J. Tsunetsugu

Some physical properties of methyl derivatives of o-pleiadienequinones

Abstract Some physical properties including spectral (UV, IR, mass 1 H and 13 C NMR) and electrochemical aspects of a typical non-benzenoid quinone, o -pleiadienequinone ( 1 ), and its methyl derivatives are described.

Dichlorocarbene addition to 1,2-dimethoxybiphenylene. A chemical evidence for bond fixation in biphenylene nucleus

1,2-Dimethoxy-biphenylen (I) reagiert mit dem aus Chloroform und Alkali erhaltenen Dichlorcarben uber diskutierte Zwischenstufen mit einer anellierten 1,1-Dichlorcyclopropanstruktur zu den Reaktionsprodukten (III)-(IX).

Efficient Syntheses and the Nucleophilic Substitution of Dibromo- and Tribromo-azulenequinones: Differences in Reactivity between Five- and Seven-membered Ring Moieties

Efficient syntheses and the nucleophilic substitution of dibromoazulenequinones 5a and 5b and tribromoazulenequinones 6a and 6b were carried out: the five-membered ring portion of the molecule is proved to be more reactive than the seven-membered ring.

Synthesis of tropocryptands having heteroatoms in linker chains: A new class of macrobicyclic ligands derived by N-acylation and N-alkylation of tropocoronand

Tropocoronand (1) reacted with acyl chlorides on endocyclic secondary alkylamines to afford diacyl tropocoronands (2a - 2c). Double N-acylation of 1 with dioyl dichlorides (3a - 3d) yielded amide-bridged tropocryptands (4a - 4d). The similar reactions of 1 with ethylene glycol di-p-tosylate (5) or oligo(ethylene glycol) di-p-tosylate (8a - 8d) afforded the corresponding tropocryptands (6 or 9a - 9d).

Formation of Hydro-1,3-diazines by the Reaction of Benzo[b]cyclohepta[e][1,4]oxazine with α,γ-Diamines

Contrary to a report that the reaction of benzo[b]cyclohepta[e][1,4]oxazine 1 with α,γ-diamine 2b produces 1,2,3,4-tetrahydrocyclohepta[b][1,4]diazepine 4, the product was found to be 2-phenyl-3,4,5,6-tetrahydropyrimidine 5b and is peculiar to the reaction of 1 with α,γ-diamines 2 as well as β-aminamide 7.

A five fused ring non-benzenoid quinone containing a seven-membered ring: synthesis and properties of cyclohept[f,g]aceanthrylene-5,8-dione and 1,2-dihydrocyclohept[f,g]aceanthrylene-5,8-dione

Cyclohept[f,g]aceanthrylene-5,8-dione 16 and 1,2-dihydrocyclohept[f,g]aceanthrylene-5,8-dione 15 have both been synthesized in four steps from aceanthrene 9 in 8 and 7% overall yield, respectively. On the basis of their reduction potentials, the compound 16 was shown to be an [18]annulenedione with a higher reduction potential than the isomeric cyclopenta[c,d]pleiadene-5,10-dione 2. An unsuccessful attempt to synthesize cyclohept[f,g]aceanthrylene 21 as well as the efficient synthesis of aceanthrene 9 from anthracene is also described.

o-Pleiadienequinones. Part 3. Ring enlargement of o-pleiadienequinones with diazoalkanes

The reactions of o-pleiadienequinones (1) and (2) with various diazoalkanes are described. In the absence of catalyst pyrazoline derivatives (3) and (4) were obtained. In the presence of Lewis acid catalysts ring-enlarged cyclo-octa[de]naphthalenones (5a), (6), and (7a) were obtained, achieving syntheses of the first known higher analogues of phenalenone. The reaction of the quinone (2) with trimethylsilyldiazomethane gave cyclo-octa[de]naphthalenedione (8). The physical properties of these compounds are described and the mechanism of formation is discussed. The quinone (1) formed 1 : 1 complexes with divalent metal ions.

Formation of two benzocyclo-octatrienedione and 2,3-benzohomotropone derivatives by dichlorocarbene ring expansion

Addition of dichlorocarbene to 1,4,5,8-tetra-methoxynaphthalene (I) and the tetramethylpurpurogallin (IV) affords the benzocyclo-octatrienediones (III) and (VI) together with the bishomonaphthalene (II) and the benzobishomotropone (V), respectively.