2,3-Benzodiazocin-1 -ones

Benzodiazocines 429 were prepared to be tested as calcium-sensitizing agents (equation 181). A mixture of isomeric lactams was obtained when the Schmidt rearrangement was applied to 427, but only one product 428 was produced using the Beckmann reaction. 

Fusion of the acylamino precursors 64 resulted in the intramolecular amidation with the C=N bond formation, affording the new ring system, ll/7-pyrazolo[3,4-2][l,6]benzodiazocin-ll-ones 65, (Equation 9) <2004ARK44>. 

The coupling reactions of 2-carboxyl benzophenones with ethylenediamine resulted in 2,5-benzodiazocin-l-ones 26 (Equation 11) (see Section 14.06.3) <2003JOC92>. 

Benzodiazocine 264 was prepared through a 4-component Ugi reaction including a primary amine tethered to a BOC-protected internal amino nucleophile, followed by a postcondensation base-catalyzed cyclization. Thus, 2 equiv of aldehyde 262 were employed to promote Schiff base formation and a one-pot, double scavenging protocol with immobilized tosylhydrazine and di-isopropylethylamine removed both the excess aldehyde and any unreacted acid 261. The intermediate 263 was then subjected to treatment with TFA, followed by proton scavenging with resin bound morpholine, to promote cyclization to afford the eight-membered ring (Scheme 47) <2001TL4963>. 

There is only one publication reporting the synthesis of this system. Reaction of 3,4,5,6-tetrahydro-l,3-benzodiazocine-2-thione (216) with... 

Cyanoaminoamides 44, when treated with potassium /m-butoxide, afforded l,5-diazacyclooctan-2-ones 45 (85HCA750). Milkowski and coworkers, in a series of papers, cyclized a number of 2-substituted N- aryl-A/ -aroyl-l, 3-propandiamines with phosphorus oxychloride to obtain the 1,5-benzodiazocines 46, along with the pharmacologically more useful... 

A few radical annulation approaches to fused indoles have been reported. 2-Indolylacyl radicals generated from selenoesters provided ellipticine quinones <05JOC9077>. A radical cyclization of haloacetamide derivatives was applied to the preparation of indolo[2,l-rf][l,5]benzodiazocines <05T941> and indolo[3,2-d][l]benzazepin-6-ones <05T5489>. 3,3-... 

In addition, a versatile route to benzodiazocine and spiropyran derivatives via chalcones was reported (13JCS517). The synthesis of spiro[o-thiophene-5, 6 -diphenyl-2H-pyran-4, 3 ] -5-methylbenzo [b] thio-phene-2-one from thioisatins is shown below. The broad scope of usable substrates of industrial relevance is discussed. 

C22H1 iiNg, 2,3-Bisbenzimidazol-2-yl-quinoxaline, 46B, 263 C22H16N2O, 2,4-Diphenyl-2,3-benzodiazocin-1(2H)-one, 42B, 211 C22H1sBrNOa, E,E-1-Acetyl-3-(1 -p-bromophenyl)-3 -ethoxycarbonyl-allylidene)-2-0X0-indoline, 45B, 283 C22H19N3O5, 4-Ethoxycarbonyl-5-hydroxy-1-phenyl-3-(a-phthalimidoeth-yDpyrazole, 46B, 263... 

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