[4.4.1]Propellatetraene and Related Propellanes

Frauenrath, Herbert; Kapon, Moshe; Rubin, M. B.

doi:10.1002/ijch.198900040

Cited by 8 publications

References 15 publications

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Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Exner¹,

Fischer

Bahr

et al. 2000

Eur. J. Org. Chem.

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Rigid NN/NN (diazene/diazene) systems (F) consisting of more or less alkylated DBH and DBO chromophoric units (1, 2, X‐ray structures), with very short π,π distances [d = 2.849 (1a, av.), 2.822 Å (2)] and almost perfect syn‐periplanar π,π alignments [ω = 168.6 (1a), 174.2° (2)] as well as the more flexible, less “proximate” metathesis isomers (3a,c, 27a,c, d >4.6 Å, ω = 90‐100°) have been synthesized. Homoconjugate π,π interaction (in 1, 2, not in 3, 27) is deduced from UV spectroscopic measurements [π → π* maxima at 239 (234) nm (sh, 260)], while PE analyses furnished only small interaction parameters (1a: <0.3 eV). The potential of the novel syn‐periplanar NN/NN motif in 1 and 2 for the synthesis of somewhat exotic polyheterocycles has been explored by calculation (B3LYP) as well as experimentally: i.a. kinetically stabilized, all‐cis‐peralkylated tetrazolidines (38, 44) and perhydro‐1,2,4,5‐tetrazines (41, 47) have become accessible (i.a. via novel azomethine/diazene and azomethine/azomethine cycloadditions). In 1a with its unreactive DBO chromophoric subunits, in the “buttressed” derivatives 1b‐d, as well as in the DBH/DBO combination 2, and likewise in more ‘distant’ 27 (differently from the analogous CC/CC and NN/CC systems), irrespective of the excitation conditions employed (light of λ ≥≥ 280, 254 nm, low temperature matrix irradiation, acetone sensitization) no [2+2]photocycloaddition was observed. Instead exclusively N2‐elimination took place. It is argued that unproductive NN/NN photocycloaddition would have become observable through metathesis isomerization of the respective tetrazetidines.

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Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Exner¹,

Fischer

Bahr

et al. 2000

Eur. J. Org. Chem.

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Dichlorovinylene Carbonate

Caster¹

2001

Encyclopedia of Reagents for Organic Synthesis

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σ‐Homoacenaphthylen und π‐Homoacenaphthen

et al. 1991

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icvn. S w YX (1976) 3935; C. Barich. E. Heilhronner. E. Vogel. l l d v . C/irrti A(.rcr 37 (1974) 228X; c ) Molekiilsfruktur. siehe [3a]. rweires Ziraf. [4] E. Vogcl. I.. Schmalsrieg. H.-J. Weyer. R . Gleifer. C/icwi. Lerr lYR7, 33. IS] Zur elekfrrphilen Hydroxylierung von Arenen mif l'crsiiuren (Beispiele fur nachfolgcnde Oxidation 7u Chinonen) aiehe R. Taylor: E / [~~~r r o p / i t / t c Arotmt/i~ .%dh\rtrWtoti.\. Wiley. Chichesfer. England IYYO. S. 327. [61 Die vcrwendete kiulliche XO 85 proz. MCPBA wurde vor dcr Reaktion mil eincm 1'hosph:itpuffcr (pH 7) gewaschen. Nach Trocknen bis r u r Ge-uichfskonsian~ iin Olpumpenvakuum bctrug der Persluregehalt 97 Y 9 U o . Sieht: hteriu N. N. Schuarfr. J. H . Blumbergs. J Or,q. C/icnt. 2Y (1964) 1976 [71 Eine w;iUril:e Aufarheitung 1st LU vrrniciden. d;i hierhci crhehliche Ausbeuteverlus'c bei 5 aufrrcren. [XI Aus der briiuncn Fraktion lassen aich nach Waachen mil gcsdfligtcr Niltriumhydrogcnc;irhonat-LbPung und erncutrr Chromatographic an Kie-\elgel folger dc Nebenprodukfe isolirren , I I 16-,ti-Chlorbenioyloxy-1 S h y -dro~~-l.h:X.Ii-efh;indi~liden[l4I;lnnulen [orangefxbene Prismen (;]us Dichlormef i:in Ether): F p = 160 16.3 C ( Z e r r . ) . Ausheute ?XI. 2)Azu-

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[4.4.1]Propellatetraene and Related Propellanes

Cited by 8 publications

References 15 publications

Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Dichlorovinylene Carbonate

σ‐Homoacenaphthylen und π‐Homoacenaphthen

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