252-16-4

Upstream product

• 83469-44-7 1-anthracene 
• 235426-11-6 9-anthracene 
• 98398-56-2 5-(9-anthryl)-2H-tetrazole 

Downstream Products

• 208-69-5 2H-cyclopentafluorene 

Relevant academic research and scientific papers

Preparative methodology and pyrolytic behavior of anthrylmonocarbenes: Synthesis and chemistry of 1H-cyclobuta[de]anthracene

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).

FORCE FIELD-SCF CALCULATIONS ON CYCLOPROPENE INTERMEDIATES IN CARBENE REARRANGEMENTS. COMPARISON WITH EXPERIMENT

Heats of formation and geometries of benzocyclopropene, cyclopropa(b)naphthalene, bicyclo(4.1.0)hepta-2,4,7-triene, and benzannelated derivatives have been calculated with a combined force field-SCF progrsm.The bicycloheptatrienes are stabilized relative to the isomeric arylcarbenes by benzannelation, and destabilized by loss of aromaticity and/or increased strain. 1-Naphthylcarbene, 2-naphthylcarbene, 9-phenanthrylcarbene and 9-anthrylcarbene were generated by gas-phase pyrolysis of the corresponding arene aldehyde tosylhydrazone sodium salts, diazomethanes, or 5-aryltetrazoles, and rearranged to cyclobutanaphthalene(21), cyclobutaphenanthrene(33), and cyclobutaanthracene(38), respectively. 10,11-Dihydrodibenzocyclohepten-5-ylidene (15), similarly generated from 5-diazo-10,11-dihydro-5H-dibenzocycloheptene (39), rearranged to 5a,9b-dihydro-5H-benzocyclobutindene(40), 5H-dibenzocycloheptene(41), and 8,9-dihydro-4H-cyclopentaphenanthrene(40). 40 rearranged thermally to 41.The mechanisms of the rearrangements are discussed.