Phenyl trifluoromethyl sulfide

Alkyl, aryl, and uiisaturated aldehydes can be transformed to the corresponding (x-trifluoro-mcthylated alcohols in 86-96% yield by trifluoromethylation of the aldehydes with sodium triethylgermanidc/phenyl trifluoromethyl sulfide. ... 

Phenyl iodide (2.04 g, 10 mmol), FS02CF2C0,Mc (10 mmol), Cul (2.0 g, 10 mmol), Sg (0.32 g. 10 mmol), and HMPA (30 mL) were placed in a 50-mL, tlirce-necked, round-bottomed flask equipped with a dry-ice condenser and under a atmosphere. After stirring at 100- HOC for 8 h (monitored by F NMR spectroscopy), the mixture was poured into ice water (50 mL), and the residue was filtered and washed with EtjO. The aqueous solution was filtered and extracted with EtjO (3 x 20 mL). The combined Ft,0 extracts were dried (anhyd Na SO ) and the Et O was removed. Distillation gave phenyl trifluoromethyl sulfide yield 1.03 g (60%) bp 70 72 C/350 Torr. 

These facts indicate that an a-trifluoromethyl group markedly promotes anodic substitutions with oxygen nucleophiles. As very few successful examples of anodic methoxylation of phenyl alkyl sulfides are known, " it is notable that an a-trifluoromethyl group facilitates the anodic methoxylation. As a result, these anodic substitution reactions have been systematically investigated from both a mechanistic and a synthetic viewpoint. ... 

This dialkoxydiphenylsulfurane has been prepared by the reaction of diphenyl sulfide, 2,2,2-trifluoro-l-phenyl-l-(trifluoromethyl)ethyl hypochlorite, and potassium l,l,l,3,3,3-hexafluoro-2-phenyl-2-propanolate and by the reaction of diphenyl sulfide with 1 equivalent of chlorine and 2 equivalents of potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanolate in diethyl ether. ... 

The derivatives of phenyl trichloromethyl ether, in contrast to their sulfide analogs, are fluorinated to trifluoromethyl compounds only in the presence of the antimony(V) chloride catalyst.82 8(1... 

In decalin at 190 °C or in acetic acid with 1,4-benzoquinone and sodium acetate trifluoromethylbutadienyl phenyl sulfides underwent intramolecular cyclization to afford 4-trifluoromethyl-2,3-disubstituted furans in high yields <02TL665>. 

Bromophenyl)[2-trifluoromethyl-4-(E-ethoxycarbonyl)ethenyl)-phenyl]sulfide... 

Chloro-l-(trifluoromethyl)ethyl Phenyl Sulfide (26) Typical Procedure ... 

Trifluoroacetaldehyde is difficult to prepare from trifluoroethanol. a-Methoxylated and a-acetoxylated 2,2,2-trifluoroethyl sulfides are trifluoroacetaldehyde equivalents, which are useful building blocks for synthesis of various trifluoromethylated compounds. The a-ace-toxy sulfide 10 is easily converted into trifluoroacetaldehyde phenyl-hydrazone (Eq. 44). The a-methoxy sulfide 9 is also readily transformed into biologically interesting a-monofluoroalkanoic acids (Eq. 45). 

This fluorination methodology was extended to various para-svb-stituted phenyl 2,2,2-trifluoroethyl sulfides, 37b-d. These substances undergo efficient fluorination regardless of the benzene ring substituent. Fluorine is exclusively introduced at the position a to the trifluoromethyl group. Neither aromatic fluorination nor benzylic fluorination was observed (run 5, Table 13). The results are noteworthy... 

TVifluoromethyl Phenyl Sulfide. The reaction of bromodiflu-orophenylsulfanylmethane with cesium fluoride (CsF) in sulfolane gives trifluoromethyl phenyl sulflde in moderate yield (eq 6). ... 

Form Supplied in colorless liquid often prepared by the oxidation of trifluoromethyl phenyl sulfide using aqueous hydrogen peroxide in acetic acid. ... 

The similar alkoxide- or hydroxide-induced trifluoromethylation was also found to work with other electrophiles. Diphenyl disulfide can be trifluoromethylated to give trifluoromethyl phenyl sulfide in 87% yield (eq 4). Methyl benzoate can be trifluoromethylated to generate 2,2,2-trifluoroacetophenone in 30% yield at temperatures between —50°C and —20°C. Trifluo-romethylcopper (CF3CU) can be generated in situ with trifluoromethyl sulfone, f-BuOK, and copper iodide (Cul), and it then further reacts with iodobenzene at 80 °C for 20 h to give a,a,a-trifluorotoluene in 26% 3neld. ... 

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