Dibenz azepines. synthesis

The only known example of this type of cyclization is the synthesis of dibenz[, /]azepines 457 from appropriate salicylaldehyde 454 and 2,4, 6-trinitrotoluene (455) via the corresponding intermediate 456 (Scheme 72) (62M766). 

Dibenz[6,/]azepine, 10,11-dihydro-N-nitroso-Fischer-Hepp rearrangement, 7, 527 Dibenz[6,/]azepine, 10,11-ethoxyring opening, 7, 526 Dibenz[6,/]azepine, N-nitroso-synthesis, 7, 527... 

H-Dibenz[6,/]azepine-5-carboxamide pharmacological properties, 7, 546 Dibenz[6,e]azepine-6,11-dione, 10-amino-reactions, 7, 526 Dibenz[6,e]azepinediones intramolecular nucleophilic substitution, 7, 516 synthesis, 7, 531 Dibenz[6,e]azepine-5,11-diones epoxides, 7, 515 reduction, 7, 525... 

Dibenz[6, ejazepines conformation, 7, 499 11H-Dibenz[6, ejazepines oxidation, 7, 525 reduction, 7, 517 synthesis, 7, 532, 533 Dibenz[6,/]azepines N-acyl derivatives UV spectra conformation, 7, 499 mass spectrum, 7, 501 nitroxide... 

H-Dibenz[6,eJazepin-6-one, 11-hydroxy-ring contraction, 7, 516 11H-Dibenz[6,ejazepin-1 l-one, 6-phenyl-synthesis, 7, 532 Dibenz[6,/]azepin-2-one synthesis, 7, 525... 

Dibenz[h,e]azepine-6,11-diones ent-Morphinan nomenclature, 1, 29 Morphinan, 1,2,3,4-tetrahydro-nomenclature, 1, 29 14-a-Morphinan, N-methyl-synthesis, 1, 480 Morphinans nomenclature, 1, 29 as pharmaceuticals, 1, 148 synthesis, 2, 377 Morphine, 2, 512 as analgesic, 1, 167 as metabolite of normorphine, 1, 235 as pharmaceutical, 1, 146, 147, 148 synthesis, 1, 480 Morphine alkaloids structure, 4, 534 Morphin-7-en nomenclature, 1, 29 Morphinone, dihydro-as pharmaceutical, 1, 147 Morpholine — see also 1,4-Oxazine, tetrahydrocarcinogenicity, 1, 229 corrosion inhibitor, 1, 409 metabolism, 1, 226 nomenclature, 3, 996 structure, 2, 5 synthesis, 2, 89 Morpholine, 4-aciyloyl-polymers, 1, 291 Morpholine, alkenyl-polymers, 1, 291... 

An elegant procedure for the synthesis of 5//-dibenz[c,e]azepines 14, which is an extension of the procedure outlined at the beginning of this section, has been developed in which the nitrile ylides, generated by the treatment of iV-(2-arylbenzyl)benzimidoyl chlorides 12 with potassium /er/-butoxide, undergo a 1.7-electrocyclization at the adjacent phenyl ring, followed by a hydrogen shift 13 - 14.102... 

An alternative synthesis of 9//-tribenz.[/ >,ia, /]azepine (65, R = H) involves cycloaddition of 10,1 l-dehydro-5i/-dibenz[/t,/]azepine (66), generated from 5-acetyl-10-bromo-5//-dibcnz[/ ,/]azepine, with cyclohexa-1,3-diene.8 The cycloadduct 67, so-formed, with potassium rm-butoxide in refluxing bis(2-methoxyethyl) ether (diglyme) undergoes hydrolysis and loss of ethene to give the tribenzazepine in 39% yield. 

Dibenz[b,/]azepinc-5-carbonitrile (14), an alternative intermediate for the synthesis of Car-bamazepine, is obtained (47%, as the hydrobromide) by stirring 5//-dibenz[b,/]azepine (5) with cyanogen bromide in chloroform solution at room temperature,203 or with cyanogen chloride in dimethylacetamide.204... 

A diastereoselective imine alkylation and a palladium-catalysed biaryl coupling were important steps in the diastereoselective synthesis of 6,7-dihydro-5//-dibenz[c,e]azepines (Scheme 7) starting from (R)-l-(2-methoxyphenyl)ethylamine. Selection for the... 

Desipramine Desipramine, 10,1 l-dihydro-5-[3-(methylamino)propyl]-5H-dibenz[b,f] azepine (7.1.13), differs from imipramine in that it contains only one methyl group on the nitrogen atom of the propylamine side chain. The suggested methods of desipramine synthesis are very simple, and the difference lies only in the manner in which the secondary methylamine group is introduced into the structure of the drug. 

Finally, a third way of synthesis is from imipramine (7.1.1), which nndergoes demethylation by snccessive reaction with ethyl chloroformate, giving 5-[3-(Af-carbethoxy-iV-methyl)aniino-propyl]-10,ll-dihydro-5H-dibenz[b,f azepine (7.1.15), the alkaline hydrolysis of which leads to desipramine (7.1.13) [23,24],... 

Preparative routes to 5/7-dibenz[6,e]azepine-6,11 -diones (morphanthridinediones) are based mainly on the cyclization of 2-aminobenzophenone-2 -carboxylic acids and their derivatives (55LA(594)89). Studies on a-aminodiphenyImethane-2 -carboxylic acid reveal that cyclization to 5,11 -dibenz[6,e ]azepinone (188) is much slower at room temperature than the cyclizations of the analogous 2-aminobiphenyl-2 -carboxylic acid and the 2 -aminobiphenylacetic acid (189), which at room temperature cyclize spontaneously to phenanthridone and dibenz[f>,d]azepin-6-one (190) respectively (61JOC1329). The hydrogen bromide-induced cyclization of dinitriles (Scheme 16) is adaptable to the synthesis of 2-amino-7-bromo-3//-azepines and 5H-dibenz[c,e]azepin-7-ones (67JOC3325). Apparently, for unsymmetrical dinitriles cyclization is such as always to give the azepine with the bromo substituent attached to the carbon of the a,j8-unsaturated nitrile as exemplified in Scheme 16. 

Pschorr cyclization of diazotized A-mesyl-o-aminodiphenylamine yields A-mesyl-5,7-dihydro-6H-dibenz[c,e]azepine (73AJC1307). Diazonium compounds also feature in the preparation of 1 lH-dibenz[6,e]azepines via nitrilium ions (Scheme 21) (72CB1634), and in the only synthesis reported so far of a tribenz[6,rf,/]azepine (10 R=Ph) (72CB880). 

The photolysis of aryl iodides is of use in the preparation of biphenyls, and the application of this reaction to the synthesis of phenanthrenes has already been discussed. Seven- and 8-membered nitrogen-containing heterocycles can also be obtained by an intramolecular arylation of this type photolysis of the iodoamine (345) affords, for example, 6,7-dihydro-5/ -dibenz[c,e]azepine (346).381... 

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