2000-43-3

Usage

Uses

2,2,2-Trichloro-1-phenylethanol is used as pharmaceutical intermediate.

Synthesis Reference(s)

Canadian Journal of Chemistry, 58, p. 485, 1980Tetrahedron Letters, 19, p. 1521, 1978 DOI: 10.1016/S0040-4039(01)94592-7

Safety Profile

Moderately toxic by subcutaneousroute. When heated to decomposition it emits toxicvapors of Clí.

InChI:InChI=1/C8H7Cl3O/c9-8(10,11)7(12)6-4-2-1-3-5-6/h1-5,7,12H/t7-/m0/s1

Upstream product

• 64-17-5 ethanol 
• 2902-69-4 2,2,2-trichloroacetophenone 
• 555-75-9 aluminum ethoxide 
• 13824-25-4 triethyl-alane; compound with diethyl ether 
• 555-31-7 aluminum isopropoxide 
• 67-66-3 chloroform 
• 100-52-7 benzaldehyde 
• 75-87-6 chloral 
• 71-43-2 benzene 
• 302-17-0 chloral hydrate 
• 56-23-5 tetrachloromethane 
• 650-51-1 sodium trichloroacetate 
• 5764-62-5 tributyl-trichloromethyl-stannane 
• 768-32-1 trimethylphenylsilane 

Downstream Products

• 72962-71-1 Diethyl-phosphinic acid 2,2,2-trichloro-1-phenyl-ethyl ester 
• 55073-97-7 2-methyl-4-hydroxy-5-phenylthiazole 
• 2933-32-6 2-(methylamino)-5-phenyl-1,3-thiazol-4(5H)-one 
• 54034-90-1 1,1,1-trichloro-2-phenyl-2-(trimethylsiloxy)ethane 
• 7639-82-9 1-Fluoro-4-(2,2,2-trichloro-1-phenyl-ethyl)-benzene 
• 55073-93-3 5-phenyl-thiazolidine-2,4-dione 2-isopropylidenehydrazone 
• 55073-94-4 benzaldehyde (4-oxo-5-phenyl-thiazolidin-2-ylidene)-hydrazone 
• 70156-56-8 2,6-diphenyl-4H-[1,3,4]thiadiazin-5-one 
• 38533-19-6 3,4-dihydro-2-phenyl-2H-1,4-benzothiazin-3-one 
• 70156-57-9 2-Phenyl-3-oxo-1,4-thiazane 
• 27904-70-7 1-methoxy-1-phenyl-2,2,2-trichloroethane 
• 2612-36-4 2,2-dichloro-1-phenylethanol 
• 100142-13-0 Diethyl-α-trichloromethylbenzyl Phosphite 
• 78401-32-8 [2,2,2-Trichloro-1-(3-methyl-but-2-enyloxy)-ethyl]-benzene 

Relevant academic research and scientific papers

Substrate-Controlled Diastereoselective Synthesis of Sugar-Based Chlorinated Perhydrofuro[2,3-b]pyrans via Copper(I)-Catalyzed Radical Cyclization

The work describes the first copper(I) chloride/2,2′-bipyridine-catalyzed atom transfer radical cyclization (ATRC) of unsaturated carbohydrate-derived chloroacetals to generate chlorinated perhydrofuro[2,3-b]pyrans via an effective diastereoselective route. Various glycals (glucal, galactal and lactal) underwent the Ferrier rearrangement with 2,2,2-trichloroethanols to give acetal precursors stereoselectively, R-selective with galactal in contrast to S-selective with glucal. The radical cyclization of the Ferrier products occurred smoothly to afford cis-fused bicyclic products with the transfer of the chlorine atom at the non-anomeric carbon in the cyclized radical intermediate predominantly from the equatorial direction. The carbohydrate templates controlled the stereochemistry of both Ferrier rearrangement and ATRC steps. The stereostructures of the products were also supported by single crystal X-ray diffraction crystallography. The products possess biologically important structural segments such as a glycosidic linkage, a fused bicyclic acetal unit and a chlorosugar unit which are potential sources for biological studies and further synthetic elaborations. (Figure presented.).

A NEW ELECTROGENERATED BASE. CONDENSATION OF CHLOROFORM WITH ALIPHATIC ALDEHYDES

A novel base was generated by electrochemical reduction of 2-pyrrolidone in DMF, and this electrogenerated base (EGB) was effective to promote the condensation of chloroform with aliphatic aldehydes in good yields.

Optical Resolution of Tertiary Acetylenic Alcohols and Secondary Alcohols by Complexation with Achiral Amines

Partially resolved tertiary acetylenic alcohols and secondary alcohols were easily resolved completely by complexation with achiral amines such as 1,4-diazabicyclooctane (DABCO), N,N'-dialkylpiperazine, N,N,N',N'-tetramethylethylenediamine, and pyrazine, to give optically pure enantiomers.Interestingly, DABCO formed more stable complex with optically pure enantiomers but the other amines formed more stable complex with racemic compounds.

Synthetic process of rosone

The invention relates to a synthetic process of rosone. A solid super base is adopted as a catalyst during preparation of trichloromethyl benzyl alcohol, so that production of basic wastewater is avoided, product separation is facilitated, conversion rate of benzaldehyde is increased, the proportion of byproduct benzoic acid is reduced, and product yield is increased greatly and can be up to 95% or higher as the maximum.

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

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.

One-Carbon Homologation of Primary Alcohols and the Reductive Homologation of Aldehydes Involving a Jocic-Type Reaction

(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.

Steric vs. electronic effects in the Lactobacillus brevis ADH-catalyzed bioreduction of ketones

Lactobacillus brevis ADH (LBADH) is an alcohol dehydrogenase that is commonly employed to reduce alkyl or aryl ketones usually bearing a methyl, an ethyl or a chloromethyl as a small ketone substituent to the corresponding (R)-alcohols. Herein we have tested a series of 24 acetophenone derivatives differing in their size and electronic properties for their reduction employing LBADH. After plotting the relative activity against the measured substrate volumes we observed that apart from the substrate size other effects must be responsible for the activity obtained. Compared to acetophenone (100% relative activity), other small substrates such as propiophenone, α,α, α-trifluoroacetophenone, α-hydroxyacetophenone, and benzoylacetonitrile had relative activities lower than 30%, while medium-sized ketones such as α-bromo-, α,α-dichloro-, and α,α-dibromoacetophenone presented relative activities between 70% and 550%. Moreover, the comparison between the enzymatic activity and the obtained final conversions using an excess or just 2.5 equiv. of the hydrogen donor 2-propanol, denoted again deviations between them. These data supported that these hydrogen transfer (HT) transformations are mainly thermodynamically controlled. For instance, bulky α-halogenated derivatives could be quantitatively reduced by LBADH even employing 2.5 equiv. of 2-propanol independently of their kinetic values. Finally, we found good correlations between the IR absorption band of the carbonyl groups and the degrees of conversion obtained in these HT processes, making this simple method a convenient tool to predict the success of these transformations. The Royal Society of Chemistry.

β-(Carbonatoxy)alkyl radicals: A new subset of β-(ester)alkyl radical fragmentation during copper(I)-mediated synthesis of 1,1-dichloro-1-alkenes

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.

Trichloromethyl ketones: Asymmetric transfer hydrogenation and subsequent Jocic-type reactions with amines

Amino-amides are important pharmaceutical building-blocks. The enantioselective reduction of trichloromethyl ketones using ruthenium transfer hydrogenation catalysts is reported. The products react in a range of Jocic-type reactions to give enantiomerically enriched amino-amides.

Transition-metal-free transformation of aryl bromides into aromatic esters and amides via aryl trichloromethyl ketones

A variety of aryl bromides have been treated with Mg and then chloral, followed by tBuOCl and subsequently alcohols or amines to produce the corresponding aromatic esters or amides in good yields via the formation of aryl trichloromethyl ketones as intermediates. These reactions are examples of a transition-metal-free one-pot preparation of aromatic esters and amides from aryl bromides. Aryl bromides have been treated with Mg and then chloral, followed by tBuOCl or tBuOCl with I2 as an additive, and subsequently alcohols or amines to form the corresponding aromatic esters and aromatic amides via aryl trichloromethyl ketones as intermediates. Copyright