Benzyl formamide

When labeled potassium cyanide reacted with the complex in an aqueous methanol solution, the bromide was rapidly replaced and the labeled cyanide ion entered slowly into the coordination complex. When the reaction was conducted at higher temperatures in ethylene glycol dimethyl ether as the solvent, the label was distributed among the benzyl isonitrile, benzyl formamide, and the polymer resulting from benzyl isonitrile and the iron isonitrile complexes. 

In a simple displacement of benzyl isonitrile by K14CN from II, all the labeled atoms should appear in the isonitrile complex and none in the benzyl isonitrile. But the label was present in all of the products isolated and in each to a different extent. For example, the benzyl isonitrile was more radioactive than the N-benzyl formamide which must have been formed by addition of water to benzyl isonitrile. The results indicate that the internal isomerization (III V, Equation 7), the generation of benzyl isonitrile and N-benzyl formamide, and the polymerization of benzyl isonitrile are concomitant reactions. 

Simha equation), where a/b is the length/diameter ratio of these cigarshaped particles. Doty et al.t measure the intrinsic viscosity of poly(7-benzyl glutamate) in a chloroform-formamide solution and obtained (approximately) the following results ... 

The intrinsic viscosity of poly(7-benzyl-L-glutamate) (Mq = 219) shows such a strong molecular weight dependence in dimethyl formamide that the polymer was suspected to exist as a helix which approximates a prolate ellipsoid of revolution in its hydrodynamic behaviorf ... 

Poly(7-benzyl-L-glutamate) is known to possess a helical structure in certain solvents. As part of an investigationf of this molecule, a fractionated sample was examined in chloroform (CHCI3) and chloroform saturated ( 0.5%) with dimethyl formamide (DMF). The following results were obtained ... 

Petroleum ether with aniline, benzyl alcohol, dimethyl formamide, dimethyl sulfoxide, formamide, furfuryl alcohol, phenol or water. 

A mixture of jV-[(2-benzyl-3-methyl)phenyl]formamide (24. R1 = R3 = R4 = H R2 = Me 15 g, 68 mmol) in PPA (120 g) and POC1, (32 g. 208 mmol) was stirred at 120"C for 1.5 h. The mixture was cooled, diluted with cold H20. and basified by addition of aq KOH. The alkaline mixture was extracted with Et20, the extracts were dried (MgS04), and evaporated to give the crude product as an oily residue, which was purified by distillation under reduced pressure (bp 110 Q0.025 Torr). The distillate solidified on cooling to give the product as yellow needles yield 6g (43%) mp 68 C. 

Isonitriles are widespread metabolites in marine organisms, although little attention has been paid to their degradation. Pseudomonas putida strain N-19-2 can hydrolyze isonitriles to N-substituted formamides (Goda et al. 2001), and the enzyme is active toward cyclohexyl isonitrile and benzyl isonitrile. 

IV Glycols, benzyl alcohol, acetic acid, formamide... 

IV Acetic acid, formamide, benzyl alcohol, glycols... 

Fig. 33. Zimm plot128) for a sample of poly-7-benzyl-L-glutamate in dimethyl formamide at 25 °C...

As has been discussed, ordinary formamides have a barrier of about 21 kcal/ mol, which is a little less than that required for the isolation of atropisomers at room temperature. This means that, at a temperature slightly lower than ambient, it may be possible to obtain stable rotamers. This possibility was first realized by Gutowsky, Jonas, and Siddall (40). They used a uranyl nitrate complex of N-benzyl-N-methylformamide (4) crystallized from dichloromethane. When the crystals were washed with ice water to strip off the uranyl nitrate, a mixture of E and Z forms (Z/E = 1.6) was obtained. Since the equilibrium mixture gives a Z/E value of 0.8, it was possible to perform a kinetic study of equilibration... 

In this approach the C(2)-N(3) and C(6)-N(l) components are usually the same. Formamide or nitriles are common C-N components. A classical example is the trimerization of acetonitrile to give 2,6-dimethyW-pyrimidinamine <1994HC(52)1 >, while a modern example involves a similar trimerization of a variety of alkyl and benzylic nitriles 707 under microwave conditions <2005JC0483>. 

Die Umwandlung von (2-Oxo-alkyl)-l, 2,4-triazolium-Salzen mit Natriumhydrid in Dimethyl-formamid fiihrt zu 4-Acyl-5-amino-imidazolen. Diese Reaktion verlauft iiber offenkettige N-Cyan-formamidine, was in einem Beispiel durch Isolierung des N-Cyan-formamidins und dessen thermische Cyclisierung zum 4-Acyl-5-amino-imidazol nachgewiesen wurde. Die Ausbeuten liegen im allgemeinen um 30%. In einem Fall wurden 60% Ausbeute erzielt [5-Amino-l-(4-chlor-benzyl)-4-(2,4-dichlor-benzoyl)-imidazol Schmp. 220°]373 ... 

The presence of a quaternary carbon atom at the 4 position of the piperidine in the form of a spiro substituent seems to enhance potency. The starting piperidin is the product from the formal additon of cyanide and aniline to the 4 position of A-benzyl-4-piperidone (see Chapter 7 [28-3] for preparation). Reaction of that with formamide serves to form the spiro-imidazoline ring (21-4). The benzyl protecting group is then removed by hydrogenolysis over palladium to give the secondary... 

Fluoride chloride exchange of 1 -chlorooctane (3) with potassium fluoride, catalyzed by tetra-butylammonium bromide gives higher yields (72%) of 1-fluorooctane (4) in the presence of formamide than those reactions conducted in the presence of water.57 In the case of 1-bro-mooctane, benzyl chloride or phenethyl chloride, fluoride halide exchange gives only a yield of < 50%. 

Detailed kinetic studies of some aprotie systems were reported by Bamford s group. The kinetics of the polymerisation initiated by sodium salt of dihydrocinnamic acid in N-methyl-formamide exhibits a few interesting features. Typical conversion curves for D,L-phenyl alanine and y-benzyl-L-glutamate NCA s are shown in Fig. 10 taken from the paper by Ballard and BamfoRD (54). For a low concentration of the salt, the reaction is self-inhibited, i. e. a relatively rapid polymerisation ceases after a while (curve C) when a substantial fraction of the still... 

Fig. 10. Conversion-time curves for polymerisation of NCA s in 80% nitrobenzene —20% N-inethyi formamide mixture 26° C. [NCA] — 0.109 mol. I"1 Initially in all cases, (a) y-benzyl-L-gtutamate NCA [sodium dl-hydrocinnamate = 4.6 x 10 mol 1-J (b) DL-phenylalanineNCA [sodiumdihydrocinnamate] — 4.6 x 10 moll-1 (c) DL-phenylalanine NCA [sodiumhydantoin 3-acetate] = 9.2 x 10 moll-1. 100% evolution of CO . [Reprinted from paper by D. G. H. Ballard and C. H. Bamford Special Publication of Chem. Soc.

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