Bis trifluoromethyl diazomethane

The reaction of bis(trifluoromethyl)diazomethane with either Ni(CNBu )4 or [Pd(CNR)2] (R = Bu, Cy), also gave interesting complexes (XL) the structure of an analogous species, Pt(PPhj)2(CF3)4C2N2, was determined by X-ray crystallography (43). 

Acetylenedicarboxylic acid esters and related activated alkynes are routinely used as dipolarophiles for diazo dipoles. Recent examples include the use of diazo compounds 20 (49), 23 (51), and 24 (52) (Scheme 8.7), 25 (56) (Scheme 8.8), diazoacetaldehyde dimethylacetal (41) (which after cycloaddition and deprotection gave the corresponding pyrazole-3-carbaldehyde), ethyl 3-diazopyruvate (270), p-tolyl-trifluoromethyldiazomethane (271), bis(trifluoromethyl)diazomethane (272), and diazomethylenephosphoranes (60). 

Bis(trifluoromethyl)diazomethane, (CF3)2CNN, reacts at room temperature with [Ni(PPh3)2(C2H4)] to yield a complex which has been assigned the structure (42).202 Complex (43) has been obtained by reaction (37).199 The N=C=C group in complex (43) is severely distorted from linearity upon coordination. 

Arylcopper compounds decompose alkyldiazo compounds [Eq. (34)] 34, 37, 255). for which pentafluorophenylcopper is a very active catalyst. Bis(trifluoromethyl)diazomethane and pentafluorophenylcopper give perfluoro-2-phenylpropene under mild conditions, perhaps via elimination of copper(I) fluoride from an intermediate copper compound 37). Benzenediazonium compounds react in one of two ways 37) (1) diazo coupling with ffi-trifluoromethylphenylcopper to give m-trifluoromethyl-azobenzene in 93% yield or (2) direct displacement with pentafluorophenylcopper to give a 16% yield of 2,3,4,5,6-pentafluorobiphenyl, as well as 75% decafluorobiphenyl and 65% azobenzene. 

Bis(trifluoromethyl)diazomethane has been prepared by the nitrosation of 1,1,1,3,3,3-hexafluoroisopropylamine4 and by the present procedure,5 which gives higher yields. Bis(perfluoro-ethyl)diazomethane has also been prepared by an extension of this method.4... 

Bis(trifluoromethyl)diazomethane is a reactive, electrophilic compound. It forms adducts with nucleophiles such as amines and phosphines5 and adds to olefins, acetylenes,5 and thiocar-bonyl compounds6 to form heterocycles. It has been used as a source of bis(trifluoromethyl) carbene in reactions with benzene,5 saturated hydrocarbons,7 carbon disulfide,8 and transition metal compounds,8 and it undergoes a unique radical chain reaction with saturated hydrocarbons to form adducts that are hydrazoncs and azines.7... 

The sulphonyl isocyanates RS02NC0 (R = F, Cl, or CF3) have been shown to react120 with bis(trifluoromethyl)diazomethane at 100—160 °C to give l,2,3-oxathiazol-4-one 2-oxides (37). The fluorine-substituted form of... 

The spectra of compounds [188] to [191], formed by the reaction of bis(trifluoromethyl)diazomethane with the tricarbonyl( -allyl)cobalt compounds, and the reaction of the products with triphenyl-phosphine or -arsine, each consist of two multiplets in the range <5 —65 to —70, in accord with the distinctly different CF3 environments. (93) In [189] to... 

The reaction of bis(trifluoromethyl)diazomethane with (stilbene)bis-(triphenylphosphine)platinum unexpectedly gave the platinum fluorides [237] and [238], with the parameters shown, as minor products, (94) the... 

Bis(trifluoromethyl)diazomethane (7.26) is protonated in fluorosulfonic acid and the equilibrium is essentially on the side of the corresponding diazonium ion (7.27) at -70°C (Mohrig et al., 1974). As mentioned in Section 2.1, this was the first reasonably stable alkanediazonium ion observed. At - 5 to +5 °C, it undergoes slow dediazoniation (7-12). The kinetics of this reaction were found to be of first-order both in the concentration of diazonium ion and of the nucleophile. This is consistent with an ANDjsr-type displacement of the diazonio group by the fluorosulfonate anion ki > k- < ki), but not with unimolecular dediazoniation of the... 

Middleton, W.J. Reactions of bis(trifluoromethyl)diazomethane with perfluoro-thiocarbonyl compounds. J. Org. Chem. 1969, 34, 3201. 

In order to explain reactions of diazomethane and its derivatives with coordination compounds, it has been proposed that the formation of intermediate carbene complexes takes place. In the reaction of bis(trifluoromethyl)diazomethane with [IrCl(CO)(PMePh2)2] the carbene complex [IrCl(CO)(PMePh2)2 C(CF3)2 ] is formed rather than the chlorobis(trifluoromethyl)methyl iridium complex Ir CCl(CF3)2 (CO)(PMePh2)2. In many cases, such complexes were isolated and investigated ... 

Photolysis of bis(trifluoromethyl)diazomethane in the presence of bis(tri-methylsilyl)acetylene gives a complex mixture from which 3,3-bis(trifluoro-methyl>l,2-bis(trimethylsilyl)cyclopropene has been isolated in 6% yield (seep. 198). ... 

Bis-trifluoromethylthioketene reacts with bis-trifluoromethyl diazomethane to give two isomeric [3+2] cycloadducts 61 and 62" . 

Hexafluoroacetone imine distilled slowly during ca. 1 hr. into stirred anhydrous hydrazine cooled below 10°, allowed to warm to room temp., poured rapidly on P2O5, mixed and distilled -> hexafluoroacetone hydrazone (Conversion 53-59%) dissolved in benzonitrile, added dropwise with stirring during 1 hr. under Ng to ice-cooled Pb-tetraacetate and benzonitrile, then stirred 1 hr. at room temp. bis(trifluoromethyl)diazomethane (Y 76-79%). F. e. s. W. J. Middleton and D. M. Gale, Org. Synth. 50, 6 (1970). 

In a slow dediazotation reaction of bis(trifluoromethyl)diazomethane with (Ph2PCH3)2lr(CO)Cl, the iridium carbene complex 14 was formed and isolated in 37% yield (reaction 8.32) [63]. 

The carbene transfer from bis(trifluoromethyl)diazomethane to octacarbonyl dicobalt gives at room temperature in 28 days the p -bis(trifluoromethyl)methylene complex IS that was isolated in 54% yield (reaction 8.33) [64,65]. 

Cooke,)., Cullen, W.R., Green, M. and Stone, F.G.A. (1969) Reactions of bis (trifluoromethyl) diazomethane with transition-metal complexes. Journal of the Chemical Society A, 1872-1874. 

See p. 118 for the outcome of the reaction of the thioketen with bis(trifluoromethyl)-diazomethane. 

Decomposition of bis(trifluoromethyl)diazomethane or bis(trifluoro-methyl)diazirine in carbon disulphide at 150—175 °C produces the cyclic polysulphides (29) and (30), but bis(chlorodifluoromethyl)diazirine, prepared by treatment of the diamine (CFjCl)jC(NH,)2 with alkaline hypochlorite, yields only the carbene rearrangement product CF, CCl CFja when heated with the disulphide. ... 

Reactions between bis(trifluoromethyl)diazomethane and the acetylenes CFa CiCR (R = H or CF,), the propynyl derivatives CF,-C C-MMej (M = Ge or Sn), the Group IV and V compounds MejGeH, Me,GeBr, (Me Ge)g, Me,SnH, MegAsH, and (MejAs)g, and transition-metal compounds have been studied (see pages 51, 96, 172, 174, and 179). Nitration of 2,2,2-trifluorodiazoethane with dinitrogen pentoxide has yielded nitro-trifluorometh diazomethane. ... 

Treatment of cacodyl with bis(trifluoromethyl)diazomethane at 100 °C (no or only a very slow reaction occurs at 20 °C) gives a low yield of the tertiary arsine MeaAs-CH(CF3)a, a compound formed in 67% yield from the diazo-compound and dimethylarsine at 100 °C. ... 

---