1- cyanoacetylenes

The compound cyanoacetylene (HC=C—C=N) has been detected in interstellar space Make a molecular model or sketch the approximate geometry expected for this compound What IS the hybridization of nitrogen and each carbon" ... 

CH3I (methyl iodide) principal axes, 103 If rotation, 113 CH2NH (methanimine) interstellar, 120 Cr203 (chromium trioxide) in alexandrite laser, 347ff in ruby laser, 346ff HC3N (cyanoacetylene) interstellar, 120 HCOOH (formic acid) interstellar, 120 NH2CN (cyanamide) interstellar, 120... 

C2F12C12F2 (1,2-dichloro-l, 2-difluoroethane) symmetry elements, 83 CF13C3CN (methyl cyanoacetylene) interstellar, 120 2142X4 (s-tetrazine) fl S3 — X Ag transition, 3971F F1COOCF13 (methyl formate) interstellar, 120... 

Pyrazoles are formed when the diazo compounds react with alkynes or with functionalized alkenes, viz. the enols of /3-diketones. Pyrazolenines (353 Section 4.04.2.2.1) are isolated from disubstituted diazomethanes. Many pyrazoles, difficult to obtain by other methods, have been prepared by this procedure, for example 3-cyanopyrazole (616) is obtained from cyanoacetylene and diazomethane (7iJCS(C)2i47), 3,4,5-tris(trifiuoromethyl)pyrazole (617) from trifluorodiazoethane and hexafluoro-2-butyne (8lAHC(28)l), and 4-phenyl-3-triflylpyrazole (618 R =H) from phenyltriflylacetylene and diazomethane (82MI40402). An excess of diazomethane causes iV-methylation of the pyrazole (618 R = H) and the two isomers (618 R = Me) and (619) are formed in a ratio of 1 1. 

When cyanoacetylene (5), which is produced when an electric discharge is passed through a mixture of methane and nitrogen, is dissolved in a phosphate buffer a stable enol-phosphate (6) is formed. Pyrophosphate is produced when neutral aqueous solutions of (6) and orthophosphate are heated, and the phosphorylation of UMP has been achieved. However, from a study of the rate of phosphorylation and a consideration of environmental factors, especially the likely phosphate concentration in oceans, it is suggested that (6) is not an important intermediate in prebiotic phosphorylation. The conversion of the 3 -phosphate of 0 2 -cyclocytidine (7) into 2, 3 -cyclic CMP under mild conditions in aqueous solution has... 

Both theoretical and experimental data (in the solid, liquid, and gas phases) prove that the tendency of halocarbons to work as XB donors decreases in the order I > Br > Cl [66-68]. Clearly, polarizability and not electronegativity plays a key role. 3-Halo-cyanoacetylene works as self-complementary module and the N X distance is beautifully consistent with the scale reported above, being 2.932, 2.978 and 2.984 A in the iodo, bromo and chloro derivatives, respectively [69,70]. The same trend is observed when a phenyl, rather than a triple bond, spaces the donor and acceptor sites. The N Br distance in 4-bromobenzonitrile is longer than in the 4-iodo derivative [71,72] and no XB is present in the chloro and fluoro analogues, wherein molecules are pinned by N H and X- H short contacts [73]. PFCs have a very poor tendency, if any, to work as XB donors [74-77] and no crystal engineering can be based on such tectons. However, F2 is a quite strong XB donor and several adducts have been described in the gas phase [11,18] (see also the chapter by Legon in this volume). 

The synthesis and characterisation of a further compound which had been detected in outer space, cyanobutadiyne (2,4-pentadiynenitrile), has been carried out at the University of Rennes in France. This molecule belongs to a class in which one or more C-C triple bonds and only one carbonitrile substituent are present (H-(C= C%-C=N). These are often found in ISM the simplest, cyanoacetylene (H-C=C-C=N), has been detected several times in experiments intended to simulate the Titanian atmosphere. The largest molecule ever found in outer space, HCnN, is also a member of this family (Trolez and Guillemin, 2005). 

Many years later, Schwartz (Schwartz and Goverde, 1982 Voet and Schwartz, 1983) discovered that the synthesis of adenine via polymerisation of HCN can be accelerated by adding formaldehyde and other aldehydes. Reactions in the gas phase (nitrogen/methane atmosphere) promoted by electrical discharges led to the formation of cyanoacetylene in relatively good yields the latter reacts with urea to give various products, including cytosine (Sanchez et al., 1968). 

Robertson et al. (1996) were successful in synthesising cytosine and uracil in amazingly high yields. They started from cyanoacetaldehyde (obtained via hydrolysis of cyanoacetylene) and, again, urea. Cytosine is not formed in detectable concentrations unless concentrated urea solutions are used then, however, the yields are between 30 and 50%. Uracil was obtained by hydrolysis of cytosine solutions. 

Roberts et al. (1966) described a similar synthesis cyanoacetaldehyde and guanidine hydrochloride gave 40-80% yields of 2,4-diaminopyrimidine under the conditions of the lagoon model mentioned above. Hydrolysis of diaminopyrimi-dine leads to cytosine, isocytosine and uracil. Thiourea reacts with cyanoacetylene to give 2-thiocytosine however, the yield is considerably lower than with urea or... 

Fig. 4.6 A relatively simple synthetic route, using readily available starting materials, cyanoacetylene and urea,...

Reports of the synthesis of cytosine from cyanoacetylene (or its hydrolysis product cyanoacetaldehyde) with cyanate, cyanogens or urea show that these substances react faster with nucleophilic compounds to give side products than to give the required main product. In addition, the formation of cytosine requires concentrations which are unrealistic in prebiotic environments. 

The synthesis of the pyrimidines involves cyanoacetylene, which is synthesised in good yield from discharge reactions of CH4 and N2. The reaction with cyanoacetylene or cyanoacetylaldehyde, in a concentrating environment, produces cytosine and uracil according to Figure 8.6. 

Review on the synthesis and reactions of cyanoacetylene and dicyanoecetylene E. Ciganek, W. J. Linn and O. W. Webster, in The Chemistry of Functional Groups. The Chemistry of the Cyano Group (Ed. Z. Rappoport), Wiley-Interscience, London, 1970, pp. 423-638. 

Cyanoacetylene. As has been discussed above, the polymerization of acetylene in the solid at high pressure occurs along the diagonal of a definite crystal plane... 

Figure 23. (a) Arrangement of the cyanoacetylene molecules in the monocUnic P21 /"t crystal... 

Figure 6.1 shows the stockholder decomposition of the theoretical deformation density of the cyanoacetylene molecule, H—Cs=C—C=N (Hirshfeld 1977b). The overlap density in the bonds is distributed between the bonded atoms. The assignment of part of the density near the hydrogen nucleus to the adjacent carbon atom manifests the difference between fuzzy and discrete boundary partitioning methods. 

Substantially fewer studies have been published for the reactions of alkyl-substituted heteroaromatics, although these compounds also have implications for coal combustion. Several references discussed in the previous section contain information on methylated heteroaromatic rings. Mackie and coworkers completed experimental and theoretical studies of the pyrolytic decomposition of 2-picoline (2-methylpyridine). They concluded that decomposition proceeded mainly through o-pyridinyl and 2-picolinyl radicals. The former tended to decompose predominantly to yield cyanoacetylene, while the latter favored decomposition to a cyano-functionalized cyclopentadiene (Fig. 16). 

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