C.H< Propyne

METHYL ACETYLENE C.H. Propyne. Allylene Strong oxMizcrs, chlorine, copper, copper alloys NA 1.7 11.7... 

Propargyl Alcohol. Propargyl alcohol [107-19-7] 2-propyn-l-ol, C H O, is the only commercially available acetylenic primary alcohol. A... 

Both cis- and rrans-l-arylsulfonyl-2-arylsulfenyl propenes (56) underwent a Smiles rearrangement under electron impact at 20 and 70 eV and formed a diarylsulfide ion [M — 104]+ (equation 27a)39 through a process where a bond between the R C H group and the sulfide sulfur is formed and a rearomatization occurs by a loss of the neutral thiirene dioxide or a simultaneous expulsion of SOz and propyne. The ion m/z 148 was also obtained from all of the sulfonyl-sulfides, 56 (equation 27b) and here the loss of R2 seemed to be related to the bond strength39. In addition to the above compounds 56 exhibited some simple cleavages before and after sulfone-sulfinate rearrangements. 

A line structure (introduced in Section C) represents a chain of carbon atoms as a zigzag line. The end of each short line in the zigzag represents a carbon atom. Because carbon nearly always has a valence of 4 in organic compounds, we do not need to show the C—H bonds. We just fill in the correct number of hydrogen atoms mentally, as we see for methylbutane (6), isoprene (7), and propyne (8). As explained in Section 2.7, a benzene ring is represented by a circle inside a hexagon, and we need to remember that one hydrogen atom is attached to each carbon atom. 

We have also observed competition between products resulting from C-C and C-H bond activation in reactions of Y with propene,138 propyne,143 2-butyric,143 four butene isomers,138 acetaldehyde,128 acetone,128 ketene,144 and two cyclohexadiene isomers,145 as well as for Zr, Nb, Mo, and Mo with 2-butyne.143 In this chapter, we use the term C-C activation to describe any reaction leading to C-C bond fission in which the hydrocarbon reactant is broken into two smaller hydrocarbon products, with one hydrocarbon bound to the metal. It is important to note, however, that C-C activation does not necessarily require true C-C insertion. As will be shown in this chapter, the reaction of Y, the simplest second-row transition metal atom, with propene leads to formation of YCH2 +C2H4. The mechanism involves addition to the C=C bond followed by H atom migration and C-C bond fission, rather than by true C-C insertion. 

Butler and co-workers have taken a unique approach to study the unimolecular dissociation of the vibrationally and rotationally hot allyl radical.150-152 They have examined the secondary C-H dissociation of the allyl radicals that are produced with high internal energies above the allyl dissociation thresholds in the primary photodissociation of allyl chloride and allyl iodide at 193 nm. The production of allene versus propyne (both at mass 40) from the secondary dissociation of the hot allyl radicals are... 

The pyrolysis of pyrrole produces a variety of products hydrogen cyanide, propyne, allene, acetylene, c/ -crotonitrile, and allyl cyanide, among them. Lifshitz et al. hypothesized that pyrrole undergoes 1,2-bond (N—C) cleavage, then an internal H-atom transfer, to yield a radical intermediate that can isomerize to either c/ -crotonitrile or allyl cyanide, or dissociate to HCN and propyne.Bacskay et al. completed quantum chemical comparisons of the isoelectronic pyrrolyl and cyclopentadienyl radicals they hypothesized that pyrrolyl radical is formed via C—H bond scission in the intermediate pyrrolenine (2/f-pyrrole) rather than directly via N—H bond cleavage (Fig. 14). Mackie et al. explained a similar finding, postulating that it was the formation of pyrrolenine that dictated the rate at which pyrrole pyrolysis occurred. 

An analogous mechanistic scheme (equation 87) has been proposed for the flash vacuum pyrolysis of dimethylsilyl(trimethylsilyl)thioketene148 (256). The pyrolysis of bis(trimethylsilyl)thioketene (257) leads to a more complicated product mixture (equation 88). With 47% conversion, a mixture of trimethylsilylacetylene, 1-trimethylsilyl-1-propyne, bis(trimethylsilyl)acetylene, (trimethylsilyl)thioketene, 2,2,4,4-tetramethyl-2,4-disila-l-thietane and 2,2,4,4-tetramethyl-2,4-disila-l,3-dithietane was obtained. All products can be rationalized, however, by the assumption that carbene 258 undergoes not only a silylcarbene-to-silene rearrangement (as in the preceding two cases) but also isomerization to 2-thiirene and insertion into a methyl-C, H bond. 

Treatment of the imide hydride Cp 2Ta(=NBu )H with [Ph3C][B(C6F5)4] yields the cationic imide [Cp 2Ta-(=NBu )(THF)][B(C6F5)4] (22). (22) reacts cleanly with H2 to yield [Cp 2Ta(NHBu )H][B(C6F5)4], and undergoes C-H bond activation reactions with propyne or pheny-lacetylene to afford [Cp 2Ta(NHBuO(C=CR)][B(C6F5)4] (R = Me, Ph). The heterolytic cleavage reactions of (22) may be the result of the presence of both electrophilic and nucleophilic sites of reactivity in the same molecule. Intramolecular activation of a C-H bond of a Cp lig-I------------------------------1... 

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