Trifluoromethoxy

AMINES - AMINES,AROMATIC - PHENYLENEDIAMINES] (Vol2) a-(l-Methylethyl)-a-4-(trifluoromethoxy) phenyl-5-pyrimidmemethanol [56425-91-3]... 

Diazoketones react with trifluoromcthyl hypofluorite to give a mixture of a,a-difluoro ketones and o-fluoro-a-trifluoromethoxy ketones [70, 71] With elemental fluorine, two fluorine atoms replace the nitrogen in both diazoketones and unactivated diazo eompounds [70, 72, 73] (equation 9)... 

Tnfluoromethyl hypofluonte will fluorinate Schiff bases, giving N,a,a-tn-fluoroatmnes and a-fluoroimines [144] and reacts with diazoketones to give adducts in modest yields [145] (equation 6) At-Substituted aziridines give nng opened products by 1,3 addition of fluonne on nitrogen and trifluoromethoxy on carbon [146] (equation 7)... 

An example of cleavage ol the sulfur-oxygen bond in trifluoromethane-sulfonic ester has been reported Tnfluororaethyl triflate reacts with neutral or anionic nucleophiles with elimination of carbonyl difluoride and formation of trifluoromethanesulfonyl fluoride [57] (equation 32) The mechanism of this reaction involves elimination of fluoride ion, which is a chain carrier in the substitution of fluorine for the trifluoromethoxy group... 

In addition to direct inhibition of the vesicular transport protein, storage of neurotransmitters can be reduced by dissipation of the proton electrochemical gradient. Bafilomycin (a specific inhibitor of the vacuolar H+-ATPase), as well as the proton ionophores carbonyl cyanide m-chlorophenylhydrazone (CCCP) and carbonylcyanide p-(trifluoromethoxy) phenylhy-drazone (FCCP) are used experimentally to reduce the vesicular storage of neurotransmitters. Weak bases including amphetamines and ammonium chloride are used to selectively reduce ApH. 

The methods that are known for introducing trifluoromethoxy groups into arenes are generally not effective. An interesting onc-pot O-alkylation of phenols followed by halogen exchange to form trifluoromethyl ethers 6 has been described227 (see also Houben-Weyl, Vol. E4, pp 626-627). 

Various sugar molecules may be successfully fluorinated vicinal fluoro trifluoromethoxy products and vicinal difluoridcs are formed, e.g. formation of 21 and 22, and 23. syn Addition predominates and the fluoro atom enters according to Markovnikov-typc regioselectivity38 41 thus forming the more stable earbenium ion. 

Fluorine addition with trifluoromethyl hypofluoritc to various uracil and cytosine bases and nucleosides has been extensively studied. Vicinal fluoro trifluoromethoxy or fluoro methoxy adducts, formed mainly by syn addition, are usually hydrolyzed thus resulting in fluoro-sub-stituted derivatives,42 48 e.g. formation of 24 and 25. 

Diazo ketones are converted into a mixture of up to four products a,a-difluoro ketones 27, a-fluoro a-trifluoromethoxy ketones 28. and fluoro- and trifluoromethoxy-substituted epoxides 29 and 30. Product distribution depends on the substituent R on the carbonyl atom.51,52... 

Studies on acetylenic molecules have been less extensive than those on alkenes diphenylacety-lene is converted at — 78 °C in Freon in the presence of calcium oxide with 2.5 equivalents of trifluoromethyl hypofluorite into l,l,2-trifluoro-l,2-diphenyl-2-(trifluoromethoxy)ethane (31) in 75% yield.37... 

Benzene (32, R = H) reacts under photochemical conditions with trifluoromethyl hypofluorite giving fluorobenzene as the main product together with (trifluoromethoxy)benzene,15 while the reaction with toluene (32, R = Me) also gives sidc-chain-substituted products.2,3,15... 

In the low-temperature fluorination of benzofuran (39, Y = O) and 1-acetylindole (39. Y = NAc), addition reactions are observed as well as vicinal fluoro trifluoromethoxy adducts 40A and 40B, vicinal difluoridcs 41 are formed.63 Trichloromethiazide is converted into the 5-fluoro derivative 42 in tetrahydrofuran/hydrogen fluoride at 0 C (in dichloromethanc/acetone 42 is accompanied by two nonfluorinated products).64... 

In the reaction with bis(trifluoromethyl) trioxide (10), addition of both CF30 and CF300 groups to the sulfur tetrafluoride molecule occurs to give a mixture of . v-(trifluoromethoxy)(tri-fluoromethylperoxy)sulfur tetrafluoride, s-bis(trifluoromethoxy)sulfur tetrafluoride (11) and (trifluoromethoxy)sulfur pentafluoride.215... 

The photolytic reaction of trifluoromethyl hypochlorite gives s-bis(trifluoromethoxy)sulfur tetrafluoride (11) in very high yield.216... 

Propanoyl Fluoride TetraUuoro-3-trifluoromethoxy- ElOa, 313 (Alkanol + HF e9)... 

Fiuorooxy-hexafluoro-2-trifluoro-mcthyl- ElOa. 280f. (OK - OF) Heptafluoro-l-trifluoromethoxy-ElOa. 272 (En F F3C-OF) Heptafluoro-2-trifluoromethoxy-F.IOa. 272 (F.n + F3C-OF)... 

Pentane l,1-Difluoro-2,4-dioxo-l-trifluoromethoxy- ElOb,. 451 (RF - COOR 4 R — CO —CH3)... 

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