Condensed Cyclobutane Aromatic Compounds. XXIX. Benzocyclobutadienequinone. Ring Cleavage Reactions with Some Nitrogenous Carbonyl Reagents

Cava, Michael P.; Stein, R.P.

doi:10.1021/jo01344a044

Cited by 13 publications

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“…The E -and Z -isomers of 658 were obtained by treating 260 with 1 equiv of arylhydrazine in 52−89% yield . In constrast, the reaction with hydrazine gave 1-(2 H )-phthalazinone ( 659 ) and not the hydrazone (Scheme ) 152 …”

Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

“…468 In constrast, the reaction with hydra- zine gave 1-(2H)-phthalazinone (659) and not the hydrazone (Scheme 152). 469 The base-induced condensation of 260 with reagents bearing active hydrogen leads to condensation products, as illustrated in the reaction with 660 (eq 65). In the presence of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), the condensation product 661 is formed.…”

Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

“…478 The reaction of lithiated quinone bisketal 676 with 260 did not yield the desired product 677 but instead gave the ring-opened product 678. 480 However, the reaction of the monoketal of benzocyclobutenediol 679 469 with lithiated quinone bisketal 676 afforded 680 in 70% yield. Hydrolysis of 680 with 5% HCl gave 681 in quantitative yield (Scheme 156).…”

Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

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Cyclobutarenes and Related Compounds

2003

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A general method for the synthesis of cyclobutarenes involves 1,4-elimination from adjacent benzylic positions, followed by ring closure of the resulting o-quinodimethane. The earliest report in which an o-quinodimethane was implicated was the reaction of R,R,R′,R′-tetrabromo-o-xylene (4) with iodide to give the 1,2-dibromocyclobutarene 6, via o-quinodimethane 5. Treatment of 6 with NaI in acetone gave diiodide 7, which on catalytic reduction gave 1 (Scheme 1). [15][16][17] Cava and co-workers confirmed that 5 was an intermediate by trapping experiments using sev-eral dienophiles. 18 A similar procedure has been used to prepare 1,2-diphenylcyclobutarene. 19 Heterocyclic analogues may also be prepared by the 1,4-elimination of halogen from suitable precursors. Compounds 9 and 11 have been synthesized from 8 and 10, respectively, as illustrated in Scheme 2. 20 A variation of the method involves the conversion of R-alkyl-R-bromosulfones into cyclobutarenes using tetrabutylammonium fluoride (TBAF) in acetonitrile at 20-25 °C to effect the elimination. 21 The desired cyclobutarene is often accompanied by olefinic side products, as illustrated in the preparation of cyclobutarene 13, which is accompanied by 14 (eq 1) (Table 1). Anil K. Sadana was born in Panipat, India. He did his M.Sc (1990) and M. Phil (1992) from Kurukshetra University, India. He obtained his Ph.D. degree in 1999 under the guidance of Prof. Om Prakash. His Ph.D. work focused on the utility of hypervalentiodine reagents in the synthesis of heterocyclic compounds. He then joined Prof. W. E. Billups lab as postdoctoral research associate in 2000. He is presently working on small ring compounds and carbon nanotubes. Rajesh Kumar Saini was born in 1966 in Ambala, India. He received his masters degree in 1989 and his Ph.D. in 1996 from Kurukshetra University, India. After his doctorate he moved to the United States for his postdoctoral studies. After a brief stay at Sam Houston State University he joined Rice University, where he is working as a Research Scientist in the laboratories of Prof. W. E. Billups and Prof. Richard E. Smalley. His research has concentrated on small ring compound and the development of carbon nanotube chemistry. W. E. Billups was born in 1939 in Huntington, West Virginia. He received his B.S. in Chemistry Degree from Marshall University in 1961. This was followed by a period in industry after which he entered the graduate school of the Pennsylvania State University in 1968 and received the Ph.D. in 1970. He then joined the chemistry department at Rice University. He served as the Department Chair from July 1985 until December 1991. His research interests are divided among the areas of small-ring compounds, reactive intermediates, chemistry of free metal atoms and more recently fullerene and carbon nanotube chemistry.

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Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

Section: Reactions Of Benzocyclobutenedionementioning

confidence: 99%

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Cyclobutarenes and Related Compounds

2003

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“…Yield: 254 mg (1.2 mmol, 30%) of (2‐hydroxyethyl) phthalate ( 4 ), recrystallized from ethyl acetate, colorless solid (m.p. 120 °C), and 422 mg (1.92 mmol, 48%) of 1,2‐bis(ethylenedioxy)benzocyclobutene ( 3 ) 35…”

Section: Methodsmentioning

confidence: 99%

Ninhydrin as a Source of Naphthoquinone Acetals and Benzocycloheptenetrione Derivatives, and the Trapping of an Oxacarbene Derived from a Cyclopentanone

et al. 2002

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1,3‐Bis(ethylenedioxy)‐2‐indanone (2) was shown to react with some dienophiles to give naphthoquinone acetals under photochemical reaction conditions, presumably by photodecarbonylation via the corresponding ortho‐quinodimethane. With maleic anhydride the highly oxygenated benzocycloheptane derivative rac‐12 was obtained in good yield. In a similar manner, upon irradiation in the presence of acrylonitrile a 2:1 mixture of ring‐expanded regioisomers rac‐13 and rac‐14 was obtained. Irradiation in the presence of fumarodinitrile unexpectedly gave the spirocyclic compound rac‐15, which was characterized by X‐ray crystallography. rac‐15 is the trapping product of oxacarbene 16, thus demonstrating a rare case of a ring expansion of a cyclopentanone to give a six‐membered ring oxacarbene, here leading to an orthoester. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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“…99B (w), 933 (w), 666 (m), 648 (m c b o n~~~-1 , 2 , 3 , 3 a~~~~r o -3 a -e~~~~~~1 0~y -3 , 8 a~-enda-methylcyclopen- T r \ c a r b o n y \ l r 6 -7 , 8~~~y d~~~~~e~~y~~,~~~s~t~m e~y~~y l o x y )~~~y c~~ octenejchromium(o) (23): General procedure C was used with 3 (290 mg, 1.08 mmol) In diethyl ether/THF (1 :1,70 mL), a 0.65 M solution of 2-propenyllithium in diethyl ether (9.96mL, 6.48 mmol), diluted with THF (IOmL), but instead of hydrolysis trimethylsilyl trinuoromethanesulfonate (8.05 g, 36.2 mmol) was added at -78°C.…”

Section: T R I C a R B O N Y L (~6 -1 2~-e~~~t H O X Y C S R B O N mentioning

confidence: 99%

Tricarbonyl(η⁶‐1,2‐dioxobenzocyclobutene)chromium(0): Preparation, Nucleophilic Addition Studies and Syntheses of cmplex Polycyclic Systems by Dianionic Oxy‐Cope Rearrangement

Brands

Wey

Bruckmann

et al. 1996

Chemistry A European J

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Abstract:The tricarbonylchromium complex 3 of I ,2-dioxobenzocyclobutene (1) is easily prepared by hydrolysis of diacetal 4. Complex 3 stereoselectively undergoes both single and double nucleophilic addition reactions at the keto groups. As a consequence, addition of excess alkenyllithium to 3 gives rise to a dianionic oxyCope rearrangement yielding benzocyclooctenedione complexes with good diastereoselectivity. Trapping of the bis(eno1ate) intermediate with chlorotrimethylsilane gives bis(eno1ether) 23.Subsequent addition of two different dianionic oxy-Cope rearrangement. This alkenyllithium derivatives yields the results in the formation of benzoanellated asymmetrically substituted rearrange-bicyclo[3.3.0]octane derivatives and, in ment product 15. To some extent, depen-the case of I-cyclopentenyllithium as the dent on the method of hydrolysis, an in-alkenylmetal, in the tetraquinane system tramolecular aldol addition follows the 19. The trans-anellation of one of the cyclopentane rings in trans-20 has been verified by an X-ray structural analysis. The highly substituted rearrangement product 21/22 is formed only in small yield; in solution the bis(eno1) tautomeric form 22 is favored over diketone 21.

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Condensed Cyclobutane Aromatic Compounds. XXIX. Benzocyclobutadienequinone. Ring Cleavage Reactions with Some Nitrogenous Carbonyl Reagents

Cited by 13 publications

References 1 publication

Cyclobutarenes and Related Compounds

Cyclobutarenes and Related Compounds

Ninhydrin as a Source of Naphthoquinone Acetals and Benzocycloheptenetrione Derivatives, and the Trapping of an Oxacarbene Derived from a Cyclopentanone

Tricarbonyl(η⁶‐1,2‐dioxobenzocyclobutene)chromium(0): Preparation, Nucleophilic Addition Studies and Syntheses of cmplex Polycyclic Systems by Dianionic Oxy‐Cope Rearrangement

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Condensed Cyclobutane Aromatic Compounds. XXIX. Benzocyclobutadienequinone. Ring Cleavage Reactions with Some Nitrogenous Carbonyl Reagents

Cited by 13 publications

References 1 publication

Cyclobutarenes and Related Compounds

Cyclobutarenes and Related Compounds

Ninhydrin as a Source of Naphthoquinone Acetals and Benzocycloheptenetrione Derivatives, and the Trapping of an Oxacarbene Derived from a Cyclopentanone

Tricarbonyl(η6‐1,2‐dioxobenzocyclobutene)chromium(0): Preparation, Nucleophilic Addition Studies and Syntheses of cmplex Polycyclic Systems by Dianionic Oxy‐Cope Rearrangement

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Tricarbonyl(η⁶‐1,2‐dioxobenzocyclobutene)chromium(0): Preparation, Nucleophilic Addition Studies and Syntheses of cmplex Polycyclic Systems by Dianionic Oxy‐Cope Rearrangement