Synthesis of phenanthro[2,3-h]isoquinoline and phenanthro[3,2-h]isoquinoline

The suspected environmental contaminants phenanthro[2,3-h]isoquinoline 12 and phenanthro[3,2-h]isoquinoline 11 were synthesized in four steps from a common intermediate 1,4-phenanthroquinone 3 , using a Diels-Alder reaction.     

Synthesis of thia-ellipticine, 5,11-dimethylbenzothieno[2,3-g]isoquinoline

1,4-Dimethyldibenzothiophene (VII) was synthesized and was converted with butyl dichloromethyl ether to the 2-aldehyde (VIII). The structure was confirmed by an independent synthesis of the 2-ester (XI) derived from it. The 2-aldehyde (VIII) with aminoacetaldehyde diethylacetal formed the Schiff′s base (IX), and Pomeranz-Fritsch cyclization with 105% superphosphoric acid then formed thia-ellipticine (II), an isostere of the antitumor alkaloid, ellipticine.     

Photoalkylation of phenanthro[9,10-d] oxazole

The photochemical reaction of phenanthro[9,10-d]oxazole with ethanol, 1-propanol, 2-propanol, or diethyl ether resulted in the substitution of the 1-and/or 2-hydroxyalkyl and/or alkyl groups at the position 2.     

Synthesis of phenanthro[b]thiophenes

All isomers of the parent phenanthro[b]thiophenes, namely, phenanthro[1,2-b]thiophene, phenanthro-[2,1-b]thiophene, phenanthro[2,3-b]thiophene, phenanthro[3,4-b]thiophene, phenanthro[3,4-b]thiophene, phenanthro[4,3-b]thiophene and phenanthro[9,10-b]thiophene have been synthesized.     

Synthesis of 1,3,4,6,7,11b-hexahydro-9,10-dimethoxy-11b-methyl [1,4]thiazino[3,4-a]isoquinoline derivatives

Alkylation of the 2-mercaptoacetamide 4a with chloropropanone afforded the ketoamide 10 which on direct acid-catalyzed cyclization furnished 12 . The cyclization can be arrested at the stage of the enamide 11 . Periodate oxidation of 12 gave the equatorial sulfoxide 14 . Reduction of 12 with diborane led to 13 which was oxidized to yield a mixture of sulfoxides 17 and 18 . The configuration of 12, 14, 17 , and 18 was established on the basis of nmr data. Compounds 12, 14 , and 18 showed an interesting degree of antihypertensive activity.     

Synthesis of benzo[b]phenanthro[d]thiophenes

The synthesis of benzo[b]phenanthro[1,2-d]thiphene ( 1 ), benzo[b]phenanthro[4,3-d]thiophene ( 2 ), benzo-[b]phenanthro[2,1-d]thiophene ( 3 ) and benzo[b]phenanthro[3,4-d]thiophene ( 4 ) from appropriately substituted olefines by photochemical cyclodehydrogenation is described. The photolysis of olefin 9 gave a mixture of 4 and anthra[1,2-b]benzo[d]thiophene ( 5 ).     

Substitution reactions of phenanthro[9,10-d]triazole with benzyl chlorides

The reaction of the potassium salt of phenanthro[9,10-d]triazole and benzyl chloride gave 2-(benzyl)-2H-phenanthro[9,10-d]triazole ( 2a ) in 15% yield. The other regio-isomer, 1-(benzyl)-1H-phenanthro[9,10-d]-triazole ( 1a ), was obtained as a by-product in 3.9% yield. Similar reactions with benzyl chlorides having a methyl, a chloro or a nitro group on the aromatic ring gave the corresponding two products, 1b-j and 2b-j . In all cases, 2b-j were major products in yields of 14–62%, 1b-j were minor ones in yields of 1.4–7.6%. The structures of the isomers were confirmed by X-ray crystal analyses.     

Synthesis of indazolo[3,2-a]isoquinoline

Treatment of 1-(2′-nitrophenyl)isoquinoline with hot triethylphosphite afforded indazolo[3,2-a]isoquino-line.     

Synthesis of 4-amino[1] benzofuro[3,2-g] cinnolines

The synthesis of the new heterocycles, 4-amino[1]benzofuro[3,2-g]cinnolines, was accomplished by the intramolecular cyclization of the Z -configuration of cyanoarylhydrazones. The latter compounds were obtained via interaction between the diazonium salt of 3-amino-dibenzofuran and various active methylene compounds via the Japp-Klingemann reaction. The alkaline treatment of azo intermediates 4 , which may be isolated in the course of condensation, gave the corresponding cyanoarylhydrazones 5 . A study of the configuration and possible isomerisations is reported.     

Synthesis of Benzo[a]Phenanthro[9,10-e]-Cyclooctene

A phenanthrene-fused cyclooctatetraene, namely benzo[a]phenanthro[9,10-e]cyclooctene has been synthesized by employing the “Reich-Paquette” procedure.     

Synthesis of 2,3,10,11 -tetraalkoxy-substituted tetrahydrobenzo [a] naphtho [1,2-g] quinolizines

2 Four3,10,11-tetraalkoxy-substituted 5,6,15,15a-tetrahydro-8H-benzo[a]naphtho[1,2-g]-quinolizines were prepared by the Pictet-Spengler cyclization of the respective 1-(6,7-dialkoxy-2-naphthylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines. The latter compounds were obtained by a chemical reduction of the corresponding dihydro compounds, which, in turn, were formed by a Bischler-Napieralski cyclization of the appropriate amides.     

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 Furo[2,3-c]isoquinoline Derivatives

2-Methylfuro [2,3-c] isoquinolin-5(4H)one (X) and 1-phenylfuro[2,3-c] isoquinolin-5(4H)one (XI) were prepared from thermal cyelization via the Curtius rearrangement of 5-methyl-3-phenyl-2-furoyl azide (VI) and 3,4-diphenyl-2-furoyl azide (VII), respectively. Stability against acid, alkylation and conversion of the NHCO group to a C=N double bond of X and XI, which were synthesized, are described. Also, 5-substituted furo[2,3-c] isoquinolines (XVIIIa-c) and (XIXa-c) were prepared.     

1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物的合成

采用无溶剂合成法,以1,6-亚甲基桥[10]轮烯-3,4-二甲酸酐为原料,Zr OCl2·8H2O/Na Cl为催化剂,于165℃下分别与取代苯经Friedel-Crafts缩合反应合成了4个新型的1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物,其结构经1H NMR,13C NMR,IR,MS和HR-MS表征。     

Synthesis of benzo[3,2]phenanthro[4,5-bcd]thiophene and chryseno[4,5-bcd]thiophene

Benzo[2,3]phenanthro[4,5-bcd]thiophene and chryseno[4,5-bcd]thiophene were synthesized, so that their mutagenic and carcinogenic activity can be determined.