Benzaldehyde benzonitrile

Table 10.14 gives the Ea for acetophenones, benzaldehydes, benzonitriles, and benzophenones measured using only the TCT method. The values were scaled to... 

FIGURE 3.7 Comparison of theoretical and experimental adsorption isotherms of benzene derivatives. = Phenol A = Benzaldehyde = Benzonitrile = m. toluic acid, x = m.amino benzoic acid. (After Urano, K., Kochi, Y., and Yamamoto, Y, J. Colloid Interface Set, 86, 43, 1982. With permission.)... 

Benzonitrile is a colourless liquid, having b.p. 190° and d, 1-02 it is almost insoluble in water, and has an odour resembling that of nitrobenzene and of benzaldehyde. 

Physical Properties. Nitrobenzene, C HjNOj pale yellow liquid, insoluble in and heavier than water, characteristic odour of bitter almonds, (similar to that of benzaldehyde and benzonitrile). /> Nitro toluene, C,H4(CH3)N02, usually pale yellow solid, insoluble in water, m-Dinitrobenzene, C8H4(N02)g, colourless solid when pure, but often pale yellow insoluble in water. 

The higjily water-soluble dienophiles 2.4f and2.4g have been synthesised as outlined in Scheme 2.5. Both compounds were prepared from p-(bromomethyl)benzaldehyde (2.8) which was synthesised by reducing p-(bromomethyl)benzonitrile (2.7) with diisobutyl aluminium hydride following a literature procedure2.4f was obtained in two steps by conversion of 2.8 to the corresponding sodium sulfonate (2.9), followed by an aldol reaction with 2-acetylpyridine. In the preparation of 2.4g the sequence of steps had to be reversed Here, the aldol condensation of 2.8 with 2-acetylpyridine was followed by nucleophilic substitution of the bromide of 2.10 by trimethylamine. Attempts to prepare 2.4f from 2.10 by treatment with sodium sulfite failed, due to decomposition of 2.10 under the conditions required for the substitution by sulfite anion. 

Nitration using this reagent was first investigated, by Francis. He showed that benzene and some of its homologues bromobenzene, benzonitrile, benzoyl chloride, benzaldehyde and some related compounds, and phenol were mono-nitrated in solutions of benzoyl nitrate in carbon tetrachloride anilines would not react cleanly and a series of naphthols yielded dinitro compounds. Further work on the orientation of substitution associated this reagent with higher proportions of o-substitution than that brought about by nitric acid this point is discussed below ( 5.3.4). 

Oxathiane 101 is readily deprotonated using s-BuLi, and the resulting anion reacts with alkyl halides, ketones, and benzonitrile (85JOC657). The majority of work in this area, however, is due to Eliel and coworkers and has involved chiral 1,3-oxathianes as asymmetric acyl anion equivalents. In the earliest work it was demonstrated that the oxathianes 102 and 103, obtained in enantiomeri-cally pure form by a sequence involving resolution, could be deprotonated with butyllithium and added to benzaldehyde. The products were formed with poor selectivity at the new stereocenter, however, and oxidation followed by addition... 

Cohn 1 instanced a similar phenomenon in the similarity of the odours of, benzaldehyde, nitro-benzene, benzonitrile, azimidobenzene, and phenyldi-imide. He developed the osmophore theory and introduced the terms kakosmophore and enosmophore to indicate those groups which impart an upleasant and a pleasant odour respectively. The kakosmophore groups are —... 

Benzyl- 112, 240, 346, 355 f., 358, 436, 611 ff., 680 aus Benzaldehyd-O-methyl-oxim und Diboran377 aus Benzonitril und Natriumboranat 115 aus O-Benzoyl-benzhydroxamsaure und Lithium-alanat 264... 

Benzaldehyde, C6H5CHO, Acetophenone, C6H5COCH3, and Benzonitrile, C6H6CN.—The results obtained for these molecules by considering eight [p h orbitals and eight electrons are given in Table III. 

Benzaldehyde, by condensation of phenyllithium with 1,1,3,3-tetra-methylbutyl isonitrile, 51,38 by reduction of benzonitrile with Raney nickel alloy, 51,22 BENZALDEHYDE, 3,4,5-TRIMETH-OXY-, 51,8... 

The comparison of the bands observed after benzonitrile and benzylamine transformation over vanadia-titania allows us to suggest that benzamide can also be obtained by oxidation of benzylamine. Moreover, the growth of the absorption near 1640 cm and the appearance of bands at 1330 and 1240 cm during benzylamine oxidation suggests that benzaldehyde is also formed. A likely assignment for the band at 1670 cm is to the stretching of a C=N double bond (75), so being likely indicative of the formation of benzaldimine. 

Fukuzumi and co-workers described spectroscopic evidence for a ix-rf- ] -peroxo-(Cu )2 species stabilized with a fcidentate nitrogen ligand, but no (catalytic) oxidation behavior towards catechol was noted (a related trinu-clear copper species converted 2,4-di-ferf-butylphenol stoichiometrically towards the biphenol derivative) [224], Stack et al. have described a similar ] -peroxo-(Cu )2 species (28, vide supra) that could be considered a structural and functional model for tyrosinase-activity, as it efficiently reacted with catechol, benzyl alcohol and benzylamine to yield quinone (95%), benzaldehyde (80%) and benzonitrile (70%) [172,173]. This dinuclear per-0X0 species is generated by association of two monomeric copper centers, in contrast to the systems based on dinucleating Ugand scaffolds described above. 

Reactions related to cyclopropanation can also be carried out with (phosphino) (silyl)carbenes (I). For example, benzaldehyde reacts with la at 0 °C leading to the corresponding epoxide, again as only one diastereomer. Even more striking are the reactions with benzonitrile and tert-butylphosphaalkyne that lead initially to azirine and phosphirene. Both three-membered heterocycles subsequently undergo ring expansion reactions affording azaphosphete and diphosphete, respectively (Scheme 8.18). This reaction is a new route for the synthesis of heterocyclobutadienes, and this demontrates the usefulness of (phosphino)(silyl)carbenes (I) for the synthesis of novel species. 

The reactions of chlorobenzene and benzaldehyde with ammonia over metal Y zeolites have been studied by a pulse technique. For aniline formation from the reaction of chlorobenzene and ammonia, the transition metal forms of Y zeolites show good activity, but alkali and alkaline earth metal forms do not. For CuY, the main products are aniline and benzene. The order of catalytic activity of the metal ions isCu> Ni > Zn> Cr> Co > Cd > Mn > Mg, Ca, Na 0. This order has no relation to the order of electrostatic potential or ionic radius, but is closely related to the order of electronegativity or ammine complex formation constant of metal cations. For benzonitrile formation from benzaldehyde and ammonia, every cation form of Y zeolite shows high activity. 

Table II. Yield of Benzonitrile from Benzaldehyde and Ammonia...

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