63383-01-7Relevant academic research and scientific papers
Preparative methodology and pyrolytic behavior of anthrylmonocarbenes: Synthesis and chemistry of 1H-cyclobuta[de]anthracene
Kendall, J. Kirby,Engler, Thomas A.,Shechter, Harold
, p. 4255 - 4266 (2007/10/03)
This study involves (1) the behavior of organolithium reagents (1-6), (2) development of efficient methods for preparing 9(7)- and 1(8)- [methoxy(trimethylsilyl)methyl]anthracenes and their analogues, (3) the intramolecular chemistry of the 9(9)- and 1(10)-anthrylcarbenes generated by pyrolyses of 7 and 8, respectively, and (4) investigation of thermal behavior and bromination of the 1H-cyclobuta[de]anthracene (11) obtained from 9 or 10. α-Methoxy-9-anthrylmethyllithium (1), prepared from 9- (methoxymethyl)anthracene (14) and t-BuLi in TMEDA/Et2O/pentane, reacts at C-10 with D2O, chlorotrimethylsilane, dimethyl sulfate, benzoyl chloride, acetaldehyde, benzaldehyde, and acetone to give, after neutralization, 9,10- dihydro-9-(methoxymethylene)-10-substituted-anthracenes 15 and 21a-f. However, lithiation of 9-(thiomethoxymethyl)anthracene (25) with t- BuLi/TMEDA/Et2O/pentane occurs by an apparent radical-anion displacement process to give 9-anthrylmethyllithium (3), which then reacts with chlorotrimethylsilane to yield 9-(trimethylsilylmethyl)anthracene (28). Similarly, 28 is formed from 25 and from 9- (trimethylsilyloxymethyl)anthracene (29) with lithium and then chlorotrimethylsilane. The electrophiles D2O, dimethyl sulfate, and benzaldehyde react with 3 at its methyl and its C-10 positions. [Methoxy(trimethylsilyl)methyl]arenes 40-42 and 7 are obtained by reactions of their aryllithium and arylmagnesium bromide precursors with bromo(methoxy)methyltrimethylsilane (39). 1-(Methoxymethyl)anthracene (45) is converted conveniently by t-BuLi and chlorotrimethylsilane to 8. Flash- vacuum pyrolyses of 7 and 8 yield 11 preparatively; 11 then thermolyzes to 2H-cyclopenta[jk]fluorene (46). Decomposition of 9-deuterio-10- [methoxy(trimethylsilyl)methyl]anthracene (55) at 650 °C/10-3 mm results in 10(56)- and 1(57)-deuteriocyclobutanthracenes, thus revealing that the 10- deuterio-9-anthrylcarbene inserts to give 56 and also isomerizes extensively before yielding 57. Of note is that 56 isomerizes thermally by C10-D movement to form 2-deuteriocyclopentafluorene 58, 57 rearranges by C10-H movement to yield deuteriocyclopentafluorene 59, and 58 and 59 equilibrate 1,5-sigmatropically. Possible mechanisms for the isomerizations of 56 and 57 are outlined. Further, bromine adds rapidly to 11 to form 9,10-dibromo-9,10- dihydro-1H-cyclobuta[de]anthracene (94), which eliminates HBr on warming to yield 10-bromo-1H-cyclobuta[de]anthracene (95).
A novel antenna cyclodextrin: Synthesis and photosensitized reaction of an included guest
Nowakowska, Maria,Loukine, Nikolai,Gravett, David M.,Burke, Nicholas A. D.,Guillet, James E.
, p. 4364 - 4368 (2007/10/03)
A novel water-soluble photochemical microreactor has been prepared. A perbutylated cyclodextrin bearing seven naphthalenesulfonate antenna chromophores (Bu-CD-N7) displays improved solubilization of hydrophobic guests in comparison with the unbutylated material (CD-N7). The photophysical properties of Bu-CD-N7 are similar to those of the CD-N7. The naphthyl chromophores of Bu-CD-N7 were used to sensitize the photolysis of 9-anthrylmethyl pivalate (AP). Inclusion of AP in the cyclodextrin leads to the selective formation of one of the two possible coupling products.
GENERATION AND THE AMBIDENT CHARACTER OF 9-ANTHRYLMETHYL CARBANIONS
Engler, T. A.,Shechter, H.
, p. 4645 - 4648 (2007/10/02)
9-Methoxymethylanthracene, 9-trimethylsilylmethylanthracene and 9-thiomethoxymethylanthracene are converted by butyllithium reagents to α-methoxy-9-anthrylmethyl, α-trimethylsilyl-9-anthrylmethyl and 9-anthrylmethyl carbanions, respectively, which react at their C-10 and C-11 positions with appropriate electrophyles.
