cas 406-87-1, 4,4,4-TRIFLUOROBUTYRALDEHYDE

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Electrochemical Synthesis of 4,4,4-Trifluorobutanal
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Muller, Norbert
p. 4559 - 4560
(1984)
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Atmospheric lifetimes and global warming potentials of CF 3CH2CH2OH and CF3(CH 2)2CH2OH
A comprehensive study of several atmospheric degradation routes for two hydrofluoroalcohols, CF3(CH2)x=1,2CH 2OH, is presented. The gas-phase kinetics of their reactions with hydroxyl radicals (OH) and chlorine (Cl) atoms are investigated by absolute and relative techniques, respectively. The room-temperature rate coefficients (±σ, in cm3 molecule-1 s-1) k OH and kCl, are respectively (9.7±1.1)× 10-13 and (1.60±0.45)× 10-11 for CF 3CH2CH2OH, and (2.62±0.32)× 10-12 and (8.71±0.24)× 10-11 for CF 3(CH2)2CH2OH. Average lifetimes of CF3CH2CH2OH and CF3(CH 2)2CH2OH due to the OH and Cl reactions are estimated to be 12 and 4 days, and greater than 20 and 4 years, respectively. Also, the IR and UV absorption cross sections of CF3(CH 2)x=1,2CH2OH are determined in the spectral ranges of 500-4000 cm-1 and 200-310 nm. Photolysis of CF 3(CH2)x=1,2CH2OH in the actinic region (I≥290 nm) is negligible compared to their homogeneous removal. Additionally, computational IR spectra are consistent with the experimental ones, thus giving high confidence in the obtained results. The lifetimes of CF3(CH2)x=1,2CH2OH and IR spectra reported herein allow the calculation of the direct global warming potential of these hydrofluoroalcohols. The contribution of CF3(CH 2)xCH2OH to radiative forcing of climate change will be negligible.
Jimenez, Elena,Antinolo, Maria,Ballesteros, Bernabe,Martinez, Ernesto,Albaladejo, Jose
p. 4079 - 4087
(2010)
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Highly selective hydroformylation of 3,3,3-trifluoropropene to 4,4,4-trifluorobutanal using Rh/Xantphos catalyst
Synthesis of 4,4,4-trifluorobutanal by Rh-catalyzed hydroformylation of 3,3,3-trifluoropropene with bis(4,5-diphenylphosphino)xanthene as a ligand was investigated. The uses of [Rh(OH)(cod)]2 (cod = 1,5-cyclooctadinene) and dimethylformamide in CO/H2 = 75/25 mixed gas under atmospheric pressure at 80 C for 15 h provided the highest aldehyde yield 90%. The molar ratio of linear aldehyde (4,4,4-trifluorobutanal) to branched aldehyde (3,3,3-trifluoro-2-methylpropanal) was 99/1. The successive addition of dimethylformamide solution of 3,3,3-trifluoropropene under atmospheric pressure revealed that 4,4,4-trifluorobutanal formation increased linearly with the reaction time and the total turnover number reached 500 after 10 h retaining 99% selectivity of 4,4,4-trifluorobutanal at 80 C.
Ohtsuka, Yuhki,Kobayashi, Osamu,Yamakawa, Tetsu
p. 34 - 40
(2014)
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Method for synthesizing 4,4,4-trifluorobutanol
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 0029-0030; 0037-0038; 0039-0040; 0045-0046

(2019/03/08)

MODULATORS OF SESTRIN-GATOR2 INTERACTION AND USES THEREOF
The present invention provides compounds, compositions thereof, and methods of using the same.
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Paragraph 00192; 00193; 00194

(2018/11/22)

MODULATORS OF SESTRIN-GATOR2 INTERACTION AND USES THEREOF
The present invention provides compounds, compositions thereof, and methods of using the same.
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Paragraph 0324

(2017/05/15)

3-(PERFLUOROALKYL)PROPANAL PRODUCTION METHOD
PROBLEM TO BE SOLVED: To provide a method of producing 3-(perfluoroalkyl)propanal with high selectivity, which is an important compound as a fluorine-containing building block for drug and functional material synthesis. SOLUTION: (Perfluoroalkyl)ethylene represented by the general formula (2) is reacted with carbon monoxide and hydrogen in the presence of a rhodium compound and diphosphine to produce 3-(perfluoroalkyl)propanal represented by the general formula (3). (In the formulas, Rf represents the same C1-16 perfluoroalkyl group.) COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0033-0036; 0038-0061; 0063-0075; 0077-0079

(2018/10/31)

Efficient synthesis of new fluorinated building blocks by means of hydroformylation
Hydroformylation of fluorinated alkenes is an efficient method for the preparation of fluorinated functionalized building blocks for the synthesis of biologically active target structures. In this article we summarize known hydroformylation reactions of f
Fanfoni, Lidia,Diab, Lisa,Smejkal, Tomas,Breit, Bernhard
p. 371 - 377
(2014/08/05)

Rapid access to β-trifluoromethyl-substituted ketones: Harnessing inductive effects in wacker-type oxidations of internal alkenes
We present a practical trifluoromethyl-directed Wacker-type oxidation of internal alkenes that enables rapid access to β-trifluoromethyl-substituted ketones. Allylic trifluoromethyl-substituted alkenes bearing a wide range of functional groups can be oxidized in high yield and regioselectivity. The distance dependence of the regioselectivity was established by systematic variation of the number of methylene units between the double bond and the trifluoromethyl group. The regioselectivity enforced by traditional directing groups could even be reversed by introduction of a competing trifluoromethyl group. Besides being a new powerful synthetic method to prepare fluorinated molecules, this work directly probes the role of inductive effects on nucleopalladation events.
Lerch, Michael M.,Morandi, Bill,Wickens, Zachary K.,Grubbs, Robert H.
supporting information
p. 8654 - 8658
(2014/08/18)

NOVEL ALPHA-(N-SULFONAMIDO)ACETAMIDE COMPOUNDS INCORPORATING DEUTERIUM AS INHIBITORS OF BETA AMYLOID PEPTIDE PRODUCTION
The present disclosure provides novel deuterated alpha-(N-sulfonamido)acetamide compounds, their pharmaceutical composition, processes thereof and a method for the treatment of Alzheimer's disease, head trauma, traumatic brain injury, and/or dementia pugilistica and/or other conditions associated with β-amyloid peptide.
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Page/Page column 8; 9

(2010/10/03)

Novel Alpha-(N-Sulfonamido)Acetamide Compound as an Inhibitor of Beta Amyloid Peptide Production
The present invention provides a novel alpha-(N-sulfonamido)acetamide compound, its pharmaceutical composition, processes thereof and a method for the treatment of Alzheimer's disease and other conditions associated with β-amyloid peptide.
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Page/Page column 14

(2009/05/28)

Fluoro- and trifluoroalkyl-containing heterocyclic sulfonamide inhibitors of beta amyloid production and derivatives thereof
Compounds of Formula (I), are provided where T is CHO, CON, or C(OH)R1R2; R1 and R2 are hydrogen, optionally substituted lower alkyl, CF3, optionally substituted alkenyl, or optionally substituted alkynyl; R3 is hydrogen or optionally substituted lower alkyl; R4 is (CF3)nalkyl, (CF3)n(substitutedalkyl), (CF3)nalkylphenyl, (CF3)nalkyl(substitutedphenyl), or (F)ncycloalkyl; n=1-3; R5 is hydrogen, halogen, CF3, diene fused to Y when Y═C, or substituted diene fused to Y when Y═C; W, Y and Z are C, CR6 or N where at least one of W, Y or Z are C; R6 is hydrogen, halogen, or optionally substituted lower alkyl; X is O, S, SO2, or NR7; R7 is hydrogen, optionally substituted lower alkyl, optionally substituted benzyl, or optionally substituted phenyl; and R8 is lower alkyl, CF3, or optionally substituted phenyl. Methods of preparing and using these compounds for inhibiting beta amyloid production and for treatment of Alzheimer's Disease and Down's syndrome are also described.
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(2008/06/13)

Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex
Using an (R,S)-BINAPHOS-Rh(I) catalyst that is covalently anchored to a highly cross-linked polystyrene support, asymmetric hydroformylation of olefins was performed in the absence of organic solvents. The reaction of cis-2-butene, a gaseous substrate, provided (S)-2-methylbutanal with 100% regioselectivity and 82% ee upon treatment with H2 (12 atm) and CO (12 atm) in a batchwise reactor equipped with a fixed bed. The polymer-supported catalyst was applicable to a continuous vapor-flow column reactor, and thus, 3,3,3-trifluoropropene was converted into (S)-2-trifluoromethylpropanal with an iso/normal ratio of 95/5 and 90% ee. Less volatile olefins, such as styrene, vinyl acetate, 1-alkenes, and fluorinated alkenes, were successfully converted into the corresponding isoaldehydes with high ee values, when they were injected through a supercritical CO2-flow column reactor. Successive injection of a series of olefins realized the conversion of an olefin library into an optically active aldehyde library.
Shibahara, Fumitoshi,Nozaki, Kyoko,Hiyama, Tamejiro
p. 8555 - 8560
(2007/10/03)

Vapor-phase asymmetric hydroformylation
Polystyrene-supported (R,S)-BINAPHOS-Rh complex was demonstrated to be applicable to the asymmetric hydroformylation of gaseous substrates in a non-solvent system: 3,3,3-trifluoropropene (2a) and (Z)-2-butene (2b) were converted into the corresponding branched aldehydes with 90% and 80%ee, respectively.
Nozaki, Kyoko,Shibahara, Fumitoshi,Hiyama, Tamejiro
p. 694 - 695
(2007/10/03)

Asymmetric hydroformylation of olefins in highly crosslinked polymer matrixes
When polymer-immobilized chiral phosphine-phosphite-Rh(I) complexes were used, the asymmetric hydroformylation of styrene gave 2- and 3- phenylpropanals with a substrate/catalyst ratio of 2000, iso/normal ratios of 84/16 to 89/11, and 89% R enantiomeric excess of 2-phenylpropanal; these results were at the highest level in catalytic activity, regio-, and enantioselectivities. Recovery-reuse of the catalyst was examined. Asymmetric hydroformylation of vinyl acetate, (Z)-2-butene, and 3,3,3-trifluoropropene was also successfully performed with the polymer-supported catalysts.
Nozaki, Kyoko,Shibahara, Fumitoshi,Itoi, Yohei,Shirakawa, Eiji,Ohta, Tetsuo,Takaya, Hidemasa,Hiyama, Tamejiro
p. 1911 - 1918
(2007/10/03)

Studies on the preparation of 2-(trifluoromethyl)acrylic acid and its esters from 3,3,3-trifluoropropene via hydrocarbonylation reactions
The synthesis of methyl α-(trifluoromethyl)acrylate (MTFMA) has been carried out in three steps starting from commercially available 3,3,3,-trifluoropropene; this route involving the cobalt-catalyzed carbonylation of 2-bromo-3,3,3-trifluoropropene (2-Br-TFP) under very mild reaction conditions, gave only about 30% yield of the desired methyl ester. 2-(Trifluoromethyl)propanal, available in 90% yield by rhodium catalyzed hydroformylation of 3,3,3-trifluoropropene, proved to be an interesting starting product for the preparation of MTFMA: while the synthetic route involving the α-halogenation of 2-(trifluoromethyl)propanoic acid (TFMPA) failed to give any results, the reaction scheme based on the α-selenenylation of the above aldehyde followed by H2O2-oxidation afforded 68% yield of 2-(trifluoromethyl)acrylic acid (TFMAA).
Botteghi, Carlo,Lando, Claudia,Matteoli, Ugo,Paganelli, Stefano,Menchi, Gloria
p. 67 - 71
(2007/10/03)

Highly enantioselective hydroformylation of olefins catalyzed by rhodium(I) complexes of new chiral phosphine-phosphite ligands
A new chiral phosphine-phosphite ligand, (R)-2-(diphenylphosphino)- 1,1'-binaphthalen-2'-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite [(R,S)- BINAPHOS, (R,S)-2a], was synthesized. Its Rh(I) complex was prepared, and its structure has been characterized by 1H and 31P NMR spectroscopy. Using Rh(I) complexes of (R,S)-2a and its enantiomer, highly enantioselective hydroformylation of styrene has been performed (94% ee, iso/normal = 88/12). The catalyst system was also effective for a variety of other olefins. Some other phosphine-phosphite ligands bearing 1,1'-binaphthyl and biphenyl backbones, such as (S)-3,3'-dichloro-6-(diphenylphosphino)-2,2',4,4'- tetramethylbiphenyl-6'-yl (R)-1,1'-binaphthalene-2,2'-diyl phosphite [(S,R)- BIPHEMPHOS. (S,R)-5a], (R,R)-2a, (R,S)-2b, (R)-2c, and (R)-5b, were tested for asymmetric hydroformylation. The results indicate that the sense of enantioface selection for the prochiral olefins is mainly determined by the absolute configuration of the phosphine site, for example, the (R)-2- (diphenylphosphino)-1,1'-binaphthalen-2'-yl group in (R,S)-2a. The relative configurations of the two biaryl groups in the phosphine-phosphites play crucial roles in the degree of the enantioselectivities, that is, the (R,S)- isomer generally gives products in high ee's and the (R*,R*)-isomer does in low ee's. Treatment of Rh(acac)[(R,S)-2a] with a 1:1 mixture of carbon monoxide and hydrogen gave a hydridorhodium complex. RhH-(CO)2[(R,S)-2a], as a single species. Trigonal bipyramidal structure is suggested for this complex, in which the hydride and the phosphite moiety are located at the apical positions and the phosphine and the two carbonyls occupy the equatorial positions. The interchange of the phosphine and the phosphite sites with each other through rapid pseudorotations has not been observed in RhH(CO)2[(R,S)-2a]. The structural deviations of the monohydride complexes from an ideal trigonal bipyramid seem to be larger in (R*,R*)-isomers than in the corresponding (R*,S*)-isomers. The existence of only one active species involved in the Rh(1)-(R,S)-2a-catalyzed hydroformylation has been manifested by the plot of ln([R]/[S]) of the hydroformylation product vs the reciprocals of the reaction temperatures. The higher thermodynamic stability of Rh(acac)[(R,S)-2a] than its diastereomer Rh(acac)[(R,R)-2a] is demonstrated in relation to the restricted configuration of (R)-2c to (R,S)- 2c in its complex formation with Rh(1).
Nozaki, Kyoko,Sakai, Nozomu,Nanno, Tetsuo,Higashijima, Takanori,Mano, Satoshi,Horiuchi, Toshihide,Takaya, Hidemasa
p. 4413 - 4423
(2007/10/03)

Azadecalin amides and thioamides as inhibitors of cholesterol biosynthesis
The present invention provides certain novel azadecalin amides and thioamides which are useful as inhibitors of cholesterol biosynthesis and as agents which lower total serum cholesterol in patients in need thereof.
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(2008/06/13)

Hydroformylation of Fluoro Olefins, RfCH=CH2, Catalyzed by Group VIII Transition-Metal Catalysts. Crucial Factors for Extremely High Regioselectivity
Hydroformylations of fluoro olefins, trifluoroprop-1-ene (TFP), pentafluorobut-1-ene (PFB), heptafluoropent-1-ene (HPFP), heptadecafluorodec-1-ene (HPDFD), vinyl fluoride (VF), pentafluorostyrene (PFS), and allylpentafluorobenzene (4a), promoted by transition-metal catalysts were studied.Remarkable dependency of the regioselectivity of the reaction on the catalyst metal species (Co, Pt, Ru, and Rh) was found in the reactions of TFP and PFS; e.g., n-aldehyde was obtained with >93percent selectivity by a cobalt catalyst whereas iso-aldehyde was obtained with >96percent selectivity by a rhodium catalyst for the reaction of TFP.On the contrary, the reaction of VF gave 2-fluoropropanal (2-FPA) exclusively, regardless of the metal catalyst species.The effects of temperature and carbon monoxide pressure on the regioselectivity were investigated.Possible mechanisms for the uniquely regioselective hydroformylations are discussed on the basis of the results obtained, and a mechanism that involves an initial formation of isoalkyl-metal species followed by isomerization to n-alkyl-metal species and/or followed by carbon monoxide insertion to form isoacyl-metal intermediate was proposed to be the one operating in these reactions.
Ojima, Iwao,Kato, Koji,Okabe, Masami,Fuchikami, Takamasa
p. 7714 - 7720
(2007/10/02)

Hydroxyalkylation with α-Hydroperoxydiazenes. Alcohols from Olefins and Carbonyl Compounds from Enol Ethers
Alkyl(1-hydroxy-1-methylethyl)diazenes 2a-f were prepared in solution by autoxidation of the corresponding hydrazones of acetone.Thermolysis of the diazenes at 50-80 deg C in alkenes leads to alcohols.For example, 2b decomposes in 1,1-diphenylethene to afford 5-hydroxy-5,5-diphenylpentanenitrile.Alkenes with abstractable allylic hydrogens gave analogous products, but in very low yield.Thermolysis of a diazene 2 in an enol ether solvent leads to an aldehyde or a ketone.Thus, 2a decomposes in 1-ethoxyethene and in 2-methoxypropene to afford, respectively, 4,4,4-trifluorobutanal and 5,5,5-trifluoro-2-pentanone.Yields lie in range from 50percent to 70percent.The thermolysis of 2 in alkenes involves radical intermediates and radical chain hydroxyalkylation of alkene double bonds.In one chain-propagating step, R*, generated from 2, adds to the alkene.The adduct radical so formed propagates by inducing decomposition of 2 by attack at hydroxyl oxygen.According to this mechanism, initial products from enol ethers are hemiacetals or hemiketals which do not survive the reaction conditions but decompose to the corresponding carbonyl compounds.Preliminary evidence for this mechanism is presented.
Osei-Twum, Emmanuel Y.,McCallion, Doug,Nazran, Avtar S.,Panicucci, Rick,Risbood, Prabhakar A.,Warkentin, John
p. 336 - 342
(2007/10/02)

Regioselectivity in the Ring Opening of 2-Alkylcyclopropylmethyl Radicals: the Effect of Electronegative Substituents
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
p. 1907 - 1916
(2007/10/02)

Remarkable Dependency of Regioselectivity on the Catalyst Metal Species in the Hydroformylation of Trifluoropropene and Pentafluorostyrene
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Fuchikami, Takamasa,Ojima, Iwao
p. 3527 - 3529
(2007/10/02)