Dinitriles compounds

In addition, other preparation methods of polyimides use bis(methylol imide) in reaction with diamines, diisocyanates, or dinitrile compounds, according to the scheme shown in Figure 3.7. 

In 1986, Sanyo Electric Company found that cyclic carbonates obtained by introducing halogens into EC can be used as solvents [84], which was followed by numerous reports on this topic [85-91]. In 1996, McMillan et al. from the National Research Council of Canada found an electrolyte that was compatible with graphite anode by utilizing fluoroethylene carbonate (60) [87] and propylene carbonate. The number of patent application for electrolytes consisting of fluoroethylene carbonate in combination with dinitrile compounds increased drastically around 2004. Details are described in Sect. 3.5.2 in the discussion of dinitriles. 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

Another example is the du Pont process for the production of adiponitrile. Tetrakisarylphosphitenickel(0) compounds are used to affect the hydrocyanation of butadiene. A multistage reaction results in the synthesis of dinitrile, which is ultimately used in the commercial manufacture of nylon-6,6 (144-149). 

Elimination of the hydroxyaminomethyl moiety from nitro oxime 15 by treatment with a diazonium salt gave hydrazone 43 (75LA1029) (Scheme 15). The same product was obtained by coupling the diazonium salt with the compound 16. On heating in aniline, oxime 15 was transformed into Schiff base 42. Acylation of the oxime 15 with benzoyl chloride in pyridine led to a mixture of furazan 44 and dinitrile 45. 

Aliphatic dinitriles (loss of CH2CN) Aromatic compounds Cyclic carbonate compounds Segmented fluoroalcohols (i.e.. loss of H2F2)... 

Some researchers have elaborated synthesis of PCSs employing bis(nitrile oxide)s as 1,3-dipoles and diynes, dinitriles, and a number of other compounds as dipolaro-philes154-156). 

Naphthalic anhydride has been prepared by the hydrolysis of the dinitrile of ,2-naphthaIic acid,1 by the oxidation of suitably substituted hydrocarbons or ketones,2 or by the dehydrogenation of the 3,4-dihydro compound with bromine 3 or with sulfur.4... 

Reactions of this type are called electrochemical hydrodimerization. They are of great value for the synthesis of various bifunctional compounds. A reaction that has found wide commercial nse is the hydrodimerization of acrylonitrile to adiponitrile (the dinitrile of adipic acid) ... 

At 130°C or at ambient temperature and in the presence of bases, malonitrile gives rise to a very violent polymerisation. The stability of this dinitrile in the molten state (mp 32°C) decreases with the temperature rise and its fall in purity. It was assumed that decomposition never occurs below 100 C. However, when this compound was heated to 70-80°C for two months, this caused a very violent detonation. 

This chapter reports about an investigation on the catalytic gas-phase armnoxidation of u-hexane aimed at the production of 1,6-Ce dinitriles, precursors for the synthesis of hexamethylenediamine. Catalysts tested were those also active and selective in the ammoxidation of propane to aciylonitrile mtile-type V/Sb and SnA /Nb/Sb mixed oxides. Several A-containing compounds formed however, the selectivity to cyano-containing aliphatic linear Ce compounds was low, due to the relevant contribution of side reactions such as combustion, cracking and formation of heavy compounds. 

Monocyclic compounds with two amino functionalities like 1 were converted to the dinitriles 2 and subsequently reduced to the amines 3. An intramolecular... 

Annelation of cyclic imines with /3-dicarbonyl compounds <2004RCB393>, with cyclic /3-oxodithioesters <20010L229>, or with arylmethylene-/3-dinitriles <2002SC581> provides a one-pot route to quinolizidine systems, as exemplified in Equation 11 for the preparation of the 8-azasteroid 322. 

Some general aspects of linked bis-tacn, bpta and bis-benzimidazole-pyri-dyl ligand and their Fe(II)Fe(II) compounds have been mentioned in Sect. 2.1 and Sect. 2.2 [21, 22, 28]. Only the helical [Fe2L3]4+ bis-benzimid-azole-pyridyl complex shows SCO and it was studied in solution. We are pursuing work on weakly linked compounds, with Toftlund, using a butane-linked dinitrile ligand, and this is mentioned in Sect. 6. 

Iridium hydride complexes effectively catalyze addition of nitriles or 1,3-dicarbonyl compounds (pronucleophiles) to the C=N triple bonds of nitriles to afford enamines.42S,42Sa Highly chemoselective activation of both the a-C-H bonds and the C=N triple bonds of nitriles has been observed (Equation (72)). To activate simple alkane dinitriles, IrHs(P1Pr3)2 has proved to be more effective (Equation (73)). The reaction likely proceeds through oxidative addition of the a-C-H bonds of pronucleophiles to iridium followed by selective insertion of the CN triple bonds to the Ir-C bond. 

Porphyrazines (pz), or tetraazaporphyrins, are compounds that can be viewed as porphyrin variants in which the meso carbon atoms are replaced with nitrogen atoms, as Fig. 1 shows (1). This difference intrinsically gives porphyrazines discrete physiochemical properties from the porphyrins. In addition, despite their similar molecular architecture, porphyrazines are prepared by an entirely different synthetic route than porphyrins—by template cyclization of maleonitrile derivatives, as in Fig. 2, where the open circle with the A in it represents the peripheral substituent of the pz—rather than by the condensation of pyrrole and aldehyde derivatives (1). The pz synthetic route allows for the preparation of macrocycles with chemical and physical properties not readily accessible to porphyrins. In particular, procedures have been developed for the synthesis of porphyrazines with S, N, or O heteroatom peripheral functionalization of the macrocycle core (2-11). It is difficult to impossible to attach the equivalent heteroatoms to the periphery of porphyrins (12). In addition, the preparation and purification of porphyrazines that bear two different kinds of substituents is readily achievable through the directed cocyclization of two different dinitriles, Fig. 3 (4, 5, 13). 

Synthesis. Porphyrazines Mg[pz(A4)], A = S203 crown, 81a, and Mg[pz(A4)], A = S204 crown, 81e, (35%) were prepared by cyclizing the appropriate crown dinitrile 80. Compounds 81a and 81e were demetalated with trifluoroacetic acid and remetalated with either copper or manganese acetate to form compounds 81b-81d and 81f-81h (Scheme 16) (25-27). 

The synthesis of dithienyl photochromes containing a maleic anhydride fragment (a furan-2,5-dione fragment) as the ethene bridge was a difficult problem. Initially, vicinal dinitriles 160 and 162 were used as the starting compounds (Scheme 49). But the latter compounds give a maleic anhydride only in the cis conformations. The separation of the cis and trans isomers is an additional time-consuming laborious problem. 

The yield of initiating radicals is, however, generally smaller than would be expected. In the case of AIBN this is because a certain amount of tetramethylsuc-cinic acid dinitrile is formed by combination of the primary radicals, while some methacrylonitrile and iso-butyronitrile are formed by disproportionation of the primary radicals. Azo compounds are especially suited as initiators for polymerization in bulk or in organic solvents. 

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