2- phenyl isocyanide

Place the distillate in a separating-funnel and extract the benzonitrile twice, using about 30 ml. of ether for each extraction. Return the united ethereal extracts to the funnel and shake with 10% sodium hydroxide solution to eliminate traces of phenol formed by decomposition of the benzenediazonium chloride. Then run off the lower aqueous layer, and shake the ethereal solution with about an equal volume of dilute sulphuric acid to remove traces of foul-smelling phenyl isocyanide (CaHjNC) which are always present. Finally separate the sulphuric acid as completely as possible, and shake the ether with water to ensure absence of acid. Run off the water and dry the benzonitrile solution over granular calcium chloride for about 20 minutes. 

Isocyanide reaction. Since chloral hydrate is readily converted into chloroform by alkali, it will give the isocyanide reaction. To a few crystals of the solid add about 5 ml. of alcoholic NaOH solution and a few drops of aniline, and heat the disagreeable odour of phenyl isocyanide, C H(NC, is rapidly detected. 

Cobalt, cyclopentadienyl(ij -tolane)-(triphenylphosphine)-reaction with phenyl isocyanide, 1, 666 Cobaltacycles selenophenes from, 4, 968 Cobaltacyclopentadienes reactions, I, 671 Cobester... 

Some of the artificial musks of commerce are mixtures of two or more of the bodies above described, a fact which is easily demonstrated by fractionally crystallising the specimen, when the fractions will show altered melting-points. The principal adulterant of artificial musk is acetanilide. This can, of course, be easily detected by the phenyl-isocyanide reaction or by dissolving it out with hot water. 

R)j 2S) is >100 1 when the reaction is carried out at — 78 C. f Phenyl isocyanide was used instead of tert-butyl isocyanide. 

Phenyl isocyanate, conversion to di-phenylcarbodiimide, 43,31 Phenyl isocyanide, 41,103 Phenyllithium, reaction with allyltri-phenyltin, 41, 30 standardization of, 41, 32 Phenylmagnesium bromide, 41, 91 reaction with ( r(-butyl perbenzoate, 41,91... 

The reaction of [p-MeC6H4C(NSiMe3)2]2Ta( = CH2)CH3 with 2,6-dimethyl-phenyl isocyanide afforded an f/ -ketenimine complex (Scheme 118). Carbon-sulfur cleavage reactions produced tantalum thioformaldehyde and tantalum sulfido complexes. ... 

The reaction of Mn(CO)jBr and methyl isocyanide was also carried out (Table V) the products are analogous to those obtained from phenyl isocyanide and the manganese complex. 

It is also appropriate to observe the substantial difference in ease of oxidation between phenyl and methyl isocyanide complexes, which has obvious chemical implication. This may perhaps be rationalized on the basis that phenyl isocyanide is a better 7r-acceptor than methyl isocyanide. This conclusion had previously been reached by infrared studies (see Section II). 

The colorless, diamagnetic copper(I) complex Cu(acac)(CNPh)2 is formed from copper(I) acetylacetonate and phenyl isocyanide (103). The copper(I) complex (CuCl)2(CNCjH,)2pip was isolated (124) it decomposes to C5H, oNCH=NCgH 11. Primarily on this basis, copper(I) complexes are presumed to be intermediates in various -addition reactions to isocyanides (Section III,D). 

A closer look at the thermal behavior variation upon introduction of a second aryl ring (see Figure 8.5 for the behavior of the derivatives with a w-decyloxy chain) reveals very interesting features for the phenyl isocyanide complexes the melting and clearing temperatures decrease in the order Cl > Br > I. This is also the trend of the clearing points for biphenyl isocyanide complexes, but their melting temperatures follow the opposite trend that is, I > Br > Cl. 

In a search for liquid crystalline phases, a series of (/>-alkoxy-phenyl)isocyanide complexes was prepared from (Me2S)AuCl and the corresponding ligands RNG, where R = C H2n + iO-C6H4 with n = 2-12 (in even numbers).206 The chlorides were converted into the bromides and iodides in metathesis reactions using KBr/KI. Mesogenic behavior was found for most of the new materials with transition temperatures in the range from ca. 95 to 160 °C. 

Finally, a reaction should be mentioned in which a nucleophile gives support to another reacting species without appearing in the final product. Diphenyl cyclopropenone interacts with 2,6-dimethyl phenyl isocyanide only in the presence of tri-phenylphosphine with expansion of the three-ring to the imine 344 of cyclobutene-dione-1,2229,230 Addition of the isocyanide is preceded by formation of the ketene phosphorane 343, which can be isolated in pure formss 231 it is decomposed by methanol to triphenyl phosphine and the ester 52. 

Both 2-azido [184] and 2-nitrophenyl isocyanides [185] are suitable synthons for the generation of the freely unstable 2-aminophenyl isocyanide and they have been used (Fig. 23) in the template-controlled preparation of NH,NH-stabilized benzim-idazolin-2-ylidene hgands. Both phenyl isocyanides coordinate readily to transition metal centers. The isocyanide ligand in complex 65 reacts with PPhs and the... 

Complex 61 is also accessible from the 2-nitrophenyl isocyanide complex 68 by reduction of the nitro group with Sn/HCl. Incomplete reduction of the nitro group in 68 with Raney-Nickel/hydrazine yields, after intramolecular cyclization, the complex 70 with the NH,NOH-stabilized benzimidazolin-2-ylidene ligand. Complex 69 with the 2-hydoxylamin-substituted phenyl isocyanide ligand presumably occurs as an intermediate in this reaction. The alkylation of both the NH,NH- and the NH, NOH-stabilized NHC ligands in 67 and 70, respectively, proceeds readily (Fig. 23) [184, 185]. 

Adsorption of Isocyanides (C=N-R) on Meta Su faces 531 Table 13.5 DFT-calculated adsorption energies of phenyl isocyanide on Aui4 and AgH clusters. 

Table 13.5 lists the ABads values obtained. On the basis of these calculations, the phenyl isocyanide should adsorb on the on-top sites on Ag and in the three-fold hollow sites on Au. On Au, phenyl isocyanide was calculated to adsorb on the three-fold hollow site with a slight rehybridization of the N atom, which causes a slight hit (27 °) from the surface normal. However, the energy difference between the most stable structure and the one with a linear C=N-C unit is only 0.3 kcalmoT. ... 

The isocyanide monolayer was formed by immersing the Cr slide in a 1 mM isocyanide solution under argon for 30 min. The redox wave, which is observed in cyclic voltammograms of the modified Cr electrode, proves that the 4-ferrocenyl-phenyl isocyanide is adsorbed on the metal surface. When a Cr electrode is exposed for 2 h to a solution of ferrocene, no redox wave was observed in the CV, which demonstrates that the isocyanide group is necessary for adsorption. No spectroscopic studies were performed on the adsorbed isocyanide. 

Sohn, Y. and White, J.M. (2007) Phenyl isocyanide on Cu(lll) bonding and interfadal energy level alignment. J. Phys. Chem. C, 111, 7816-25. 

A method for obtaining optically active polyiminomethylenes from achiral monomers was recently devised by Nolte, Drenth and co-workers (420). It consists in the copolymerization of an achiral monomer (e.g., phenyl isocyanide) with an optically active isocyanide endowed with a low tendency to polymerize. The chiral monomer is incorporated in one of the two helices and, due to its low reactivity, stops or slows down its growth. The other helix is unaffected by this phenomenon and continues to grow, permitting the almost complete conversion of the achiral monomer into an optically active polymer. 

Phenyl isocyanide (0.4 mL, 3.9 mmole) is added dropwise under nitrogen with stirring to tarns-[Pt2Cl4(PEt3)2] (1 g)5 in suspension in 30 mL of dry benzene. Initially a yellow oil is formed, but after about 1 hour a colorless oil is obtained that solidifies to give white crystals of the product. These white crystals can be recrystallized from benzene as colorless needles, mp 162-163°. Yield 0.9 g (70%). Anal. Calcd. for C13H20Cl2NPPt C, 32.0 H, 4.1 N, 2.9 Cl, 14.6. Found C, 32.2 H, 4.3 N, 3.0 Cl, 14.5. 

Comparison between the half-wave potentials (equations 2 to 4) of [Cr(CNR)6](PF6)2, e.g. for R = Bu , -1.04, -0.28 and 0.84 V (versus SCE),22 with those for [Cr(CNPh)6](PF6)2, i.e. -0.35, 0.25 and 1.00 V,20 shows that alkyl and aryl isocyanides favour respectively the higher and the lower oxidation states as expected from the greater a-donor and weaker jr-acceptor capabilities of the alkyl over the aryl isocyanides. Similarly, the phosphines in the mixed ligand complexes (Table 3), 23 relative to isocyanide ligands, stabilize the Cr111 oxidation state. The great difference in the relative stabilities of Cr—C bonds in the cyano and phenyl isocyanide complexes is indicated by the magnitude of the shift (ca. 2.0 V) between the Cr(CN) "/Cr(CN)r (-1.130 V) and the Cr(CNPh)i+/Cr(CNPh)i+ reduction potentials.28... 

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