- General and Efficient Synthesis of 1,1,1-Trichloro-2-alkanols
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1,1,1-Trichloroalkanols were readily obtained in good yields by reaction of trichloroacetic acid with aldehydes in hexamethylphosphoric triamide. 1,3-Dimethyl-2-imidazolidinone was found to be useful as an alternate solvent giving, however, lower yields.
- Ferraccioli, Raffaella,Gallina, Carlo,Giordano, Cesare
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Read Online
- Pd-catalyzed synthesis of 1-(hetero)aryl-2,2,2-trichloroethanols using chloral hydrate and (hetero)arylboroxines
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1-(Hetero)aryl-2,2,2-trichloroethanols are useful key intermediates for the synthesis of various bioactive compounds. Herein, we describe N-heterocyclic carbene (NHC)-coordinated cyclometallated palladium complex (CYP)-catalyzed (hetero)aryl addition of chloral hydrate using (hetero)arylboroxines, providing a new approach to 1-(hetero)aryl-2,2,2-trichloroethanols. Notably, PhS-IPent-CYP which coordinated the bulky yet flexible 2,6-di(pentan-3-yl)aniline (IPent)-based NHC showed good catalytic activities and promoted the transformation in 24-97% yields.
- Shimizu, Minori,Okuda, Yuta,Toyoda, Koki,Akiyama, Ryo,Shinozaki, Hiraku,Yamamoto, Tetsuya
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p. 17734 - 17739
(2021/05/29)
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- PESTICIDAL COMPOUNDS AND METHODS OF USE
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Described herein are compounds, pesticidally acceptable salts thereof, and compositions thereof that are useful, for example, for pest management and for controlling pests. In certain embodiments provided are enantioenriched and/or enantiopure compounds and pesticidally acceptable salts thereof, and methods of making same. Methods of controlling pests with the compounds of the disclosure are also provided.
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Paragraph 0165; 0166; 0226-0229
(2021/04/02)
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- A novel β-(oxy)alkyl radical during copper(I)-mediated stereoselective synthesis of (Z)-ene-1,4-diones in a reaction of 2,2,2-trichloro-1-phenylethanone
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A novel β-(oxy)alkyl radical derived from trichloro methyl compound containing neither a suitably located C-C multiple bond nor a leaving group or a H-atom at the β-position of the radical in a reaction of 2,2,2-trichloro-1-phenyl-ethanone with 2 mol equiv each of CuCl and bpy in refluxing DCE under a N2 atm underwent intramolecular heterolysis (just like formation of intact radical cation-anion pair) during stereoselective radical dimerization to Z-ene-1,4-dione along with small amount of reductive dechlorination product. The stereochemistry was established by X-ray diffraction spectroscopy of various solid crystalline products.
- Ram, Ram N.,Tittal, Ram K.
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supporting information
p. 2437 - 2440
(2016/05/19)
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- One-Carbon Homologation of Primary Alcohols and the Reductive Homologation of Aldehydes Involving a Jocic-Type Reaction
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(Trichloromethyl)carbinols, which are formed in one operation from either alcohols or aldehydes, can be converted into primary alcohols in a Jocic-type reaction involving LiBH4. The net result is a convenient two-step, one-carbon homologation of primary alcohols or a reductive one-carbon homologation of aldehydes featuring a broad substrate scope. The method is step-economical, and it nicely complements established one-carbon homologation strategies. (Trichloromethyl)carbinols, which are formed in one operation from either alcohols or aldehydes, can be converted into primary alcohols in a Jocic-type reaction involving LiBH4. The net result is a convenient two-step, one-carbon homologation of primary alcohols or a reductive one-carbon homologation of aldehydes featuring a broad substrate scope.
- Li, Zhexi,Gupta, Manoj K.,Snowden, Timothy S.
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p. 7009 - 7019
(2015/11/16)
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- Decarboxylative trichloromethylation of aromatic aldehydes and its applications in continuous flow
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Two new protocols for the efficient synthesis of 2,2,2- trichloromethylcarbinols, starting from aromatic aldehydes, have been developed. A combination of sodium trichloroacetate in the presence of malonic acid proved efficient for the transformation of el
- Jensen, Andreas B.,Lindhardt, Anders T.
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p. 1174 - 1183
(2014/03/21)
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- β-(Carbonatoxy)alkyl radicals: A new subset of β-(ester)alkyl radical fragmentation during copper(I)-mediated synthesis of 1,1-dichloro-1-alkenes
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A new subset of β-(ester)alkyl radicals is presented. It is the first study on the chemistry of β-(alkoxycarbonyloxy)alkyl radicals that fill the gap in the spectrum of the migrating groups in β-(ester)alkyl radical reactions. The change from less nucleofugal (acetate) group to the more nucleofugal (carbonate) group in the spectrum of the migrating group changed the reaction path from rearrangement to fragmentation. This approach has been used for the synthesis of 1,1-dichloroalkenes in high yields. The formation of dichloroalkenes was accounted by the involvement of alkene radical cation and carbonate anion pair (a CIP) as a result of heterolysis of the CO bond of the carbonate at the β-position of the β-(alkoxycarbonyloxy)alkyl radical. The alkene radical cation was trapped by nucleophilic reaction with MeOH to form methyl ester.
- Ram, Ram N.,Tittal, Ram K.
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supporting information
p. 4342 - 4345
(2014/07/22)
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- Platinum on carbon-catalyzed precise reduction control of trichloromethyl to Geminal-dichloromethyl groups
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Geminal-dichloromethyl derivatives could be efficiently synthesized by the highly chemoselective platinum on carbon-catalyzed mono-dechlorination of trichloromethyl substrates in dimethylacetamide (DMA) as a specific solvent at 25 °C under a hydrogen atmosphere. Copyright
- Imanishi, Takahiro,Fujiwara, Yuta,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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supporting information; experimental part
p. 771 - 776
(2012/06/30)
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- One-pot synthesis of trichloromethyl carbinols from primary alcohols
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Versatile trichloromethyl carbinols can be prepared in one pot from primary alcohols by treatment with Dess-Martin periodinane (DMP) in CHCl3 followed by introduction of commercially available 1,5,7-triazabicyclo[4.4.0] dec-5-ene (TBD). A modification of the method was used to convert chiral primary alcohol (R)-(-)-2,2-dimethyl-1,3-dioxolane-4-methanol to the corresponding trichloromethyl carbinol with complete stereochemical fidelity, despite the reactant proceeding through a base-sensitive aldehyde intermediate.
- Gupta, Manoj K.,Li, Zhexi,Snowden, Timothy S.
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scheme or table
p. 4854 - 4860
(2012/07/30)
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- Friedel-crafts hydroxyalkylation of anisole over oxalic acid modified Hβ zeolite
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Oxalic acid modified Hβ (OA-Hβ) zeolite is found to have better catalytic performance than Hβ zeolite in the Friedel-Crafts hydroxyalkylation of anisole with chloral. This is attributed to the increase of weak and moderately-strong acid sites, caused by oxalic acid modification. Furthermore, it is believed that the carbonaceous deposits on the acid sites and the blockage of the pores, together with poisoning by chlorinated materials, are responsible for the deactivation of OA-Hβ zeolite, as indicated by NH3-TPD, BET, SEM, TG and XPS measurement results. Moreover, partial regeneration of OA-Hβ zeolite can be achieved via subsequent calcination.
- Bai, Guoyi,Dou, Haiyang,Qiu, Mande,Fan, Xinxin,He, Fei,Niu, Libo,Ma, Zheng
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experimental part
p. 187 - 192
(2011/01/04)
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- General and practical conversion of aldehydes to homologated carboxylic acids
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(Chemical Equation Presented) The reaction of aldehydes with trichloromethide followed by sodium borohydride or sodium phenylseleno(triethyl) borate under basic conditions affords homologated carboxylic acids in high yields. This operationally simple procedure provides a practical, efficient alternative to other homologation protocols. The approach is compatible with sensitive aldehydes including enals and enolizable aldehydes. It also offers convenient access to α-monodeuterated carboxylic acids.
- Cafiero, Lauren R.,Snowden, Timothy S.
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supporting information; experimental part
p. 3853 - 3856
(2009/07/01)
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- Copper(I)-promoted synthesis of chloromethyl ketones from trichloromethyl carbinols
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(Chemical Equation Presented) Reaction of several trichloromethyl carbinols with 2 equiv of CuCl/bpy in refluxing DCE for 3 h afforded chloromethyl ketones in excellent yield by 1,2-H shift in the copper-chlorocarbenoid intermediate.
- Ram, Ram N.,Manoj
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p. 5633 - 5635
(2008/12/21)
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- Suzuki-Miyaura cross-coupling of 1,1-dichloro-1-alkenes with 9-alkyl-9-BBN
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We addressed an unexplored application of the Suzuki-Miyaura protocol to the cross-coupling of 1,1-dichloro-1-alkenes with 9-alkyl-9-BBN. The use of bisphosphine ligands with a large P-Pd-P bite angle allowed us to synthesize Z-chlorinated internal alkenes in good yields resulting from a selective monocoupling process, a recurrent challenge with 1,1-dichloro-1-alkenes. Moreover, these monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.
- Liron, Frederic,Fosse, Celine,Pernolet, Alban,Roulland, Emmanuel
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p. 2220 - 2223
(2007/10/03)
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- Decomposition of sodium trichloroacetate in the presence of quaternary ammonium under microwave irradiation: A convenient one-pot synthesis of α-hydroxy acids in water
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A good yielding phase-transfer-catalyzed procedure for one-pot preparation of α-hydroxy acids from carbonyl compounds and sodium trichloroacetate by in situ addition and hydrolysis under microwave irradiation is described. Decomposition of sodium trichloroacetate is strongly accelerated by the presence of quaternary ammonium. The reaction can be conducted in water. Copyright Taylor & Francis Group, LLC.
- Yu, Haitao,Fang, Yun,Xia, Yongmei,Wu, Jing
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p. 2421 - 2426
(2007/10/03)
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- CARBOXYLATION OF ARENES
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A two-step procedure for the carboxylation of aromatic rings is described, involving the intermediate preparation of 1-aryl-2,2,2-trichloroethanols (1), which form the corresponding benzoic acids by treatment with NaOH/H2O2.
- Menegheli, Paulo,Rezende, Marcos Caroli,Zucco, Cezar
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p. 457 - 464
(2007/10/02)
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- Chain Reactions Induced by Cathodic Reduction
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Cathodic reduction of a system comprising carbon tetrachloride, chloroform, and an aldehyde led to an effective anionic chain reaction.The best current efficiency observed was about 1*104 percent .Such a chain reaction is an effective synthetic method for 1,1,1-trichloro-2-alkanols.The reaction system consisting of methyl trichloroacetate, methyl dichloroacetate, and an aldehyde and several other systems also exhibited a similar pattern of chain reaction.
- Shono, Tatsuya,Kise, Naoki,Masuda, Mitsuharu,Suzumoto, Takeshi
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p. 2527 - 2533
(2007/10/02)
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- The Reaction of Trihalgenomethyl Anions with Carbonyl Compounds: Competitive Reactivity Comparisons and Applications to the Synthesis of α-Trihalogenomethyl Alcohols
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Trihalogenomethyl anions, generated by decarboxilation of trichloro- and tribromo-acetic acid in dimethyl sulphoxide solution, react with added aldehydes.In the presence of 1,3,5-trinitrobenzene, the reaction with aldehydes competes with the formation of the coloured Meisenheimer adduct.The reduction in absorbance from the value in the absence of aldehyde has been used tomeasure the reactivity of trihlogenomethyl anions towards a series of aldehydes relative to their reactivity towards trinitrobenzene.For 4-substituted benzaldehydes, the reactivities obey a linear p?- relationship.The most reactive aldehyde used is only two times less reactive towards CCl3(1-) or CBr3(1-) than hydrogen ions, and it is concluded that, in dimethyl sulphoxide solutions, the reaction between trichloromethyl anions and hydrogen ions is not encounter-controlled.The reactions with aldehydes have been used to prepare several new compounds of the formula RCH(OY)CX3 where R = aryl or pyridyl, X = Br or Cl, and Y = H or COCH3.
- Atkins, Paul J.,Gold, Victor,Wassef, Wasfy N.
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p. 1247 - 1252
(2007/10/02)
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- NOVEL SELECTIVE SYNTHESIS OF α-CHLOROMETHYL, α,α-DICHLOROMETHYL, AND α,α,α-TRICHLOROMETHYL KETONES FROM ALDEHYDE UTILIZING ELECTROREDUCTION AS KEY REACTIONS
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A variety of α-chloromethyl, α,α-dichloromethyl, and α,α,α-trichloromethyl ketones were synthesized from aldehyde utilizing cathodic reduction as key reactions.
- Shono, Tatsuya,Kise, Naoki,Yamazaki, Akira,Ohmizu, Hiroshi
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p. 1609 - 1612
(2007/10/02)
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- A NOVEL CHAIN REACTION INDUCED BY CATHODIC REDUCTION. ADDITION OF TRICHLOROMETHYL ANION TO ALDEHYDES OR VINYL ACETATE
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A novel chain reaction induced by cathodic reduction was found in the reaction system consisting of carbon tetrachloride, chloroform, and electrophiles such as aldehydes or vinyl acetate.The current efficiency of addition of trichloromethyl anion to electrophiles was extremely high.Synthesis of an analogue of ethyl chrysanthemate using this new reaction was also described.
- Shono, Tatsuya,Ohmizu, Hiroshi,Kawakami, Souta,Nakano, Shinji,Kise, Naoki
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p. 871 - 874
(2007/10/02)
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