1,1,1-trifluoropropane as a raw material to prepare 4,4,4-trifluorobutyraldehyde by two methods of a Grignard method and a DMF step method or a metal lithium/DMF one-pot method, respectively; then, reducing with borohydride salt to obtain 4,4,4-trifluorobutanol, wherein the product is easy to self-decompose and tar; hydrolyzing again to free out the product for purification after adding trimethyl borate or acetonylidene to a reaction system for alcohol exchange, distillation and purification. The method is stable and reliable, successfully performed during amplification in a kilogram scale, and stable in yield.
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Paragraph 0049-0056; 0062-0063
(2019/03/08)
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- Method for preparing 4,4,4-trifluoro-1-butanol
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The invention provides a method for preparing 4,4,4-trifluoro-1-butanol. The method comprises the following steps: A) under the action of a first catalyst, carrying out an addition reaction on 3-chloropropanol with 3,4-dihydropyran so as to prepare 2-(3-chlorine propoxy) terthydro-2H-pyran; B) under the action of a second catalyst, carrying out a cross coupling reaction on halogen fluoroform withthe 2-(3-chlorine propoxy) terthydro-2H-pyran obtained in the step A) so as to obtain 2-(4,4,4-trifluoro-butoxy) terthydro-2H-pyran; and C) under the action of a third catalyst, carrying out an elimination reaction on the 2-(4,4,4-trifluoro-butoxy) terthydro-2H-pyran obtained in the step B), thereby obtaining 4,4,4-trifluoro-1-butanol. The method is low in preparation cost, beneficial to industrialization, in addition, short in process route, high in total reaction yield, gentle in reaction condition and high in product purity.
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Paragraph 0066; 0071; 0072; 0074; 0079; 0080; 0081; 0086
(2019/02/26)
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- A novel coupling synthesis of 4, 4, 4 - trifluoro-butyl alcohol
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The present invention provides a novel coupling synthesis of 4, 4, 4 - trifluoro-butyl alcohol, comprising the following steps: in the presence of a base catalyst, the 2, 2, 2 - trifluoro - 1 - chloroethane and 1 - chloro ethanol in the solvent mixing, cross-coupling reaction, to obtain the 4, 4, 4 - trifluoro-butyl alcohol; said catalyst is a copper salt and organic ligand; the copper salt is cuprous halide and/or copper chloride; the organic ligand is 2, 2' - bipyridyl, tetramethyl ethylenediamine and 4, 4 - di-tert-butyl - 2, 2, - bipyridyl in one or several. This invention adopts the copper salts and organic ligand as catalyst, the catalytic 2, 2, 2 - trifluoro - 1 halo ethane with 1 - chloro ethanol free radical cross-coupling reaction of, can be efficiently prepared 4, 4, 4 - trifluoro-butyl alcohol, the invention the preparation method in high selectivity, high yield. Experimental results show that, in the invention of the preparation method a yield as high as 80%.
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Paragraph 0044-0068
(2019/03/15)
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- Novel synthesis method for 4,4,4-trifluorobutanol
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The invention relates to a novel synthesis method for 4,4,4-trifluorobutanol. The method comprises the following steps: (1) enabling diethyl malonate to be subjected to substitution reaction with 2,2,2-trifluoro ethyl p-toluenesulfonate under the catalysis of a basic catalyst, so as to obtain 2-(2,2,2-trifluoro ethyl)-diethyl malonate; (2) enabling 2-(2,2,2-trifluoro ethyl)-diethyl malonate to be subjected to decarboxylic reaction, so as to obtain 4,4,4-trifluoro ethyl butyrate; and (3) reducing 4,4,4-trifluoro ethyl butyrate by a reduction reagent under the catalysis of a catalyst, thereby obtaining 4,4,4-trifluorobutanol. Compared with the prior art, the method disclosed by the invention has the advantages that the raw materials are cheap and readily-available, the cost is low, the number of synthesis steps is small, the operation is convenient and safe, the aftertreatment is simple, the solvent can be cyclically applied mechanically and is environment-friendly, the reaction yield is high, and the product is high in purity and good in quality and is applicable to industrial application.
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Paragraph 0058; 0059; 0060; 0061; 0062; 0063
(2016/10/08)
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- MANUFACTURE OF FLUORINATED ALCOHOLS
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Present invention relates to a process for the manufacture of fluorinated alcohols as well as borates which are employed in the manufacture of the fluorinated alcohols. Fluorinated alcohols of the formulae HOCHRCF(CF3)CHFCF(CF3)2 and HOCHRCF(CF(CF3)2)CHFCF3, HOCHRCF(CF2CF3)CH(CF3)2 and HOCHRC(CF3)2CHFCF2CF3 are made by heating a mixture of a borate of the formula (RCH2O)3B, wherein R═H or a C1 to C7 alkyl group, with perfluoro-4-methyl-2-pentene or perfluoro-2-methyl-2-pentene and a free-radical initiator to form a mixture of borates, optionally separating the mixture of borates from any reactants, solvents, and by-products; hydrolyzing the mixture of borates to form a hydrolysis product mixture; and separating the alcohols from the hydrolysis product mixture.
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Page/Page column 5
(2008/06/13)
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- METHOD FOR PRODUCING FLUORINE-CONTAINING ALCOHOL
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PROBLEM TO BE SOLVED: To provide a method for the production of a fluorine-containing alcohol, preventing the formation of scale, suppressing side reactions, producing the alcohol in a short time in high yield and selectivity and suitable for mass-production. SOLUTION: A fluorine-containing alcohol expressed by general formula (2): Rf(A)OH (Rf is a 1-10C perfluoroalkyl group; and A is a 3-10C straight or branched-chain saturated hydrocarbon group) is produced by reacting a fluorine-containing alkyl halide expressed by general formula (1); Rf(A)X (X is a halogen atom) with an alkali metal 4-hydroxybutyrate using γ-butyrolactone as a solvent while keeping the reaction temperature to 90-130°C.
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Page/Page column 6
(2008/06/13)
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- PROCESS FOR PRODUCING FLUORINATED ALCOHOL
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A method for producing fluorinated alcohols from fluorinated alkyl halides can produce fluorinated alcohols at high product yield and at high selectivity in a single-step reaction. The method eliminates the need to use heavy metals and other toxic compounds that are difficult to handle or process. Specifically, the method produces a fluorinated alcohol represented by the following general formula (2):Rf(A)OH wherein Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms; and A represents a straight-chained or branched saturated hydrocarbon group having 3 to 10 carbon atoms. The method is characterized in that it allows a fluorinated alkyl halide represented by the following general formula (1) to react with an alkali metal salt of 4-hydroxybutyrate in a gamma-butyrolactone solvent:Rf(A)X wherein Rf and A are as defined above; and X represents a halogen atom.
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- Deamination Reactions, 43 - The Effect of Trifluoromethyl Groups on the Reactivity of Aliphatic Diazonium Ions and Carbocations
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Various trifluoroalkanamines (9, 26, 35, 38, 45, 56, and 67) have been prepared and diazotized (water, pH 3.5) to probe the effect of trifluoromethyl groups on the reactivity of aliphatic diazonium ions.The product distributions reveal that α-CF3 groups enhance inverting displacement and enforce rearrangement (hydride shifts) separating the positive charge from CF3.Migrations of the positive charge from the β- to the γ-position are less strongly promoted than those from α to β.Enhancement factors of ca. 15 (α -> β) and 4 (β -> γ) may be derived by comparison with analogous alkanediazonium ions.The positive charge does not migrate in the reverse direction (β -> α) except for minor amounts of a pinacolic rearrangement (68 -> 7).A migration of the positive charge from γ to β has been detected with 36 but a tenfold decrease as compared to the analogous butanediazonium ion 37 is indicated.All observations are reasonably explained in terms of the relative stabilities of the intermediate trifluoroalkyl cations.
- Gassen, Karl-Rudolf,Kirmse, Wolfgang
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p. 2233 - 2248
(2007/10/02)
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- Process for preparing pyrazolopyridine compounds
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Compounds of the formula (I): STR1 wherein R4 is hydrogen, D is oxygen or NR6, R1, R3, R6, R7 and R8 have defined values, and n is 1 or 2 are produced by internally cyclizing a compound of the formula (XV): STR2 wherein R19 is a value of R1 or hydrogen and, if R19 is hydrogen, reacting the cyclization product with R1 --Br and a weak base such as potassium carbonate.
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- CNS-Depressant pyrazolopyridines
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Compounds of the formula (I): STR1 wherein R1, R3, R4, R7 and R8 are as described herein, D is oxygen or NR6, n is 1 or 2 and the physiologically acceptable salts thereof useful in reducing anxiety in an animal such as man. The compounds are potent anxiolytics having reduced side effects compared to known anxiolytics. Also pharmaceutical compositions, intermediates and methods of treatment and synthesis are described.
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- Pyrazolo[3,4-b]pyridine carboxylic acid esters and their pharmaceutical use
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Compounds of the formula (I): STR1 wherein R1, R3, R4, R5 and R6 have defined values and the N-oxides at the 7-position of the pyrazolo[3,4-b]pyridine ring system and the pharmaceutically-acceptable acid-addition salts thereof, processes for their preparation and use, pharmaceutical compositions, and intermediates for preparing said compounds of the formula (I). The compounds of formula (I) are central nervous system depressants, for example anxiolytic agents.
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- Regioselectivity in the Ring Opening of 2-Alkylcyclopropylmethyl Radicals: the Effect of Electronegative Substituents
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The regioselectivity of the ring-opening of the trans-2-alkylcyclopropylmethyl radical A to give the primary alkyl radicals B, or the secondary alkyl radicals C, has been investigated, where the groups R and/or CXY carry electronegative substituents.All these reactions gave principally the secondary alkyl radicals C, whereas, in the absence of electronegative substituents, ring-opening occurs in favour of the primary alkyl radicals B.This regioselectivity is interpreted in terms of the frontier orbital interactions which are involved.
- Ratier, Max,Pereyre, Michel,Davies, Alwyn G.,Sutcliffe, Roger
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p. 1907 - 1916
(2007/10/02)
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