2-amino derivatives, reaction with secondary amines

This reaction has been used as the key step in an original synthesis of formycln (80CJC2624). By a similar mechanism, via a 3H-lndazole, the 2,5-dlnitro derivative reacts with secondary amines to afford 3-amino-5-nltrolndazoles (80MI40404, 81JOC2706, 82PNA4487). 

Amino derivatives are obtained by standard reactions with secondary amines, lithium amides or... 

The trans-phenanthrene-9,10-amino alcohols (261) are formed from 1 and its derivatives by reaction with secondary amines.154... 

On treatment with ammonia or primary amines, 6-substituted 2-chloromethyl-4-phenylquin-azoline 3-oxides 1 undergo rearrangement to 2-amino derivatives of 7-substituted 5-phenyl-3//-1,4-benzodiazepine 4-oxide 2, Reaction with secondary amines proceeds without rearrangement with formation of the expected 2-(aminomethyl)-4-phenylquinazoline 3-oxides (cf. Section 6.3.1.1.10.3.). 2o. s2i... 

Fluorescamine under the alkaline conditions rapidly reacts with primary amines and amino acids to give fluorescent derivatives at room temperature. The advantageous features of this reaction are as follows (1) fluorescamine is nonfluorescent (2) fluorescamine can be hydrolyzed to the nonfluorescent product (3) the reaction with secondary amines can form nonfluorescent derivatives, which allows selectivity to primary amines. For those reasons, fluorescamine can be applied to pre- and postcolumn derivatization of primary amino compounds with LC-FL or CZE-LIF detection. 

The reaction of both bromomethyl derivative 64a and a-bromoethyl derivative 64b with secondary amines leads to nucleophilic substitution products that form aldehyde and ketone 71a,b when allowed to remain in solution. This occurs via the intramolecular oxidation of the amino group by the nitrone-group oxygen. Aldehyde and ketone 71a,b are also formed in the acid hydrolysis of imines 68a,b (Grigor ev and Volodarsky, 1975). 

The reaction of pyrazino[2,3-r-][l,2,6]thiadiazine-2,2-dioxides 61 with secondary amines proceeds very readily and allows access to, for example, the 4-pyrrolidinyl derivative 62 as shown in Equation (10). A similar reaction with primary amines allowed access to a range of 4-amino-pyrazino[2,3-r-][l,2,6]thiadiazine-2,2-dioxides 63, as shown in Equation (11) <2000JME4219>. 

Phthaloylisothiosemicarbazide was refluxed in AcOH with secondary amines to yield 59-95% of substituted 6-amino-4-ethylthiobenzo[/][l,2,4]triazocin-l(2//)-ones 169. Corresponding acetyl derivatives were produced if reaction was performed in acetic anhydride (Equation 34, <1994APH77>). 

The nucleophilic capture of the trichlorocyclopropenium ion is not restricted to aromatics. In fact treatment of tetrachlorocyclopropene with secondary amines and thiols results in tris-amino- and thio- cyclopropenium ions, e.g. 76. One advantage of such species is in their reaction with nucleophiles, e.g. HO", which deliver the corresponding sp -hybridized derivative, e.g. enone 77, by an addition-elimination sequence The transammination reaction, initially performed in good-to-excellent yields with secondary amines, often employs a trimethylsilylamine which has allowed for the synthesis of the tris-(mono-organylamino)cyclopropenium salt (76a) in almost quantitative yield. 

Aminoiysis reactions of l,3,5,7,2X ,4X ,6X. ,8kMetraazatetraphosphocine (octachlorocyclotetraphosphazene) (N4P4Clg) with primary amines, as well as the reactions of bis(primary amino) hexachloro derivatives, N4P4Cl6(NHR)2, with secondary amines proceed in three distinct pathways (a) a stepwise replacement of chlorine atoms to yield partially and fully substituted cyclotetraphosphazenes(tetraazatetraphosphocines), (b) inter-... 

Little is known of simple 2- and 3-amino derivatives 2-diaUcylamino-benzothiophenes can be obtained by reaction of benzothiophene-2-thiol with secondary amines.In many ways 2-aminobenzothiophene behaves like a normal aromatic amine, but diazotisation leads directly to benzothiophen-2-one. ... 

Formamidine acetate was prepared in similar high yield by a similar procedure but with glacial acetic acid as solvent.804 A A-Disubstituted formamidine and acetamidine derivatives have been obtained analogously from orthoesters and alkylamines in the presence of glacial acetic acid805 or boron trifluoride etherate 806 In the reaction of orthoesters with secondary amines in the presence of toluenesulfonic acid the formation of ketene aminals (alkyl l -amino-vinyl ethers) was also observed.807... 

Pfizer chemists reacted 5-acetyl-2-aminooxazole 862 with a primary or secondary amine and isolated mixtures of l(/f)-5-acetyl-2-aminoimidazoles 863 and 2-amino-4-methyl-5-pyrimidinols 864 (Scheme 1.232). The reaction was independent of the amine substituent, since both primary and secondary amines yield 863 as the major product. The ratio of 863 864 was ca. 3 1 with primary amines but nearly 1 1 with secondary amines. It is noteworthy that water was requisite for this reaction sequence. Otherwise, the product is the Schiff base derived from 862. 

In a similar manner 8-oxo-8//-acenaphtho[l,2-b]pyrrole-9-carbonitrile reacts with primary alkylamines under rather mild conditions to give the corresponding 3-aIkylammo derivatives in 40-45% yields (Scheme 19) [71,72]. The reaction with secondary cyclic amines is less selective and, in addition to 3-amino derivatives, 6-substituted and 3,6-disubstituted products are also formed. Both monoamines can... 

Various V-substituted 6-amino-6-deoxy-D-glucose derivatives, e.g. 6-8, were synthesized by reaction of the corresponding 5,6-anhydro-D-glucose derivative with secondary amines, and shown to be useful as non-ionic surfactants capable of forming reverse micelles for solubilization of amino acids in hexane. Reaction of such tertiary amines with methyl iodide provided quaternary ammonium-sugar derivatives. The 6-amino-2,5-anhydro-6-deoxy-D-gluconate derivative 10, a potential dipeptide isostere, was obtained from the C2-symmetric, D-mannitol derived bis-epoxide 9 following silica-assisted azidolysis (Scheme 3). Its enantiomer was obtained similarly from an L-iditol bis-epoxide. ... 

Sugars also react readily, under mild conditions, with compounds containing the primary amino group, such as amino acids and with a wide variety of amines. With secondary amines the reaction is less facile, but similar products are derived. A typical reaction is between a hexose and... 

The reactions of 3-chloro-l,2-dithiolium salts (23) feature in a number of papers. With secondary amines, the products are 3-amino-l,2-dithiolium salts (24), which undergo an interesting reaction with the carbanion of nitromethane to give thiophen derivatives (25). Aromatic amines, phenols, and phenol ethers are substituted at thepam-position by 3-chloro-5-phenyl-l,2-dithiolium cations. The product obtained with phenol can be deprotonated to the quinonoid compound (26), and 3-arylamino-l, 2-dithiolium salts (27 = aryl or PhCHg)... 

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