I//-Azepine

Reduction of 2/f-dibenz[/i,/]azepin-2-one (55) with aqueous sodium dithionite (Na2S204) yields 5tf-dibenz[6,/]azepin-2-ol (56), which, in the presence of oxygen and a strong base, undergoes retrooxidation to the dibenzazepinone 55.13h... 

Direct conversion of the 5/7-dibenz[i,/ ]azepin-10(l 177)-one 45 to the lO-(alkylsulfanyl) derivatives 46 has been achieved using an alkanethiol and aluminum trichloride.21-1... 

The syn addition of pentafluoroethyl hypofluorite (CF3CF2OF), generated in situ by the action of anhydrous, hydrogen-fluoride-free fluorine gas on sodium trifluoroacetate, to 5-acetyl-5//-dibenz[/i,/]azepine (11) has been reported to yield 12.135... 

The stereospecific trans addition of bromine to 5//-dibcnz[/i,/]azepine has been the subject of intense mechanistic study.230 231... 

Treatment of 2- 5//-dibenz[i>,/]azepin-5-yl acetaldehyde (16), prepared in 68% yield by /V-alkylation of 5/7-dibenz[A,/]azepine with bromoacetaldehyde diethyl acetal followed by acid hydrolysis, with methyl hydroxylamine yields the isolable nitrone 17, which in refluxing toluene undergoes intramolecular 1,3-dipolar cycloaddition at the CIO —Cl 1 alkene bond to give 2,3,3a, 12b-tetrahydro-2-methyl-3,8-methano-8//-dibenz[i>,/]isoxazolo[4,5-r/]azepine (18).235... 

Irradiation of 5-acetyldibenz[i>,/]azepine (19) in the presence of. V-methylmaleimide results in a mixture of the homo dimer 20 and the mixed dimer 21. No [2 + 2] cycloadducts are obtained, however, with other alkenes such as styrene, acetylenedicarboxylic acid, dimethyl fumarate or acrylonitrile.32 Later studies have demonstrated that the dimerization occurs via the excited triplet state.196... 

Isomerization of vinylaziridines is widely used in organic synthesis. Six types of isomerization of vinylaziridines are shown in Scheme 2.40. Outlined in this section are i) azepine formation by aza-[3,3]-Claisen rearrangement of 1,2-divinyl- or 2,3-divinylaziridines 153 (Section 2.4.1), ii) pyrroline formation from 155 (Section 2.4.2), Hi) aza-[2,3]-Wittig rearrangement of anionic species 157 (Section 2.4.3),... 

Dipolar cycloadditions to azepines are confined to diazomethane and diphenyl-nitrilimine. The former reagent, depending on the nature of the substituents on the H-azepine, either adds at the 4,5-bond to yield pyrazolines (160) or traps the benzeneimine tautomer of the azepine as the bis-pyrazoline (Section 5.16.2.4) (76CB3505). A pyrazoline is also the product from the addition of diphenylnitrilimine to 5//-dibenz[i,/]azepine (B-67MI51600). 

Little work has been done with simple pyrimidines. 4,6-Dimethyl- and 2,4,6-trimethylpyrimidine in acetonitrile with DMAD gave low yields of 1 2 molar adducts, originally considered336 to be pyrimido[l,2-[Pg.383]

Diazotization, of 6-amino-2,3-dihydro-1,4-diazepinium salt, 56, 33 Dibenz[c,e][ 1,2]azaborine, 5,6-dihydro-, chlorination, bromination, 59, 309 Dibenz[i/]azepine, and 10,11-dihydro-, lithiation, 56, 273 Dibenziodole( + 1) ions, 56, 338 Dibenzo[fl,c]carbazole, 7-methoxymethyl-, lithiation, 56, 183... 

Scheme 59 Cl-cycloaddition-elimination three-component synthesis of pyrrolo(2,3- )p5 dines 109, 1,8-naphthyridines 110, and pyrido(2,3-i>)azepines 111...

H-Dibenz[i,/]azepine is reduced quantitatively to its 10,11-dihydro derivative by magnesium in methanol (79JOC3972). In contrast, reduction of its iV-acetyl-lO-dibromo derivative to the AT-ethyl compound without reduction of the C-10—C-11 double bond or loss of... 

Synonym 5/-/-Dibenz[ i, azepine-5-carboxamide Source Yamini, Y. Hassan, J. Haghgo, S. 

Synonym 5-[3-(Dimethylamino)propyl]-10,11 -dihydro-5H-dibenz[ i, azepine Hydrochloride... 

Condensation of 57 with homoveratraldehyde (60) in the presence of molecular sieves, followed by sodium borohydride reduction, affords the chromium tricarbonyl complex 61 in moderate overall yield. The acid-promoted cyclization of 61 proceeds with retention of configuration to afford, after air decomplexation, optically pure (/ )-( + )- -phenyl- 3-methyl-l,2,4,5-tetrahydrobenz[d]azepine (62) (Scheme 12) [14]. The l,2,4,5-tetrahydro-3//-benz-[benzazepine alkaloids . Moreover, the dopaminergic activity possessed by this class of compounds resides mostly in the (i )-enantiomer [15,16]. 

The first indeno[l,2- i]azepine (7), shown by n.m.r. to have a fully conjugated 147T-system, has been synthesized via the successive bromination-dehydro-bromination of (8)." The same group has developed two routes to (9), as a possible precursor for the same system via dehydrogenation. ... 

I- 2]7t Cycloaddition reactions too have found a place in azepine synthesis. In studies related to the enantiomeric synthesis of norsecurine <9UA5384>, intramolecular cycloaddition of the alkyne group in (168) to the oxazole ring, followed by loss of acetonitrile from the adduct, furnishes the tricyclic azepine (169), as shown in Equation (16), and 2,3,4,5-tetrahydro-7,8-bis(trifluoromethyl)-l/7-pyrido[2,3-i]azepine (171) is obtained by intramolecular [4 + 2]n cycloaddition of (170) followed by elimination of nitrogen <90CBi33>. 

Oxcarbazepine [28721-07-5], anticonvulsant, 176. The penultimate urea derivative 175 is prepared by phosgenation of 10-methoxy-5H-dibenzo[i),/]azepine 174 and subsequent treatment with ammonia [131-133]. 

Chemical Name 5H-Dibenz[/i, azepine-5-carbo-xamide... 

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