Isonitril

Cyclic Carhene Complexes. The reaction of aziridines with carbonyl, thiocarbonyl, or isonitrile ligands in Mn, Re, Fe, Ru, Pd, or Pt complexes leads to formation of cycHc carhene complexes (324—331). 

Divalent molybdenum compounds occur in mononuclear, dinuclear, and hexanuclear forms. Selected examples are shown in Figure 6. The mononuclear compounds are mostiy in the realm of organometaUic chemistry (30—32). Seven-coordinate complexes are common and include MoX2(CO)2(PR3)2, where X = Cl, Br, and I, and R = alkyl MoCl2(P(CH3)3)4, heptakis(isonitrile) complexes of the form Mo(CNR) 2 (Fig. 6d), and their chloro-substituted derivatives, eg, Mo(CNR)3CR. The latter undergo reductive coupling to form C—C bonds in the molybdenum coordination sphere (33). 

CH3)3Si)2N]2U(CH2Si((CH3)2)N(Si(CH3)3)) Generally, uranium metaUacycles are quite reactive inserting a host of organics, ie, CO, secondary amines, nitriles, isonitriles, aldehydes, ketones, and alcohols. 

Traces of unsaturated nitriles can be removed by an initial refluxing with a small amount of aq KOH (ImL of 1% solution per L). Acetonitrile can be dried by azeotropic distn with dichloromethane, benzene or trichloroethylene. Isonitrile impurities can be removed by treatment with cone HCl until the odour of isonitrile has gone, followed by drying with K2CO3 and distn. 

HCl until the smell of the isonitrile had gone, then dried with K2CO3 and fractionally distd [Turner J Chem Soc 1681 1956]. Alternatively it was twice heated at 75° and stirred for several hours with a mixture of 7.7g Na2C03 and 11.5g KMn04 per L of butyronitrile. The mixture was cooled, then distd. The middle fraction was dried over activated alumina. [Schoeller and Wiemann 7 Am Chem Soc 108 22 1986.]... 

Isobutyronitrile (2-methylpropionitrile, isopropyl cyanide) [78-82-0] M 69.1, b 103.6 , d 0.7650, n 1.378. Shaken with cone HCl (to remove isonitriles), then with water and aq NaHC03. After a preliminary drying with silica gel or Linde type 4A molecular sieves, it is shaken or stirred with CaH2 until hydrogen evolution ceases, then decanted and distd from P2O5 (not more than 5g/L, to minimize gel formation). Finally it is refluxed with, and slowly distd from CaH2 (5g/L), taking precautions to exclude moisture. 

This method is particularly applicable to the more reactive benzyl halides which are easily hydrolyzed in the aqueous media usually employed for the metathetical reaction with alkali cyanides. For example, anisyl chloride treated with sodium cyanide in aqueous dioxane gives, as a by-product, 5-10% of anisyl alcohol as determined by infrared analysis. The use of anhydrous acetone not only prevents hydrolysis to the alcohol but also decreases the formation of isonitriles. This method was also applied successfully by the submitters to the preparation of -chlo-rophenylacetonitrile in 74% yield. 

Perfluorinated isonitriles are of special interest as ligands in metallorganic chemistry [73]. Generally, W-perfluoroalkylated itmnes result from addition reactions A -Trifluoroniethylhalomethaneimines are obtained on reaction with HX (X = F, Cl, Br) [74] Via this route, the remarkably stable and distillable V-trifluo-romethylforraamide is obtained from trifluoromethyhsonitrile and trifluoroacetic acid [75] (equation 7)... 

Highly reactive dipolar bis(tnfluoromethyl)-subsmtuted heterodienes are excellent traps for one-skeleton-atom species , even when these are short lived The hetero-1,3-dienes add electron nch and electron poorcarbenes[/2,, 125,126,127,128 129,130], carbene complexes [131], carbene analogues [SnClj, Sn(C< H, )2, GeCl2, Gey [132, 133], isonitriles [128], etc, to give [4-t-l] cycloadducts (equation 29)... 

Isonitriles and some nitriles can be viewed formally as having a nucleophihc center and an electrophilic center at the same skeleton atom Tnmethylsilylcyanide and cyanoformates add to hetero-1,3 dienes in a stepwise process to give five-mem bered rmg systems with the same stmcture as the isonitnle adducts [41],... 

Isonitriles are stable, often naturally occurring, compounds that contain a divalent carbon. An example is axisonitrile-3, which can be isolated from a species of sponge and possesses anti-malarial activity. Write a resonance form for axisonitrile-3 that satisfies the octet rule. Don t forget to include formal charges. 

Azides have been shown to react with itniniutn salts to give addition products. The same product is obtained if the iminium salt is treated with azide ion or if the enamine is treated with hydrazoic acid 14). The yields of the products were all very high (85-95 %). The interest in this reaction centers on the fact that the azides react with isonitriles to give substituted tetrazoles (83) 44). 

Many novel cluster compounds have now been prepared in this way, including mixed metal clusters. Further routes involve the oxidative fusion of dicarbon metallacarborane anions to give dimetal tetracarbon clusters such as (103) and (104) O (jjg insertion of isonitriles into inetallaborane clusters to give monocarbon meiallacarboranes such as (105) and the reaction of small ii/t/o-carboranes with alane adducts such as Et3NAlH3 to give the commo species (106) ... 

Other cyanide complexes arc discussed under the appropriate metals. In organic chemistry, both nitriles R-CK and isonitriles (isocyanidcs) R-NC are known. Isocyanides have been extensively studied as ligands (p. 926). More... 

TosMIC reagents. For example, glyoxylic acid ethyl ester undergoes cycloaddition with (2-naphthyl) tosylmethyl isonitrile (17) to produce oxazole 18 in good yield. ... 

The only known representative of this type of compound, 91, was prepared by 1,3-dipolar addition of mesityl nitrile oxide to telluroketone 85 (93JA7019 94MI1). The reaction proceeds smoothly on heating equimolar amounts of the reactants at 80°C, giving rise to 91 in 70% yield. The heterocycle is a thermally unstable and light-sensitive compound. Thermolysis of a deuterochloroform solution of 91 at 60-90°C in a sealed ampule affords 1,1,3,3-tetramethylindanone and mesityl isonitrile (94MI1). 

Since the cyanide anion is an ambident nucleophile, isonitriles R—NC may be obtained as by-products. The reaction pathway to either nitrile or isonitrile can be controlled by proper choice of the counter cation for the cyanide anion. 

With alkali cyanides, a reaction via a SN2-mechanism takes place the alkyl halide is attacked by cyanide with the more nucleophilic carbon center rather than the nitrogen center, and the alkylnitrile is formed. In contrast, with silver cyanide the reaction proceeds by a SnI-mechanism, and an isonitrile is formed, since the carbenium intermediate reacts preferentially with the more electronegative center of the cyanide—i.e. the nitrogen (Kornblum s rule, HSAB concept). ... 

Chloroform is readily recognised by its odour and by the phenyl isonitrile test. It is found in the first fractions distilled. 

Reaction of iodoethane with CN yields a small amount of isonitrile, CH3CH2N = C, along with the nitrile CH CE C N as the major product. Write electron-dot structures for both products, assign formal charges as necessary, and propose mechanisms to account for their formation. 

The chloroform fraction has a very strong odor of isonitrile. Only a trace is noted in the redistilled product. 

Of the four components reacting in the Ugi reaction, the isocyanide and the carboxylic acid have only limited influence on the overall stereoselection. For instance, in the synthesis of 13-demethyldysidenin (R)-l and 13-demethylisodysidenin (S)-l from a chiral aldehyde, chiral carboxylic acid, isonitrile and methylamine79. 

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