Theoretical reaction indices for dibenz[a,h]acridine

Huckel molecular orbital calculations and application of Seybold-Smith reactivity theory suggest that the Bay-Region diol epoxide derived from the 8,9,10,11-benzo ring of dibenz[a,h]acridine ( 1 ) is the same in reactivity as that of the 1,2,3,4-ring in agreement with experimental findings. The calculations dispute an earlier claim of regioselective reactivity at the 8,9,10,11-benzo ring.     

Synthesis of Alkyl and Aryl Substituted Benzo[h]Naphtho[1,2-b][1,6]naphthyridines

The reaction of 4-chloro-2-methylquinolines and 1-naphthylamine under neat conditions yielded 2-methyl-N-(1-naphthyl)quinolin-4-amines. These potential intermediates on reaction with aliphatic and aromatic carboxylic acids yielded the respective 7-alkyl and -aryl substituted benzo[h]naphtho[1,2-b][1,6]naphthyridines. The highly deshielded protons in the final compounds were assigned on the basis of 2D NMR studies.     

Synthesis of 5,12-diazadibenz[a,h]anthracene

5, 12-Diazadibenz[a,h]anthracene ( 20 ) was synthesized in 21% overall yield for seven steps. Salient features of the synthesis include the initial, one-step conversion of trans, trans-1,4-bis-(β-nitrovinyl)benzene into 2,2″-dinitro-p-terphenyl by Diels-Alder condensation plus elimination, monocyclization of the derived 2,2″-diformylamino-p-terphenyl to give 8-(2-amino-1-phenyl)-phenanthridine ( 10 ) in the presence of fortified polyphosphoric acid, and accomplishment of a second cyclization step only after reduction of the heteroring in 10 (by means of diisobutyl-aluminum hydride) plus formylation. The 6-methyl and 6,13-dimethyl derivatives of 20 were prepared similarly.     

Mono-, and dibenzacridine imines. Synthesis of 1a,11b- dihydrobenz[c]azirino[α]acridine, 4b,5a-dihydrodibenz[c,h]- azirino[α]acridine and 1a,13b-dihydrodibenz[c,j]azirino[α]acridine

The syntheses of the K-imine derivatives of benz[c]acridine, dibenz[c,h]acridine and dibenz[a,h]acridine are described. The parent hydrocarbons 1, 6 and 11 were oxidized with sodium hypochlorite under phase transfer conditions to the corresponding K-oxides 4,9 and 14 , which in turn were reacted with sodium azide. The resulting azido alcohols were then cyclized with tributylphosphine to the title compounds 5,10 and 15.     

Synthesis of 5,6,7-trimethylbenz[c]acridine

A new potential carcinogenic aromatic heterocyclic compound, 5,6,7-trimethylbenz[c]acridine ( 1 ), has been synthesized from the known 5,5-dimethyl-6-keto-5,6-dihydrobenz[c]acridine ( 4 ) using a series of reactions which includes an interesting new type of 1,4-conjugate addition cmploying lithium dimethylcopper.     

Behavior of 5,6-dihydrobenzo[h]cinnolinones towards hydrazine. Synthesis of benzo[h]cinnolinones and of 4-Aminobenzo[h]cinnolinones

Dehydrogenation and amination of 4,4a,5,6-tetrahydro and 5,6-dihydrobenzocinnolinones in refluxing hydrazine hydrate to give new benzo[h]cinnolinones and 4-aminobenzo[h]cinnolinones are reported, and reaction mechanisms proposed. Experiments were also extended to 4,4a-dihydro-5H-indenopyridazinone which underwent hydrazine induced dehydrogenation to 5H-indenopyridazin-3-one but not subsequent amination.     

Synthesis of bisimines of pyrene and dibenz[a,h]anthracene

The preparation of 3b,4a,7b,8a-tetrahydro-4H,8H-pyreno[4,5-b:9,10-b']bisazirine and of 1a,6b,7a,12b-tetrahydro-1H,7H-dibenz[3,4:7,8]anthra[1,2-b:5,6-b']bisazirine is described. The corresponding diepoxides were reacted with sodium azide in aqueous acetone and the mixtures of trans-azido alcohols, so formed, were cyclized by tri-n-butylphosphine.     

Synthesis of 9,10,12,13,14,14a-hexahydrodibenzo[f,h]pyrrolo-[2,1-a]isoquinoline

The synthesis of 9,10,12,13,14,14a-hexahydrodibenzo[f,h]pyrrolo[2,1-a]isoquinoline 6 has been accomplished by a sequence involving as a key step the Friedel-Crafts intramolecular acylation of the amino acid 9 to the corresponding pentacyclic aminoketone 10 . Compounds 7, 11 and 12 showed a significant protein synthesis inhibitory effect.     

Heterocycles. IX. Synthesis of new substituted benzo[h]quinolones

2-Arylidine-1-tetralones I were condensed with phenyl-, p-chlorophenyl-, and p-methoxyphenylacetamides A in the presence of a base to yield the corresponding benzo[h]quinolones II-IV. Dehydrogenation of compounds II gave the benzoquinolones V which upon acetylation yielded the corresponding 2-acetyl derivatives VI. The structure of all products was substantiated by chemical and spectral methods.     

Synthesis of 8,9-dialkoxy-substituted tetrahydrobenz[h] isoquinolines

6,7-Dimethoxy-2-naphthylethylamine, prepared by the diborane reduction of 6,7-dimethoxy-2-naphtlialeneacetamide, underwent a Pictet-Spengler cyclization to form 8,9-dimethoxy-1,2,3,4-tetrahydrobenz[h]isoquinoline. This compound is identical with that obtained by reduction of the corresponding dihydrobenzisoquinoline prepared from formamide cyclization. 6,7-Dialkoxy-2-naphthaleneacetic acids, the key intermediates for the preparation of these amides, were obtained from 6,7-dialkoxy-2-acetonaphthones by a modified Willgerodt reaction.     

Benzo- and indoloquinolizine derivatives. I. Synthesis of 4b,5,6,7,8,8a,10,11,16,16b-decahydrodibenz[f,h] indolo[2,3-a] quinolizine

Two 4b 5,6,7,8,8a,10,11,16,16b-decahydrodibenz[f,h]indolo-[2,3-a]quinolizine epimers have been synthesized starting from trans-1,2,3,4,4a,10b-hexahydrophenanthridine. The structural assignment of both isomers is discussed by use of ir and pmr spectroscopy.     

Synthesis of 3,4-Dihydrobenzo[h]isoquinoline Derivatives

1-Substituted 3,3,4-trimethyl-3,4-dihydrobenzo[h]isoquinolines have been obtained by the reaction of 1,2-dimethyl-1-(2-naphthyl)-1-propanol with nitriles in conc. H₂SO₄. It was shown that the presence of a benzene ring annelated at positions 7 and 8 of the isoquinoline does not influence reaction of the 1-methyl derivative with isocyanate, however reactions of the 1-methylthio derivative with C and N nucleophiles are affected significantly.     

Synthesis of some benzo[h]quinoline derivatives

Reaction between 6-methoxy-1-tetralone, methyl propiolate and an ammonia-saturated methanolic solution led to 5,6-dihydro-8-methoxybenzo[h]quinolin-2(1H)-one in good yields. Subsequent aromatization, chlorination, substitution and demethylation enabled us to prepare 2-amino-substituted benzo[h]quinoline derivatives. These compounds, which are structurally related to the antitumor benzo[c]phenanthridine alkaloids by deletion of a ring, were tested on cultured murine lymphoblastic leukaemia cells (L1210). Results showed that they are devoid of cytotoxicity.     

新型苯并香豆素醛的设计合成及光物理性质研究

设计合成了具有较长发射波长的苯并香豆素醛--8-二乙氨基-2-氧-2H-苯并香豆素醛(BCA),通过吸收和荧光光谱研究其在不同溶剂中的光物理性质.结果表明,BCA具有明显的溶致变色效应和宽的颜色变化范围.随着溶剂极性的增加,其荧光发射可从蓝绿光变到红光,而荧光量子效率则从0.98减小到0.26.