NO group

Fischer-Hepp rearrangement The nitros-amines of aromatic secondary amines when treated with hydrochloric acid give nuclear substituted nitrosoamines. Among the benzene derivatives, if the para position is free the -NO group displaces the hydrogen atom there in naphthalene derivatives it enters the 1-position ... 

For class S-1 weights, two-thirds of the weights in a set must be within one-half of the individual tolerances given below. No group tolerances have been specified for class P weights. See Natl. Bur. Standards Circ. 547, sec. 1 (1954). 

D C Red No. 36 (27) is an unsulfonated pigment. It contains no groups capable of salt formation and is thus insoluble direcdy on coupling. Its chlorine group ortho to the azo group results in a stericaHy hindered molecule with low solubiUty and excellent light stabiUty. The unsulfonated dyes Citms Red No. 2 (8) and D C Red No. 17 (20) are insoluble in water but soluble in aromatic solvents. 

NO2 NR, PIP, 1,4-BR Raney Ni, Zn-AcOH Partial reduction of NO, groups complete hydrogenation of double bonds... 

Figure 11.10 Complexes containing bent NO groups (a) fIr(CO)Cl(NO) PFh3)iJ , and (b) [RuCl NO)2(PFh3)2]. ...

This latter complex also has a linearly coordinated NO group. The diagrams show only the coordination geometry around ihe metal (the phenyl groups being omitted for clarity). 

The [N40(,] cation comprises a central planar nitrate group (N-O 123 pm) surrounded by 3 NO groups at distances which vary from 241 to 278 pm (Fig. 11.20) the interatomic distance in the NO groups is very short (90 99 pm) implying NO and the distances of these to the central NO3 group arc slightly less than the sum of the van der Waals radii for N and O. 

The least squares value for the p constant obtained by this procedure is +6.2 it wiU be obviously subject to change as more meta and epi substituents become available. Only the cata-NO group was excluded from the above plot because it causes a strongly enhanced resonance effect in nucleophilic substitution (Section IV,C, l,a) and an anomalous effect of uncertain origin in the dissociation of carboxylic acids. It can be assumed that the reaction constant for 4-chloro-... 

The reaction seems to proceed via formation of the NO group followed by oxidative cyclization. Compounds 147 and 148 were synthesized from the corresponding hydrazines 149 and 150 and aldehydes. 

Ruthenium probably forms more nitrosyl complexes [115] than any other metal. Many are octahedral Ru(NO)Xs systems, where X5 can represent a combination of neutral and anionic ligands these contain a linear (or very nearly) Ru-NO grouping and are regarded as complexes of ruthenium(II). They are often referred to as (Ru(NO) 6 systems. 

Nitrosourea derivatives are alkylating agents that include a nitroso (R-NO) group and a urea. 

The question as to whether or not hydrazoic add and nitric add are more closely related to the corresponding covalent compounds than to the ions could be answered by determining the configurations of the acids. From general information we would predict that the H-N and H-0 bonds are essentially covalent (with perhaps about one-third ionic character) and that the Ns and NOs groups in the acids have the same structures as in methyl azide and nitrates. This prediction is supported by the instability of the acids. 

Thus the observed orientation in both kinds of HBr addition (Markovnikov electrophilic and anti-Markovnikov free radical) is caused by formation of the secondary intermediate. In the electrophilic case, it forms because it is more stable than the primary in the free-radical case because it is sterically preferred. The stability order of the free-radical intermediates is also usually in the same direction 3°>2°>1° (p. 241), but this factor is apparently less important than the steric factor. Internal alkenes with no groups present to stabilize the radical usually give an approximately 1 1 mixture. 

The chlorine can be disconnected with the alternative polarity via the diazonium salt to amine (19) (guideline 4), The amino group is more powerfully electron-donating than OMe so we can disconnect the NO group. The amino group is itself derived from another nitro group. 

There is no problem of chemoselectivity here it is not possible to reduce the aliphatic NO group in (10) without reducing the aromatic NO group too. This is easily solved by introducing the aromatic nitro group after the reduction. 

The present data give us no indication of what the other pathways of DMN metabolism might be. Other pathways, including denitrosation and reduction of the NO group to the unsymmetrical hydrazine have been reported (27). 

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