Assignment of the 13C-NMR spectrum of phenanthro[4,3-A]dibenzothiophene through the utilization of two-dimensional relayed coherence transfer and double quantum coherence spectroscopy

Total assignment of the ¹³C-nmr spectrum of the helical molecule phenanthro[4,3-a]dibenzothiophene at 125.762 MHz is reported. Assignments were made by the combined application of ¹³C-¹³C autocorrelated double quantum coherence and heteronuclear relayed coherence transfer (RELAY) experiments.     

Synthesis and total 1H-NMR assignment of naphtho[1′,2′:4,5]thieno[2,3-c][1,10]phenanthroline and naphtho[2′,1′:4,5]-thieno[2,3-c] [1,10]phenanthroline

Naphtho[1′,2′:4,5]thieno[2,3-c][1,10]phenanthroline and naphtho[2′,1′:4,5]thieno[2,3-c][1,10]phenanthroline, two novel polycyclic heterocyclic ring systems, have been synthesized in four steps from known starting materials. The total ¹H nmr spectral assignments were made using a COSY experiment to identify the spin systems.     

Synthesis of benzo[4,5]phenaleno[1,9-bc]thiophene and benzo[4,5]phenaleno[9,1–6c]thiophene

Two pentacyclic thiophenes, benzo[4,5]phenaleno[1,9–6c]thiophene ( 1 ) and benzo[4,5]phenaleno[9,1-bc]-thiophene (2) were synthesized via the corresponding 3-methylphenanthro[2,1-b]thiophene (7) and 1-methylanthra[2,1–6]thiphene ( 19 ).     

Synthesis of anthra[b]thiophenes and benzo[b]naphtho[d]thiophenes

All isomers of the parent anthra[b]thiophenes and benzo[b]naphtho[d]thiophenes, namely anthra[2,3-b]thio-phene, anthra[2,1-b]thiophene, anthra[1,2-b]thiophene, benzo[b]naphtho[2,3-d]thiophene, benzo[b]naphtho[2,1-d]thiophene and benzo[b]naphtho[1,2-d]thiophene were synthesized using a new procedure.     

Photocyclization of 2-[1]benzothien-3-yl)-3-phenylpropenoic acids

Photocyclization of the substituted 2-([1]benzothien-3-yl)-3-phenylpropenoic acids 3a-c in the presence of iodine and air in a benzene-cyclohexane mixture afforded a separable mixture of three compounds, benzo[b]naphtho[2,1-d]thiophene-6-carboxylic acids 4a-c , 6H-benzo[b]naphtho[2,3-d]thiopyran-6-ones 5a-c , and 10-methoxy-2-methyl-6H-benzo[b]naphtho[2,3-d]pyran-6-one ( 6 ).     

Synthesis of benzo[1,2]phenaleno[bc]thiophenes

The synthesis of both isomers of benzo[1,2]phenaleno[bc]thiophene namely, benzo[1,2]phenaleno[3,4-bc]-thiophene and benzo[1,2]phenaleno[4,3-bc]thiophene is described.     

Facile regiocontrolled synthesis of trialkyl-substituted pyrazines

[reaction: see text] Alpha-nitro ketones can be transformed selectively into trialkyl-substituted pyrazines via reaction with alpha-amino ketones using octyl viologen as an electron-transfer reagent. The new synthetic method, and the optimal reaction conditions that allow for the regiochemical control, are described.     

Nonextractable cyanopropyl polysiloxane stationary phases for capillary chromatography

Summary Crosslinkable cyanopropylpolysiloxane stationary phases have been difficult to produce because of steric effects of the large cyanopropyl groups or because of the interaction between the polar cyanopropyl groups and the groups added for crosslinking. Various polymers containing 50% to 90% cyanopropyl were synthesized which contained vinyl,p-tolyl, or 4-vinylphenyl groups for crosslinking. Thep-tolyl group was found to give satisfactory crosslinking if there were two such groups attached to one silicon atom.     

Quino[1,2-c]quinazolines. I. Synthesis of quino[1,2-c]quinazolinium derivatives and the related indazolo[2,3-a]quinoline derivatives as analogs of the antitumor benzo[c]phenanthridine alkaloids

9,10-Dimethoxy-1,2,3,4,12,13-hexahydro-1-oxoquino[1,2-c]quinazolinium perchlorate, 1,2,3,4,13,24-hexahydro-1-oxo[1,3]dioxolo[4,5-g]quino[1,2-c]quinazolinium perchlorate, 6-methyl-2,3,9,10-tetramethoxyquino-[1,2-c]quinazolinium perchlorate and 2,3-dimethoxy-13-methyl[1,3]dioxolo[4′,5′:6,7]quino[1,2-c]quinazolinium perchlorate were synthesized as analogs of the potent antitumor benzo[c]phenanthridine alkaloids nitidine and fagaronine. The related 2,3,8,9-tetramethoxyindazolo[2,3-a]quinoline and 2,3-dimethoxy[1,3]dioxolo-[4,5-g]indazolo[2,3-a]quinoline were also synthesized. Further, the novel formation of 6,7-dimethoxy-2-(2-ethylamino-4,5-dimethoxyphenyl)quinoline via reductive alkylation with Raney nickel in refluxing ethanol is also reported.     

Total synthesis of (+/-)-hasubanonine

[reaction: see text] Total synthesis of the alkaloid (+/-)-hasubanonine is described. A key feature of the route is generation of a phenanthrene intermediate via a Suzuki coupling-Wittig olefination-ring-closing metathesis sequence. Conversion of the phenanthrene into the target molecule required six steps including dearomatization by means of oxidative phenolic coupling, anionic oxy-Cope rearrangement, and a final acid-promoted cyclization. Production of an undesired rearranged product in the last step could be suppressed by moderating the acid strength.