5H-Dibenz azepines

As the prototypical amide-containing compound, carbamazepine (5H-dibenz [ >,/]azepine-5-carboxamide) ... 

Scheme 1. The molecular structure of amphiphilic tricyclic antidepressant drug, 5-[3-(dimethylamino)propyl]-10,ll-dihydro-5H-dibenz[, / azepine hydrochloride (imipramine hydrochloride, IMP) used in the present study.

H-Dibenz[6/]azepine, 10,1 l-dihydro-5-niethyl- C NMR, 7, 498 <74JCS(P2)1648) 5H-Dibenz[r c]azepine H NMR, 7, 497 <81LA240) 6H-Dibenz[c,e]azepine, 6-allyl-5,7-dihydro- CNMR, 7, 498 <79JPS890) 5H-Dibenz[6,/]azepine-5-carboxylic acid, 10,11-dihydro-, ethyl ester C NMR, 7, 498 <74JCS(P2)1648)... 

Grignard reagent, 7, 514 5H-Dibenz[6,/]azepine, 3-chloro-10,l 1-dihydro-oxidation, 7, 525... 

H-Dibenz[6,/]azepine, 10,11-dihydro-acylation, 7, 511 alkylation, 7, 511 amination, 7, 512 lithiation, 7, 528 PE spectrum, 7, 502 pharmacological properties, 7, 546 reactions... 

H-Dibenz[c,e]azepine, N-alkyl-6,7-dihydro-oxidation, 7, 511 6H-Dibenz[c,e]azepine, dihydroconformation, 7, 499... 

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... 

The fully unsaturated tricyclic compounds are also used clinically as antidepressants. Carbamazepine (62), for example, is prepared from 10,ll-dihydro-5H-dibenz[b,f]azepine (49) by N-acetylation followed by bromination with W-bromosuccinimide to give 60. Dehydrohalogenation by heating in collidine introduces the double bond. Saponification with potassium hydroxide in ethanol leads to dibenz[b,f]azepine (61), the parent substance for the fully unsaturated analogs. Treatment of the secondary... 

Chamical Nama 6,7-Dihydro-6-(2-propenyl)-5H-dibenz[c,e]-azepine phosphate Common Nama —... 

One gram of 6,7-dihydro-5H-dibenz[c,e] azepine hydrochloride was dissolved in water, made alkaline with concentrated ammonia, and the resultant base extracted twice with benzene. The benzene layers were combined, dried with anhydrous potassium carbonate, and mixed with 0.261 g of allyl bromide at 25°-30°C. The reaction solution became turbid within a few minutes and showed a considerable crystalline deposit after standing 3 A days. The mixture was warmed VA hours on the steam bath in a loosely-stoppered flask, then cooled and filtered. The filtrate was washed twice with water and the benzene layer evaporated at diminished pressure. The liquid residue was dissolved in alcohol, shaken with charcoal and filtered. Addition to the filtrate of 0.3 gram of 85% phosphoric acid in alcohol gave a clear solution which, when seeded and rubbed, yielded 6-allyl-6,7-dihydro-5H-dlbenz[c,e] azepine phosphate, MP about 211°-215°C with decomposition. 

Therapeutic Function Analgesic, Anticonvulsant Chemical Name 5H-dibenz[b,f] azepine-5-carboxamide Common Name 5-carbamyl iminostilbene Structural Formula ... 

Chemical Name 1 -[3-(3-Chloro-10,11-dihydro-5H-dibenz[b,f] azepin-5-yl)propyl] [1,4-bipiperidine] -4-carboxamide... 

A mixture of 5.0 g of 3-chloro-5-(3-chloropropyl)-10,11 -dihydro-5H-dibenz(b,f)azepine, 5.0 g of 4-carbamoyl-4-piperidinopiperidine and 50 mi of dimethylformamide is heated at 100°C for 10 hours. The solvent is distilled off. After the addition of a 2% sodium carbonate solution to the flask, the content is scratched to yield a semisolid, which is dissolved in 50 ml of isopropanol. A solution of 5 g of maleic acid in 50 ml of isopropanol is added, and the precipitate is collected by filtration and recrystallized from isopropanol to give 5.6 g of crystalline 3-chloro-5-[3-(4-carbamoyl-4-piperidino-piperidino)propy I] -10,1 l-dihydro-SH-dibenz-Ib.fjazepine dilhydrogen maleate) with 1/2 molecule of water of crystallization melting at 181°C to 183°C. 

Chemical Name 3-Chloro-10,11 -dihydro-N,N -dimethyl-5H-dibenz [b,f] azepine-5-propan-amine... 

Chemical Name 10,11-dihvdro-N-methyl-5H-dibenz b,fl azepine-5-propanamine hydrochloride... 

Chemical Name 10,11-Dihydro-5-methyl-10(methylamino)-5H-dibenz[b,f] azepine Common Name —... 

Similar problems arise with the four isomeric dibenzazepines 4-7. since only 5//-dibenz-[6,d]azepine (4) and 5//-dibenz[/>,./]azepine (7) can be drawn as fully benzenoid ring structures. Even so, 5//-dibenz[/ ,t/]azepines are rare and are known only as the 7-oxo derivatives.4 In contrast, 5//-dibenz[6,e azepine (5) and 6//-dibenz[r,t>]azepine (6) exist only as the 11//- 5a and 5H- 6a isomers, respectively. In fact, there is no chemical or spectrosopic evidence for the isomerization of 5//-dibenz[e,e]azepine,5 or its 6-oxide,6 to the 6//-dibenz[r, e]azcpinc isomer (6). In addition, an X-ray crystal structure of 7-methoxy-5//-dibenz[e,e]azepine supports unequivocally the benzenoid rather than the quinonoid form.7 9//-Tribenz[6,d /]azepine (8) has only recently been prepared.8... 

Surprisingly, X-ray structural analysis of the dark-green, hygroscopic tetrabutylam-monium salt of 5//-dibenz[6,/]azepine reveals that the potentially antiaromatic 5//-dibenz-azepine anion has a less pronounced nonplanar butterfly structure (161° vs. 144 ) than 5H-dibenz[6,/]azepine.243... 

A detailed study of the dehydrogenation of 10.1 l-dihydro-5//-benz[6,/]azcpinc (47) over metal oxides at 550 C revealed that cobalt(II) oxide, iron(III) oxide and manganese(III) oxide are effective catalysts (yields 30-40%), but formation of 5//-dibenz[7),/]azepinc (48) is accompanied by ring contraction of the dihydro compound to 9-methylacridine and acridine in 3-20 % yield.111 In contrast, tin(IV) oxide, zinc(II) oxide. chromium(III) oxide, cerium(IV) oxide and magnesium oxide arc less-effective catalysts (7-14% yield) but provide pure 5H-dibenz[b,/]azepine. On the basis of these results, optimum conditions (83 88% selectivity 94-98 % yield) for the formation of the dibenzazepine are proposed which employ a K2CO,/ Mn203/Sn02/Mg0 catalyst (1 7 3 10) at 550 C. 

Attempts to prepare 5-vinyl-5F7-dibenz[b,/]azepine by alkylation of 5i/-dibenz[b,/]azepine with 2-chloroethyl-p-toluenesulfonate followed by dehydrochlorination, or by direct vinylation with acetylene under pressure in toluene or in dimethyl sulfoxide, have failed.194 Also, 5H-dibenz[b,/]azepine fails to react with acryloyl chloride, although the 5-acryloyl derivative 8 (R = COCH = CH2 mp 122 — 123 C) has been prepared in 65% yield by condensing dibenz-azepine 5 with 3-chloroacryloyl chloride, followed by dehydrochlorination of the product with l,8-diazabicyclo[5.4.0]undec-7-ene in dimethyl sulfoxide at 80-90°C.194... 

Fig. 3. Fit of InCKfsCT) against 1/T obtained in 1,2-dichloroethane at 5,25 and 50°C for the 5H-dibenz[b,f]azepine-5-carbonyl chloride-Br2 CTC.

Other examples are given by the reaction of rra j-10-bromo-10,ll-dihydro-ll-hydroxy-5H-dibenz[b,f]azepine-5-carbonyl chloride with gaseous HBr in CCI4 to give the expected trans dibromide and the corresponding olefin in an about 3 7 ratio (Table 6) (ref. 20). The same reaction of 10-bromo-10,11-dihydro-11-... 

C15HHCI2NO 92428-58-5) see Clomipramine 3-chloro-10,ll-dihydro-5H-dibenz[i4/]azepine-5-carb-oxylic acid 3-(dimethylamino)propyl ester (C20H23CIN2O2 94758-20-0) see Clomipramine... 

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