Synthesis of [2.2]isoindolinophanes and dihydro[c]furanophane and their charge-transfer complexes with .pi.-acceptors

Abstract

Reaction of 4.5.12.13tetraki»(bromomethyl)[2.2]paracyclophane (6) with methane and p -toluenesulfonamide results In formation of dlhydrobenzo[c ]furanophane (4); however the desired Isolndolophane 3 was not formed. Formation of 4 was supported by the Interaction of 4.5.12.13tetrakls(hydroxymethyl)[2.2]paracyclophane (2) with -toluenesuHonic acid. On the other hand, Interaction of 6 with some aromatic amines gave the corresponding [2.2]lsolndollnophane derivatives 8a-f. Charge-transfer complexes of 8a-f (donors) with tetracyanoethylene (TONE), chloranil (CHL), 2-dlcyanomethylene-1,3-lndanedk>ne (CNIND), and 2,3-dlchloro-5,8-dlcyanobenzoqulnone (DDQ) as -acceptors have been studied spectrophotometrlcally.Unt* 1951 isoindole (1) was not prepared (1). Since that time there have been many reports of successful synthesis of isoindole and its derivatives. 1,2-Bls(bromomethyl)benzenes have

Syntheses of various symmetrical naphthalenophanes and anthracenophanes via a Diels–Alder reaction between syn-[2.2](5,8)phthalazinophane derivatives and some selected dienophiles as well as the synthesis of other symmetrical heterophanes

“…The yellow precipitate formed was isolated by filtration. (14), 510 (12), 410 (14), 308 (100), 280 (20), 204 (16), 126 (20), 102 (34), 77 (30).…”

“…It was reported that the reaction of 9 with aniline afforded the corresponding syn-isoindolenophane. 16 Interestingly, we have also investigated the synthesis of the heterophanes 17a,b as a general method for preparing this class of compound, so as to facilitate their future synthesis. Attempts to prepare the heterophanes 17a,b from the reaction of 9 with binucleophilic compounds such as 2-aminophenol and 2-aminothiophenol proceeded, but in very low yields of the desired products.…”

“…Yield 0.56 g (95%), mp > 300 ЊC (Found: C,73.30;H,4.74 18,128.40,130.60,134.00,134.80,135.40,136.10,136.42,144.68 (PC-C, ᎐ ᎐ C-OCOCH 3 ), 166.90 (OCO-ester), 170.00 (COO-ester); m/z (FAB) 1177 (M ϩ , 100%). syn 5,6,7,14,15,16,(5,8)phthalazinophane-4,7,14,17-tetraone (10) By applying the same procedure mentioned in case of the synthesis of compound 2, a mixture of 9 (0.44 g, 1 mmol) and hydrazine hydrate (3.20 g, 10 mmol) was heated for 6 h. Compound 10 was recrystallized from acetone as orange needles. Yield 0.28 g (75%), mp > 300 ЊC (Found: C,63.30;H,4.20;N,14.85 (10), 303 (14), 203 (40), 188 (100), 159 (20), 143 (12), 133 (44), 103 (22), 77 (18).…”

“…syn-5, 6,15,7,14,6,15,(1,4)naphthalenophane (11) By applying the same procedure mentioned in preparing 12, a stirred mixture of 10 (0.76 g, 2 mmol) and DMM (0.58 g, 4 mmol) in acetic acid (50 cm 3 ) and acetic anhydride (5 cm 3 ) was refluxed for 3 d (the reaction progress was followed by TLC analysis). CH),128.40,133.90,, 172.00 (COO-ester); m/z (EI) 776 (M ϩ , 70%), 760 (40), 746 (16), 716 (12), 658 (22), 388 (100), 308 (16), 262 (20), 188 (20), 144 (16), 60 (18).…”

“…11-14 Although, many tetrasubstituted- [2.2]paracyclophanes have been synthesized by cycloaddition reactions between symmetrical acetylenes and hexa-1,2,4,5tetraene, 15 their chemistry has been hitherto little investigated. 15, 16 Recently, we have worked to find efficient, facile and elegant methods for the preparation of novel symmetrical polycyclic heterophanes such as [2.2] (3,8)pyridazinophane and quinolinophane-2(1H )-one as well as the synthesis of [2](5,8)quinolinophanes and fused spiro-pyranoindanoparacyclophanes. 17 Herein, we report an investigation into the synthesis of various symmetrical naphthalenophanes and anthracenophanes from the newly prepared syn -4,7,14,17tetra(phenyl and chloro) [2.2](5,8)phthalazinophanes (2 and 13) in addition to syn -4,5,6,7,14,15,16,17-octahydro[2.2](5,8)phthalazinophane -4,7,14,17-tetraone (10).…”