The synthesis of novel polycyclic heterocyclic ring system via photocyclization. 18. Benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c]quinoline and benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c] [1,2,4]triazolo[4,3-a]quinoline

The synthesis of two previously unknown polycyclic ring systems, benzo[h]naphtho[1′2′:4,5]-thieno[2,3-c]quinoline ( 1 ) and benzo[h]naphtho[1′,2′:4,5]thieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline ( 2 ), was achieved via oxidative photocyclization of 1-chloro-N-(1-naphthyl)naphtho[2,1-b]thiophene-2-carboxamide ( 5 ). The total assignment of their ¹H and ¹³C nmr spectra was determined by the concerted use of two-dimensional nmr methods.     

The Synthesis of Novel Polycyclic Heterocyclic Ring Systems via Photocyclization. 12. Benzo[h]naphtho-[2′,1′:4,5]thieno[2,3-c]quinoline and benzo[f]-naphtho[2′,1′:4,5]thieno[2,3-c]quinoline

The synthesis of two previously unknown heterocyclic ring systems, namely benzo[h]naphtho[2′,1′:4,5]thi-eno[2,3-c]quinoline (1) and benzo[f]naphtho[2′,1:4,5]thieno[2,3-c]quinoline (2) was accomplished via photocyclization of the appropriate amides followed by chlorination and catalytic dechlorination. The total assignment of ¹H and ¹³C nmr spectra of 2 was determined utilizing two-dimensional nmr methods, providing unequivocal structural proof of the two novel polycyclic ring systems.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 19. Thieno[3′,2′:4,5]thieno[2,3-c]-naphtho[1,2-f]quinoline,thieno[3′,2′:4,5]thieno[2,3-c]naphtho-[1,2-f][1,2,4]triazolo[4,3-a]quinoline and thieno[3′,2′:4,5]-thieno[2,3-c]naphtho[1,2-f]tetrazolo[1,5-a]quinoline

Photocyclization of 3-chloro-N-(3-phenanthryl)thieno[2,3-b]thiophene-2-carboxamide ( 5 ) yielded only one of the two possible structural isomers, thieno[3′,2′:4,5]thieno[2,3-c]naphtho[1,2-f]quinolin-6(5H)-one ( 6 ), which was further elaborated to afford the unsubstituted ring system 10 , its triazole 11 and tetrazole 12 . The structural confirmation of 10 was achieved by the total assignment of its ¹H and ¹³C nmr spectra by the concerted utilization of two-dimensional nmr spectroscopic methods.     

Total assignment of the 1H and 13C NMR spectra of pyrrolizino-[3,4,5-a,b]isoquinoline,benzo[1,2]pyrrolizino[3,4,5-a,b]isoquinoline and 2-methylthiopyrrolizino[3,4,5-a,b]isoquinoline

The total ¹H and ¹³C nmr spectral assignments of pyrrolizino[3,4,5-a,b]isoquinoline, benzo-[1,2]pyrrolizino[3,4,5-a,b]isoquinoline and 2-methylthiopyrrolizino[3,4,5-a,b]isoquinoline are reported. The concerted use of the COSY, HMQC, HMBC and nOe-difference experiments is used to generate total assignments of the ¹H and ¹³C nmr spectra.     

Unusual schmidt rearrangement of 7,7a,8,9,10,12-hexahydro benzo[h]pyrrolo[1,2-b]-isoquinoline-7,10-dione

The reaction of 7,7a,8,9,10,12-hexahydrobenzo[h]pyrrolo [1,2-b]isoquinoline-7,10-dione 2 with sodium azide in sulfuric acid afforded the unexpected cyano derivative 5 . The proposed structure for 5 is supported by ¹³C nmr, ¹H nmr and HMBC spectra.     

The synthesis of novel polycyclic heterocyclic ring systems.. Benzo[e][1]benzothieno[3,2-g][1]benzothiophenes

The novel polycyclic heterocyclic ring system compound, methyl 3-chlorobenzo[e][1]benzothieno-[3,2-g][1]benzothiophene-2-carboxylate was synthesized. The assignment of its ¹H and ¹³C nmr spectra was also accomplished by utilizing two-dimensional nmr methods.     

The synthesis of novel polycyclic heterocyclic ring systems. 2. Naphmo[2,1-b:4,3-g]bisbenzo[b]thiophene

The novel polycyclic heterocyclic ring system, naphtho[2,1-b:4,3-g]bisbenzo[b]thiophene was synthesized from 5-[2-(2-bromo-3-thienyl)ethenyl]naphtho[2,1-b][1]benzothiophene. The assignment of its ¹H and ¹³C nmr spectra was also accomplished by utilizing two-dimensional nmr methods.     

The first synthesis of thieno[c]isoquinolines and an improved synthesis of phenanthridine and thieno[c]quinolines through pd(0) catalyzed coupling of ortho-formylarylboronic acids with functionalized aryl halides

All three isomeric hitherto unknown thieno[c]isoquinolines have been synthesized in high yields by the Pd(0)-catalyzed coupling of 2-formylbenzeneboronic acid with t-butyl-N-(ortho-halothienyl)carbaniates. When 2-bromoacetanilide, instead of 2-bromoaniline, was coupled with orth-formylarylboronic acids under Pd-catalysis, phenanthridine and thieno[c]quinolines were obtained in improved yields. Total assignments of ¹H nmr spectra of thieno[c]isoquinolines and thieno[c]quinolines are reported. Assignments are based on high resolution 300 MHz ¹H nmr spectra, two-dimentional ¹H-¹³C chemical shift correlation spectra and one-dimentional INADEQUATE ¹³C nmr spectroscopy.     

The synthesis of novel polycyclic heterocyclic ring systems. 3. Synthesis and NMR spectroscopy of 15-chloro[1]benzo-thieno[2″,3″:3′,4′]naphtho[1′,2′:4,5]thieno[2,3-c]quinoline

The polycyclic heterocyclic compound with a novel ring system, 15-chloro[1]benzothieno[2″,3″:3′,4′]-naphtho[1′,2′:4,5]thieno[2,3-c]quinoline was synthesized via photocyclization of 3-chloro-N-phenyl[1]-benzothieno[2′,3′:3,4]naphtho[2,1-b]fhiophene-2-carboxamide followed by chlorination with phosphorus oxychloride. The assignment of its ¹H and ¹³C nmr spectra was accomplished by utilizing two-dimensional nmr methods.     

Complete assignment of the 1h- and 13c-nmr spectra of [1]benzothieno[2,3-c]naphtho[1,2-h]quinoline and [1]benzothieno[2,3-c]naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline. Concerted use of two-dimensional nmr techniques

The ¹H- and ¹³C-nmr spectra of [1]benzothieno[2,3-c]naphtho[1,2-h]quinoline and [1]benzothieno[2,3-c]-naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline were totally assigned using a combination of two-dimensional nmr techniques. After correlation of the proton signals by a COSY spectrum and one-bond heteronuclear correlation, complete assignment of the ¹H- and ¹³C-nmr spectra of the novel heterocyclic compounds required the application of long-range CH coupling information particularly for quarternary resonance assignments and the orientations of individual spin systems relative to one another.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 23 . Naphtho[2′,1′:4,5]thieno‐[2,3‐c]naphtho[2,1‐f]quinoline

A previously unknown heterocyclic ring system, naphtho[2′,1′:4,5]thieno[2,3‐c]naphtho[2,1‐f]quinoline ( 14 ), was synthesized via oxidative photocyclization of 3‐chloro‐N‐(2‐phenanthryl)naphtho[1,2‐b]‐thiophene‐2‐carboxamide ( 9 ). Further elaboration of the lactam 10 yielded the unsubstituted ring system 14 . Structural confirmation of compound 14 was accomplished by a total assignment of its ¹H and ¹³C nmr spectra utilizing the concerted two‐dimensional nmr spectroscopic methods.     

Synthesis and total 1H-NMR assignment of [1]benzothieno-[2,3-c] [1,10]phenanthroline

The synthesis of [1]benzothieno[2,3-c][1,10]phenanthroline ( 5 ) is described. It was obtained in four steps from known starting materials. The basic skeleton of the molecule and of the phenanthroline ring were formed via photocyclization. The total assignment of ¹H-nmr spectra was accomplished with the aid of two-dimensional nmr methods.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 5. [1]Benzothieno[2,3-c]naphtho[2,1-f]-quinoline and [1]benzothieno[2,3-c]naphtho[1,2-g]quinoline

Two previously unknown heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[2,1-f]quinoline ( 4 ) and [1]benzothieno[2,3-c]naphtho[1,2-g]quinoline ( 5 ) were synthesized via photocyclization of 3-chloro-N-(2-phenanthryl)benzo[b]thiophene-2-carboxamide ( 8 ) followed by chlorination and dechlorination. The total assignment of their ¹H- and ¹³C-nmr spectra was determined by utilizing inverse-detected HMQC and HMBC two-dimensional nmr spectroscopic methods.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 4 . Benzo[f]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and Benzo[h]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and the total assignment of their 1H- and 13C-NMR spectra

The synthesis of two novel polycyclic heterocyclic ring systems via photocyclization are reported. These are benzo[f]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and benzo[A]thieno-[2′,3′:4,5]thieno[2,3-c]quinoline. The total assignment of their ¹H- and ¹³C-nmr spectra was determined by utilizing two-dimensional nmr spectroscopic methods.     

Furopyridines. XI. 13C NMR Spectra of 2- or 3-Substituted Furo[2,3-b]-, Furo[3,2-b]-, Furo[2,3-c]- and Furo[3,2-c]pyridine

The ¹³C nmr spectra of 2- or 3-monosubstituted furo[2,3-b]- 1a-1j , furo[3,2-b]- 2a-2j , furo[2,3-c]- 3a-3j and furo[3,2-c]pyridine derivatives 4a-4j are reported. Effects by change in annelation and substituent effects on ¹³C chemical shifts and carbon-proton coupling constants are discussed. The spectra of benzo[b]furan derivatives 5a-5j having the corresponding substituent are also reported for comparison.     

Pyrrolothienopyrazines. IV. Synthese de derives de 1′amino-5 pyrrolo[1,2-a]thieno[2,3-e]pyrazine

5-Aminopyrrolo[1,2-a]thieno[2-3-3]pyrazine derivatives were obtained by intramolecular cyclisation of N³(1-pyrrolyl)-2-thienylurea derivaties. Synthesis of these latter compounds was achieved from 2-(1-pyrrolyl)-3-thenoylazide via a curtius rearrangement. The H nmr spectra are discussed.     

Syntheses of triazolo[6,7-d]phthalide and triazolo[6,7-d]dihydrocoumarin

Triazolo[6,7-d]phthalide has been synthesized in a seven step sequence from phthalide in 24% overall yield, and triazolo[6,7-d]dihydrocoumarin has been prepared in nine steps from dihydrocoumarin in 20% overall yield. The ¹H and ¹³C nmr spectra and the tautomeric equilibria of the final compounds and intermediates are discussed.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 17. Thieno[3′,2′:4,5]thieno[2,3-c]naphtho-[2,1-f]quinoline and thieno[3′,2′:4,5]thieno[2,3-c]-naphtho[1,2-g]quinoline

The synthesis of two previously unknown novel polycyclic heterocyclic ring systems via photocyclization is described. The structural assignment of the isomeric ring systems, 4 and 5 , was achieved by the total assignment of their ¹H and ¹³C nmr spectra by the concerted usage of two-dimensional nmr methods.     

Synthese de dihydro-6,7 benzo-b [1H] azonines par extension de cycle de dihydro-4,5 benzo-b [1H] azepines

Activated acetylnic reagents add to heterocyclic enamines 4,5-dihydro-1H-benzo[b]azepines and by electrocyclisation, give 6,7-dihydro-1H-benzo[b]azoninines. The structure of those new heterocycles is demonstrated by mass spectra, ¹H and ¹³C nmr.     

Complete assignment of the 1H and 13C NMR Spectra of 11,12-Dimethoxy[1]benzothieno[3,2-a]-4,7-phenanthroline and its 8-Chloro Analogue: Concerted Use of Two-Dimensional NMR Techniques

The ¹H and ¹³C nmr spectra of 11,12-dimethoxy[1]benzothieno[3,2-a]-4,7-phenanthroline and its 8-chloro precursor were totally assigned using a combination of two-dimensional nmr techniques. After correlation of the majority of the proton signals by a COSY spectrum and one-bond heteronuclear correlation, the full assignment of the ¹H and ¹³C nmr spectra of the novel heterocyclic compounds required the application of long-range CH coupling information particularly for quaternary carbon resonance assignments and the orientations of individual spin systems relative to one another. Key long-range heteronuclear couplings in both compounds served to confirm the one-bond heteronuclear correlations. Unequivocal interpretation of the spectral data leads to the complete assignments of the resonances.