Bonding nitrogen

There is the possibility of building up an extensive systematic chemistry of compounds containing boron-nitrogen bonds, analogous to the chemistry of carbon-carbon bonds but the reactivity of the B—bond is much greater than that of the C—C bond, so that we get physical, but not chemical, resemblances between analogous compounds. 

Azide ion ( N=N=N ) Sodium azide IS a reagent used for carbon-nitrogen bond formation The product IS an alkyl azide... 

This IS an unusually high rotational energy barrier for a single bond and indicates that the carbon-nitrogen bond has significant double bond character as the reso nance picture suggests... 

Arylamines Aniline like alkylamines has a pyramidal arrangement of bonds around nitrogen but its pyramid is somewhat shallower One measure of the extent of this flat tenmg is given by the angle between the carbon-nitrogen bond and the bisector of the H—N—H angle... 

Methods for Carbon-Nitrogen Bond Formation Discussed in Earlier Chapters... 

Nucleophilic acyl substitution (Sections 20 4 20 6 and 20 12) Acylation of am monia and amines by an acyl chloride acid anhydride or ester is an excep tionally effective method for the for mation of carbon-nitrogen bonds... 

In Its overall design this procedure is similar to the Gabriel synthesis a nitrogen nude ophile IS used m a carbon-nitrogen bond forming operation and then converted to an ammo group m a subsequent transformation... 

The preparation of amines by the methods described m this section involves the prior synthesis and isolation of some reducible material that has a carbon-nitrogen bond an azide a nitrile a nitro substituted arene or an amide The following section describes a method that combines the two steps of carbon-nitrogen bond formation and reduction into a single operation Like the reduction of amides it offers the possibility of prepar mg primary secondary or tertiary amines by proper choice of starting materials... 

Rotation about the carbon-nitrogen bond is slow in amides The methyl groups of NJ dimethylformamide are nonequivalent because one is cis to oxygen the other cis to hydrogen... 

Gabriel synthesis (Section 22 8) Method for the synthesis of primary alkylamines in which a key step is the formation of a carbon-nitrogen bond by alkylation of the potassium salt of phthalimide... 

Xenon Bonded to Nitrogen. Several ligand groups form compounds containing xenon-nitrogen bonds (12). The first xenon-nitrogen... 

Suitable methods for linking a phosphoms—nitrogen bond to the ayiridine ring are the aminolysis of halogenated phosphoms compounds (2,280—282), the transamination of phosphoramines with excess a iridine (283), the reaction with phosphites (284) and phosphoramidites (285) which have a free OH group, or the reaction of phosphines with a iridines and carbon tetrachloride (286). 

A20 initiators decompose thermally by cleavage of the two carbon—nitrogen bonds, either stepwise or simultaneously, to form two alkyl radicals and a nitrogen molecule ... 

C. G. Overberger, J.-P. Ansehne, andj. G. Lombardino, Organic Compounds with Nitrogen—Nitrogen Bonds, The Ronald Press Co., New York, 1966, Chapt. 4. 

Hydrogenolysis is analogous to hydrolysis and ammonolysis, which involve the cleavage of a bond induced by the action of water and ammonia, respectively. Chemical bonds that are broken by hydrogenolysis reactions include carbon—carbon, carbon—oxygen, carbon—sulfur, and carbon—nitrogen bonds. An example of hydrogenolysis is the hydrodealkylation of toluene to form benzene and methane ... 

In the synthesis of Win 57,273 the attachment of the group, a 2,6-dimethylpytidinyl group, involves formation of a carbon-carbon bond rather than a carbon-nitrogen bond. The method for the attachment of this group is a palladium mediated coupling reaction (77,78) of 4-tributylstarmyl-2,6-dimethylpyridine [122033-61 -8] with a 7-halo quinolone (26). 

Ring openings of pyrrole commonly occur at the carbon—nitrogen bond. Treatment of pyrrole or 2,5-dimethylpyrrole [625-84-3] (23, R = CH3) with hydroxjlamine leads to ring opening and formation of dioximes (31) (39). 

The zirconium—nitrogen bond is weaker than the zirconium—oxygen bond even under anhydrous conditions. When zirconium tetrachloride reacts with carbonyl-containing amides such as... 

Structural parameters and interatomic distances derived from electron diffraction (7) (77JST(42)l2i) and X-ray diffraction (8) studies (76AX(B)3178) provide unequivocal evidence that pyrazine is planar with >2a symmetry. There is an increased localization of electron density in the carbon-nitrogen bonds, with carbon-carbon bonds being similar in length to those in benzene. ... 

Many azo dyes, such as tartrazine (Section 4.04.4.1.3), are susceptible to reduction by bacterial reductases in the intestinal flora. Azo reduction is believed to proceed through a hydrazo intermediate that undergoes subsequent reductive cleavage of the nitrogen-nitrogen bond to yield the arylamine derivatives (B-80MI40406). 

In the modified Raschlg process , used by Bayer A.G. and by Mobay Chem. Co. for large scale production of hydrazine, the intermediacy of an oxaziridine could be clearly evidenced (81MI50800). In this process ammonia and hypochlorite are reacted in the presence of acetone to form ketazine (302). Nitrogen-nitrogen bond formation is faster by a factor of about 1000 in the presence of acetone than in its absence. Thus acetone does not merely trap hydrazine after formation, but participates in the N —N bond forming reaction. Very fast formation of oxaziridine (301), which is isolable, is followed by its likewise fast reaction with ammonia. 

On the other hand, oxidizing fluonnating agents like silver difluoride, xenon difluoride, or bromine trifluoride replace one chlorine group and then cleave the sulfur-nitrogen bond [56],... 

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