Amines azido

Azides are useful intermediates for synthesis of various kinds of nitrogen-containing functional groups. They undergo cycloaddition reactions as will be discussed in Section 7.1.5 and can also easily be reduced to primary amines. Azido groups are usually introduced into aliphatic molecules by nucleophilic substitution. 

Nucleophilic ring opening of epoxides by ammonia (Section 16 12) The strained ring of an epoxide is opened on nucleo philic attack by ammonia and amines to give 3 ammo alcohols Azide ion also re acts with epoxides the products are p azido alcohols... 

P-(P -D-aiabinofuianosyl)-9ff-puiin-6-amine] [5536-17 ], an antineoplastic and antiviral compound known by a number of trade names, and AZT (3 -azido-3 -deoxythymidine [30516-87-1]) an antiviral compound also known by a variety of trade names (see Antiviral agents). 

Dichloropyridazine 1-Oxide produces both isomers with alkoxides. However, the ratio is dependent on the size of the alkoxy group. In the reaction with sodium methoxide 80% of 6-chloro-3-methoxypyridazine 1-oxide and 7.5% of 3-chloro-6-methoxypyridazine 1-oxide are formed. Similar results are also obtained with sodium ethoxide, while sodium propoxide affords only 6-chloro-3-propoxypyridazine 1-oxide. Amines react similarly, while only chlorine at the 3-position can be substituted with an azido group to give 3-azido-6-chloropyridazine 1-oxide. 

Iodine azide, on the other hand, forms pure adducts with A -, A - and A -steroids by a mechanism analogous to that proposed for iodine isocyanate additions. Reduction of such adducts can lead to aziridines. However, most reducing agents effect elimination of the elements of iodine azide from the /mwj -diaxial adducts of the A - and A -olefins rather than reduction of the azide function to the iodo amine. Thus, this sequence appears to be of little value for the synthesis of A-, B- or C-ring aziridines. It is worthy to note that based on experience with nonsteroidal systems the application of electrophilic reducing agents such as diborane or lithium aluminum hydride-aluminum chloride may yet prove effective for the desired reduction. Lithium aluminum hydride accomplishes aziridine formation from the A -adducts, Le., 16 -azido-17a-iodoandrostanes (97) in a one-step reaction. The scope of this addition has been considerably enhanced by the recent... 

Hydrazoic acid has been shown to add to dienamines to give a complex mixture of 1 -azido- and 1,3-diazido-amines 135). 

Relatively little work has been done on displacement of the azido group on benzenes ° (by hydroxide, ammonia, amines, or hydrazine) or on heterocycles. The latter involve reaction of... 

Azide ion is a rather weak nitrogen nucleophile, but in aqueous acetone (20°, 5 min) it readily produces 2-azido-4,6-dichloro-s-triazine (330) and also yields more slowly (0°, 12 hr, 90% yield) the 2,4,6-triazido-s-triazine. The latter is rapidly hydrolyzed (50°) to cyanuric acid and is easily mono-aminated (0°, 1 hr, in ether). 

The photolysis of 2 -azido-2,4,4, 6-tetramethylbiphenyl (47) in diethylamine gives 10% of a mixture of A,iY-dicthyl-4-methyl-7-mesityl-3//-azcpin-2-amine (48) and the isomeric 3H-azepine 49, together with the unexpected 4//-azepine SO as the major product." Formation of the 4//-azepine is attributed to severe steric interactions in all conformers of the 3H-tautomers. 

N. A-Diethyl-2.3-dihydro-8//-thieno[2,3-r/]azcpin-7-amine (20), which is obtained in 49 % yield by photolysis of 6-azido-2,3-dihydrothiophene in a mixture of diethylamine and tetrahydro-furan. on treatment with bromine yields the fully unsaturated derivative 21.1,4... 

In contrast to 6-azidobenzo[/)]thiophene, which yields only benzo[i]thiophen-6-amine (9 %) and JVh,Ar(1-diethylbenzo[/)]thiopheiie-6,7-diamine (25 % bp 175-177 C/0.7 Torr), 6-azido-2,3-dibromobcnzojhjthiophene (1 a, R = R2 = Br) on irradiation in diethylamine in the presence of pyrene, a triplet nitrene quenching agent, yields a mixture of 2,3-dibromo-./V6,./V6-diethyl-benzo[5]thiophene-6,7-diamine (2a, R1 = R2 = Br 13%) and the 8W-thieno[2,3-r]azepine 3a.14<1 Likewise, methyl 6-azidobenzo[6]thiophene-2-carboxylate (lb, R1 = C02Me R2 = H) yields the thienoazepine ester 3b.147... 

In contrast, the photolysis of 2,7-diazidonaphthalene (18) furnishes a mixture of 8-azido-2-methoxv-1//-2-benzazepine(l9), 3,8-dimethoxy-l,6-dihydroazepino[3,4-c]azepine(20) and, unexpectedly, the 1 /i-2-benzazepin-8-amine 21 as the major product (40-50%). 

Alkoxypyridoazepines, e.g. 34, behave in a similar manner to yield pyridoazepinamines, e g. 35, which, in many cases, are not obtainable directly by photolysis of the appropriate azido-quinoline or azidoisoquinoline in amine solution108 151 (see Section 3.2.1.4.1.5.). 

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

The synthesis of aromatic amines is an active and important area of research.2 Many methods are available in the literature for the synthesis of these compounds. Though some of these are widely used, still they have limitations based on safety or handling considerations. For example, catalytic hydrogenation3 of nitro or azido compounds in the presence of metals such as palladium on carbon or Raney nickel require stringent precautions because of their flammable nature in the presence of air. In addition, these methods require compressed hydrogen gas and a vacuum pump to create high pressure within the reaction flask. To overcome these difficulties, several new methods have been reported in the... 

Azido- und Diazo-Verbindung prim. Amin, Kohlcnwasserstoff 483, 484... 

Azide werden je nach Bedingungen zu Triazenen, Hydrazinen oder Aminen reduziert. Durch vorsichtige Redukdon mit atherischer Zinn(II)-chlorid-Losung in Salzsaure bei -20° bilden Arylazide Triazene, die jedoch sehr instabil sind undleicht in Amine zerfallen (s. Bd. X/3, S. 814). Aus 1-Azido-naphthalin wird dagegen Naphthyl- l)-hydraz,in (Bd. XI/1, S. 539) erhalten. 

This lactamization process can be promoted by enzymes such as pancreatic porcine lipase. Reduction of co-azido carboxylic acids leads to macrocyclic lactams. Although treatment of carboxylic acids with amines does not directly give amides, the reaction can be made to proceed in good yield at room temperature or... 

Carboxylic acids and esters can also be converted to amines with loss of the carbonyl group by reaction with hydrazoic acid, HN3, which is known as the Schmidt reaction,278 The mechanism is related to that of the Curtius reaction. An azido intermediate is generated by addition of hydrazoic acid to the carbonyl group. The migrating group retains its stereochemical configuration. 

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