Nitrogen derivatives

Nitrogen derivatives A remarkable series of transformations has been discovered with fluorinated pyridazines, giving pyrimidines and small amounts of pyrazines on pyrolysis [262, 263] and pyrazines on photolysis [264]. Highly specific substituent labelling occurs on pyrolysis and diazabenzvalenes, or vibrationally excited species approaching these, 

Moilliet in Organofluorine Chemistry Principles and Commercial Applications, ed. R.E. Banks, B. E. Smart and J.C. Tatlow, Plenum Press, New York, 1994, p. 195. 

Bordon in Houben-Weyl Methods of Organic Chemistry, Vol. ElOa, Organo-fluorine Compounds, ed. B. Baasner, H. Hegemarm and J.C. Tatlow, Georg Thieme, Stuttgart, 1999, p. 655. 

Hutchinson and G. Sandford in Organofluorine Chemistry Techniques and Synthons, ed. R.D. Chambers, Springer Verlag, Berlin, 1997, p. 1. 

Interactions of Bivalent Germanium and Tin Compounds, with Transition -metal Derivatives. Several investigators have studied the ligand qualities of 

The first primary plumbylamine BuSPbNH2 has been prepared from the iodide using KNHa in liquid ammonia, and melts at - 2 An X-ray structure determination of bis(trimethylsilyl)dithio-oxamide shows it to occur as the AW -isomer. While the fornoamide occurs as the ATV-isomer, bis(trimethylsilyl)acetamide adopts the AO-substituted acetimidate structure, though chemically both behave similarly, giving A-acylamides with acyl chlorides. A series of A-alkyl and A-aryl-t-butyldimethylsilyl amides have been prepared by amination, and while the A-alkyl derivatives have been shown to occur as amides, the A-aryl derivatives exist as amide-imidate mixtures.  

The amide prepared by the trans-silylation of BSA with ClCH2SiMe2Cl has been shown not to be a AA-bis-silyl acetamide but to possess the intramolecularly co-ordinated five-membered heterocycle (59) derived from AA-bis(chloro-dimethylsilylmethyl) acetamide, with no Si—N bonds. The series of amides R CONR CCHaSiMegCl) were prepared similarly, and likewise are thought to involve intramolecular 0- Si co-ordination.  

Silyl substituted hydroxylamine can be readily desilylated with acid chlorides, the hydroxamic acid fragmenting to isocyanate on heating. C-Silylimines thermally rearrange to A-silylenamines through what is thought to be a carbene intermediate.  

In non-polar solvents, the cyclodiazastannylene (60) occurs as dimers for R=Pr, through N - Sn co-ordination, but as monomers for R=Bu. However, if the t-butyl derivative is cooled below 0 °C, then two crystalline modifications result. The triclinic phase occurs as dimeric units only, but the monoclinic one comprises a mixture of dimeric and monomeric units in equal proportions. 

The major product of photolysis of McaSiNs at lOK has been shown to be either Me2SiHN=CHa or MeaSiHCH=NH. There is no evidence to support the presence of a silicon-nitrogen double bonded intermediate, in contrast to recent photolytic and thermal degradations of silylazides in the gas and condensed phases.  

6-Tetra-O -acetyl-B-D-gluco- and -galacto-pyranosylamines (1) have been obtained from the corresponding glycosyl azides (2) by Staudinger reaction followed by hydrolysis of the intermediate phosphinimines (3) alternative reactions of intermediates (3) with carbon dioxide yielded the 1,2-trans-carbamates ( ) 

Reaction of -(tetra- -benzyl-a-D-glucopyranosyl)trichloro-acetlmidate with -chlorobenzolc acid in acetonitrile gave, in 

D-gluco-(4) have been obtained on treatment of 3-glycosyl-l-methyl- 

The N-glycosldes (17) have been obtained from the reaction of 

Glc] with phenyl isocyanlde dlchloride (PhN=CCl2)and an N-glucosylated xanthine derivative has been obtained by cyclization 

3- (N-glycosylamino)-2-nitroacrylates. Mass spectral studies of acylated glycosylamlnes are covered in Chapter 22. 

Pyridinium aldoximes N-llnked to C-1 or C-6 of hexoses or to a 3-carbon aglycone unit of a glycoside have been synthesized as potential antidotes of organophosphate poisoning thus the N - 

Reaction of D-xylose with tetracyanoethylene and ethanol in liquid hydrogen fluoride gave the bicyclic glycosylamlne derivative 

Several studies on the Maillard reaction have been reported, some being covered in Chapter 9 section 3 Glycoaldehyde and 

1-alkyl-3-oxypyridlnium betaines, which arise from the reaction of 

Iminium salts [Cl2C=CH-CH=NR2] and R(H)C=NR2 can be conveniently prepared fiom 

Agl mediates in the amination of allylic and benzylic chlorides with (Me3Si)2NLi, while 

N-silylated a-acetylenic amides, esters and ketones undergo Cu assisted electrophilic 

Using Mc3SiCl and Li under N2 with TiCl4 provides a route to incorporate N into heterocycles, phthallic anhydride giving phthalimide in 204% yield based on Ti. though 

Coupling the disilane (MesCl2Si)2 with MesNHU gives both the azadisilcyclopropane and cyclodisilazane, the former showing endocyclic Si-N distance of 174.8 pm, while cyclodisilazanes result from bisaminosilanes with dichlorosilanes or from l-amino-3-flu(MO- 

Aminosilanes have been used to silylate the surface of hydrated silica, to transaminate DMF, to give the silyl enol ethers of 

Me SxNHCOCHj couple electrophiles without N to C rearrangement. Alkyl(trialkylsilyl)aminyl radicals are iC-radicals, the R Si +I/-M substituent effects being insufficient to switch from a X- to a 

forme complexes with mono- bis- and trie(amino)silanes, 

Bu gSiN NNHSiBu g shows coalescence of proton n.m.r. signals at 55°C, supporting a 1,3-proton migration, and decomposes at 150°C to (Bu 3Si)2NH and N2-  

Aryl nitrites result in good yield from ArCHO and Me SiN, which 

The silaamidide [Ar N-Si(R)-NAr ] [MOEt2l (M=Li JC) occurs as a 4-membaed cyclic ion pair with the structure of the 12-crown-4 derivative showing Si-N ixmds of 159.4 and 162.6 pm and Si planar, and the iminosilane t Bu2(T[IF)Si=NSiMeBu-t2 results from the flutwosilylamide through LiF loss while t-Bu2Si=NBu t adds to aldehydes and ketones. Aminosilanes and disilazanes 

The disilazanes (Me3Si)2NH and (Me2SiH)2NH result from Me3SiNCO or Me2Si(H)Cl and liquid NH3 at a range of silylaminosilanes and chlorodisilazanes prepared,  

PhC(NHSiMe3)2 PhC(NSiMc3)2TlCl3 with TIQ3, while the Sn derivative adds HCl  

Silylated azadienes form complexes with Zr, Nb, and Ga, while with bisaminosilanes, GaG3 yields the ionic complex cyclosilazanes from 

Silylated phosphinimines undergo disproportimiation on transsilylation, silyl intermadiates used to make 4-membered P2 2 silylaminophosphines electrochemically reduced to P=P 

Warming Bu Si Cl )N( Li) SiBu., gives the first stable sila ketimine t t 

Bu 2Si=NSiBu 2 which adds to MeOCH=CH2 giving the [2+2] cycloadduct, to N 0 giving the unstable (2+3] cycloadduct which decomposed to Bu jSiN adds H2 Heating C-phenyl-2-Me2Si-tetrazole gives the 

1- M62BU Si-pyrrole undergoes Friedel-Crafts acylation p , giving 3-pyrroloketones on NaF assisted hydrolysis. Surface-hydrated Si02 

Both (MeSiH2)2NMe and (Me2SiH)2NMe are planar while calculations indicate stabilisation of the lone pair of electrons probably occurs 

Disilazanes condense with RCHO and 1 2 o give Schiff bases in the presence of Me Si triflate, and with ROCSCl to give thiourethanes ROC(S)NR (SiMe ) and bis(thionocarboxylic acid esters) R N(C(S)0P)2. (Me2Si)2f H silylates thiourea, the product decomposing to (Me,SiN)Whereas (Me,Si) NNa and RX (X=Br,I,p-MeC,H,SO ) 

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The field of application for liquid chromatography in the petroleum world is vast separation of diesel fuel by chemical families, separation of distillation residues (see Tables 3.4 and 3.5), separation of polynuclear aromatics, and separation of certain basic nitrogen derivatives. Some examples are given later in this section. 

Triazines. Triazine herbicides are one of several herbicide groups that are heterocycHc nitrogen derivatives. Triazine herbicides include the chloro-, methylthio-, and methoxytriazines. They are used for the selective pre-emergence control and early post-emergence control of seedling grass and broadleaved weeds in cropland (299). In addition, some of the triazines, particularly atrazine, prometon [1610-18-0] and simazine [122-34-9] are used for the nonselective control of vegetation in noncropland (2). Simazine may be used for selective control of aquatic weeds (2). 

Other Heterocyclic Nitrogen Derivative Herbicides. The herbicides in this group are heterocycHc nitrogen derivatives that do not readily fall into one of the previously discussed groups. They have a wide range of uses and properties. Most of these herbicides are used for selective, pre-and/or post-emergence weed control. Amitrole is used for post-emergence, nonselective weed control in non-croplands and also as an aquatic herbicide (2,296). 

Fatty amines are nitrogen derivatives of fatty acids, olefins, or alcohols prepared from natural sources, fats and oils, or petrochemical raw materials. Commercially available fatty amines consist of either a mixture of carbon chains or a specific chain length from C The amines are classified as... 

Patty amines and chemical products derived from the amines are used in many industries. Uses for the nitrogen derivatives may be broken down as follows as a percentage of total market fabric softeners (46%), oil field chemicals (15%), asphalt emulsifiers (10%), petroleum additives (10%), mining (4%), and others (15%) (8). 

S. H. Shapiro, "Commercial Nitrogen Derivatives of Fatty Acids," in E. Pattison, ed., Patty A.cids and Their Industrial Applications, Marcel Dekker, Inc., New York, 1968, pp. 77—154. 

Fine andFunctional Chemicals, Nitrogen Derivatives, General Catalog Bulletin 89—74, Ak2o Chemicals, Inc., Chicago, lU., 1989. 

Apart from a short section in an early book on phthalazines (53HC(5)198), the only previous general account of significance occurs in a chapter in a now dated volume on fused pyridazines, which covers work up to 1969 (73HC(27)968), and which also includes bridgehead nitrogen derivatives not relevant to this review. A later review (75MI21504) does exist but is in Japanese. 

Mcntasty el al. [35] and others [13, 36] have measured methane uptakes on zeolites. These materials, such as the 4A, 5A and 13X zeolites, have methane uptakes which are lower than would be predicted using the above relationship. This suggests that either the zeolite cavity is more attractive to 77 K nitrogen than a carbon pore, or methane at 298 K, 3.4 MPa, is attracted more to a carbon pore than a zeolite. The latter proposition is supported by the modeling of Cracknel et al. [37, 38], who show that methane densities in silica cavities will be lower than for the equivalent size parallel slit shaped pore of their model carbon. Results reported by Ventura [39] for silica xerogels lead to a similar conclusion. Thus, porous silica adsorbents with equivalent nitrogen derived micropore volumes to carbons adsorb and deliver less methane. For delivery of 150 V./V a silica based adsorbent would requne a micropore volume in excess of 0.70 ml per ml of packed vessel volume. 

The subscripts c, r,f, d, and i denote chain, ring, formation, decomposition, and isomerization, respectively. and F, are the amoimts of nitrogen derived from the arenediazoazide and arylpentazole, respectively. 

Akzo. Industrial Surfactants, Nitrogen Derivatives. Technical literature and catalog. Akzo-Nobel, Inc., USA. 1992. 

Linfield, Jungermann, and Guttmann [181,183,184] extended this reaction to a number of long-chain fatty nitrogen derivatives to form products with surface-active and antibacterial properties, as shown in Eqs. (109) and (110) ... 

The numerous reactions between nitrogenous derivatives with different states of oxidation are represented in the table (pi 68), which is more difficult to read than the usual summary tables in which there are less troublesome crossings between lines and groups. 

Plants synthesize all the amino acids they require. They do so using as raw material carbohydrates, which they make during photosynthesis, and nitrogen, derived from nitrate ions absorbed from the soil. Animals cannot synthesize all the amino acids required for their regular living, health, and growth. Those they cannot synthesize, known as the essential amino acids, are acquired from plants and/or animals they consume as food. Human beings, for example, acquire nine essential amino acids from their diet. 

Leute R., Bolz G. Nitrogen derivates of benzoyl ecgonine. U.S. patent 3888 866, 1975. 

Nitro compounds are versatile precursors for diverse functionalities. Their conversion into carbonyl compounds by the Nef reaction and into amines by reduction are the most widely used processes in organic synthesis using nitro compounds. In addition, dehydration of primary nitro compounds leads to nitrile oxides, a class of reactive 1,3-dipolar reagents. Nitro compounds are also good precursors for various nitrogen derivatives such as nitriles, oximes, hydroxylamines, and imines. These transformations of nitro compounds are well established and are used routinely in organic synthesis. 

Ladd JN, Amato M, Parsons JW (1977) Studies of nitrogen immobilization and mineralization in calcareous soils. 111. Concentration and distribution of nitrogen derived from soil biomass. In Soil organic matter studies, vol 1. International Atomic Energy Agency, Vienna, pp 301-311... 

Although relatively few compounds contain only carbon and nitrogen, derivatives such as the cyanides have commercially important uses. Also, calcium cyanamide, CaCN2, can be prepared by the reaction... 

In addition to the foregoing examples, periodate oxidation has been applied to isotopically labeled sugars (for the determination of label distribution), 226 -226 to certain branched-chain sugars,227-229 and to some nitrogenous derivatives of the simple sugars.230-236... 

Furazan- and furoxan-carboxylic acids are unstable compounds (see CHEC-II(1996) Section 4.05.7.1.3), but their ester and nitrogen derivatives are readily accessible and can be used for subsequent transformations. Thus,... 

Prolinol-Type Chiral Auxiliaries. In this section, applications of chelation-enforced chirality transfers with nitrogen derivatives are discussed... 

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