Isocyanide, benzyl

The synthesis of highly substituted rigid tricyclic nitrogen heterocycles via a tandem four-component condensation (the Ugi reaction)/intramolecular Diels-Alder reaction was investigated in both solution and solid phase [24]. The Ugi reaction in MeOH (Scheme 4.2) involves the condensation of furylaldehydes 17, benzylamine 18, benzyl isocyanide 19 and maleic or fumaric acid derivatives 20, and provides the triene 21 which immediately undergoes an intramolecular Diels-Alder reaction, affording the cycloadduct 22 in a diastereoisomeric mixture with high yield. 

A first terminal imido complex of nickel (121) was prepared according to Equation (3).468 The synthesis goes via the Ni11 amido compound (122) and uses the steric bulk of the arylimido group for stabilization. The Ni11 center in (121) is planar and three-coordinate. Reaction of (121) with CO or benzyl isocyanide leads to formal nitrene transfer with formation of (124) and (125), respectively. Further reaction with CO liberates the isocyanate and carbodiimide (Equation (4)). 69... 

N,N,o-trimethyl-, 34, 61 N-Benzylaniline, 36, 22 Benzyl chloride, 34, 65 Benzyl cyanide, 31, 53 32, 64, 65, 92 N-Benzylidenemethylamine, 34, 65 Benzyl isocyanide, 31, 54 Benzylmagnesium chloride, 34, 65 3-Benzyl-3-methylpentanenitkile, 35, 8 3-BENZYL-3-METHYLPENTANOIC ACID, 35, 6 /S-Benzyl-/ -methylvaleric acid, 35, 6 Benzylthiosulfuric acid, 32, 103 Benzyltrimethylammonium hydroxide,... 

Benzyl isocyanide, 41, 14 Benzyl mercaptan for synthesis of 2,4-dinitrophenyl benzyl sulfide, 44, 48... 

Products isolated from the thermal fragmentation of A-arylbenzamide oximes and A-arylbenzamide O-phenylsulfonyl oximes have been accounted for by invoking a free-radical mechanism which is initiated by the preferential homolysis of the N-O bond." Time-resolved IR spectroscopy has revealed that photolysis of A, A -diphenyl-l,5-dihydroxy-9,10-anthraquinone diimine affords acridine-condensed aromatic products via excited-state intramolecular proton transfer." The absolute and relative rates of thermal rearrangements of substituted benzyl isocyanides have been measured,and it has been found that the relative rates are independent of temperature and exhibit excellent Hammett correlations. Thionitrosoarene (25), thought to be generated by desulfurization of the stable A-thiosulfinylaniline (24), has been established" " as an intermediate in the formation of 3,3a-dihydro-2,l-benzisothiazole (26) from o-alkylthionitrosoarene (24). 

Figure 13.4 Ordinary Raman spectrum of BZI (benzyl isocyanide) in (a) neat liquid state, and SERS spectra of (b) 5 X 10 M BZI in aqueous Ag nanocolloids, and (c)...

Joo, S.-W. and Kim, Y.-S. (2004) Surface-enhanced Raman scattering study of benzyl mercaptide and benzyl isocyanide on gold and silver nanocolloid surfaces. Colloids Surf. A, 234, 117-22. 

In a three-component synthesis the amide (86-1) obtained from the ester (85-5) and benzyl isocyanide is reacted with the piperdone (86-2). The product from this transform consists of the addition product (86-3) where amide nitrogen in (86-1) as well as the carbon from the isocyanide have added to the carbonyl group on the piperidine. Treatment of the adduct (86-3) with a strong acid hydrolyzes the urethane function on the fert-butyloxycarbonic protecting group, leaving behind the primary... 

Muetterties and co-workers (21, 22, 60, 139) found that addition of deficiencies of isocyanides to Ni(COD)2 gave the clusters Ni4(CNR)7 (R = Bu, C6H,) and Ni4(CNBu )6. With isopropyl and benzyl isocyanides, dark brown and red solids of compositions Ni4(CNPr )6 and (Ni4(CNCH2Ph)4 Jt (x unknown) were obtained. Corresponding reactions in the presence of L [L = P(OMe)3, CNMe] gave Ni7(CNBu )6L. 

A mixture of benzaldehyde la (106 mg, 1 mmol) and 2-aminopyridine 3a (94 mg, 1 mmol) was irradiated in an unmodified household microwave oven for 1 min (at full power of 900 W) in the presence of montmorillonite K-10 clay (50 mg). After addition of benzyl isocyanide 2a (117 mg, 1 mmol), the reaction mixture was further irradiated successively (2 min) at 50% power level for a duration of 1 min followed by a cooling period of 1 min. The resulting product was dissolved in dichlorometliane (2x5 mL) and the clay was filtered off. The solvent was removed under reduced pressure and the crude product was purified either by crystallization or by passing it through a small bed of silica gel using EtOAc-hexane (1 4, v/v) as eluent to afford 4a. 

This product is sufficiently pure for most purposes but it contains some benzyl isocyanide and usually develops an appreciable colour on standing. 

The first example of a tandem Ugi-4CR/intramolecular Diels-Alder reaction was reported by Paulvannan at Affimax [95], who obtained precursors for intramolecular Diels-Alder cycloadditions by an Ugi-4CR between furan-2-carboxaldehydes, monoamides or monoesters of fumaric or maleic acids, benzylamine, and benzyl isocyanide. The Ugi-4CR adducts 172 were never isolated since they underwent... 

The TOSMIC anaiog -(tosyl)benzyl isocyanide readily reacts with simple acceptors (ethyl acrylate, acrylonitrile, etc.) to give 4-substituted 2-arylpyrroles. Extension to 2,3-diaryl derivatives by use of styryl acceptors required the use of n-butyllithium as a base. <95SC795>... 

The benzyl cyanide used should be washed with warm 50% sulfuric acid to remove benzyl isocyanide 5 and redistilled. 

BENZYL ISOCYANIDE OXIDATION OF 5-AMINOTETRAZOLES (Benzene, isocyanomethyl)... 

---