Basketene

Basketene
Names
	Preferred IUPAC name Pentacyclo[4.4.0.02,5.03,8.04,7]dec-9-ene
	Other names Bishomocubene
Identifiers
CAS Number	5603-34-9 ;
3D model (JSmol)	Interactive image;
ChemSpider	122156 ;
PubChem CID	138538;
CompTox Dashboard (EPA)	DTXSID30971411 ;
	InChI InChI=1S/C10H10/c1-2-4-7-5-3(1)6-8(4)10(7)9(5)6/h1-10H Key: LXQOIQYQFRKBLV-UHFFFAOYSA-N; InChI=1/C10H10/c1-2-4-7-5-3(1)6-8(4)10(7)9(5)6/h1-10H;
	SMILES C2=CC5C1C4C3C1C2C3C45;
Properties
Chemical formula	C10H10
Molar mass	130.186 g/mol
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Basketene (IUPAC name: pentacyclo[4.4.0.0^2,5.0^3,8.0^4,7]dec-9-ene^[1]) is an organic compound with the formula C₁₀H₁₀. It is a polycyclic alkene and the dehydrogenated version of basketane, which was named for its structural similarity to a basket. Due to its hydrocarbon composition and unique structure, the chemical compound is of considerable interest to those examining energy surfaces of these (CH)₁₀ cage molecules and what possible factors influence their minima.^[2] Additionally, the complex structure of this compound has intrigued researchers studying the chemistry of highly strained ring systems .^[3] Basketene and its family of derivatives also have important chemical and physical properties. These molecules all tend to have a high standard enthalpy of formation, combined with their high density, leading to possible uses in explosives.^[4]

Synthesis

Basketene has been synthesized as follows. First cyclooctatetraene (1) undergoes thermal, electrocyclic isomerization (to 2), followed by a Diels–Alder reaction with maleic anhydride (3). [2 + 2] photochemical cycloaddition (4 to 5) closes the cage structure, which sodium carbonate hydrolyzes (to 6); lead(IV) acetate in pyridine then decarboxylates oxidatively to basketene (7).^[5]

Reactions

Basketene and other cage molecules are important for discovering and testing new concepts of bonding and reactivity.^[4] Oxidizing basketene with osmium tetroxide selectively cleaves the alkene to two carboxylic acid groups; ketonization then gives a cubane precursor.^[6]

Basketene also undergoes a number of different rearrangements.

Rearrangements

Heating Basketene alone produces Nenitzescu’s Hydrocarbon. The reaction proceeds through a reverse Diels-Alder intermediate in order to give 8 at 110 ˚C. From 8, a 3,3 shift occurs to give Nenitzescu's hydrocarbon (9). ^[2]

The intermediate 8 can be captured by trapping it as a 1:1 adduct with maleic anhydride.^{[citation needed]}

Basketene can also undergo the following thermal and photochemical rearrangement reactions. The photo-induced conrotary opening of 8 gives cis,cis,trans-cyclooctatriene (10). Furthermore, the photo-rearrangement of 10 provides the derivative 11. 11 will undergo a direct photochemical (2+2) cyclization closure to 12.^{[citation needed]}

Basktene also rearranges into snoutene when in solution with Silver nitrate^[1]

References

^ ^a ^b Verevkin, Sergei P.; Martin Kümmerlin; Ernst Hickl; Hans-Dieter Beckhaus; Christoph Rüchardt; Sergei I. Kozhushkov; Rainer Haag; Roland Boese; Jordi Benet-Bucholz; Karsten Nordhoff; Armin de Meijere (2002). "Thermochemical and X-ray Crystallographic Investigations of Some (CH)₁₀ Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene". European Journal of Organic Chemistry. 2002 (14). Wiley VCH: 2280–7. doi:10.1002/1099-0690(200207)2002:14<2280::AID-EJOC2280>3.0.CO;2-R.
^ ^a ^b Allred, Evan L.; Beck, Boyd R. (1973). "Concurrent thermolysis and photolysis of basketene. Formation and the interrelation of some new (CH)10 isomers". Journal of the American Chemical Society. 95 (7). doi:10.1021/ja00788a065.
^ Gassman, Paul G.; Yamaguchi, Ryohei (1978). "1,8-Bishomocubane". Journal of Organic Chemistry. 43 (24). doi:10.1021/jo00418a028.
^ ^a ^b Aydinli, Betül; Çelik, Murat; M. Serdar, Gültekin; Uzun, Orhan; Balci, Metin (2003). "Controlled Synthesis of Substituted Benzobasketene Derivatives". Helvetica Chimica Acta. 86. doi:10.1002/hlca.200390276. hdl:11511/56422.
^ Smit, W. A.; Bochkov, A. F.; Caple, R. (1998). Organic Synthesis: The Science Behind the Art. The Royal Society of Chemistry. p. 184.
^ Chin, Clinton G.; Cuts, Harold W.; Masamune, Satoru (1966). "Strained systems: cubane". Chemical Communications (London) (23): 880. doi:10.1039/c19660000880. ISSN 0009-241X.

[thermo-1] Verevkin, Sergei P.; Martin Kümmerlin; Ernst Hickl; Hans-Dieter Beckhaus; Christoph Rüchardt; Sergei I. Kozhushkov; Rainer Haag; Roland Boese; Jordi Benet-Bucholz; Karsten Nordhoff; Armin de Meijere (2002). "Thermochemical and X-ray Crystallographic Investigations of Some (CH)₁₀ Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene". European Journal of Organic Chemistry. 2002 (14). Wiley VCH: 2280–7. doi:10.1002/1099-0690(200207)2002:14<2280::AID-EJOC2280>3.0.CO;2-R.

[Allred_and_Evan-2] Allred, Evan L.; Beck, Boyd R. (1973). "Concurrent thermolysis and photolysis of basketene. Formation and the interrelation of some new (CH)10 isomers". Journal of the American Chemical Society. 95 (7). doi:10.1021/ja00788a065.

[3] Gassman, Paul G.; Yamaguchi, Ryohei (1978). "1,8-Bishomocubane". Journal of Organic Chemistry. 43 (24). doi:10.1021/jo00418a028.

[HCA-4] Aydinli, Betül; Çelik, Murat; M. Serdar, Gültekin; Uzun, Orhan; Balci, Metin (2003). "Controlled Synthesis of Substituted Benzobasketene Derivatives". Helvetica Chimica Acta. 86. doi:10.1002/hlca.200390276. hdl:11511/56422.

[5] Smit, W. A.; Bochkov, A. F.; Caple, R. (1998). Organic Synthesis: The Science Behind the Art. The Royal Society of Chemistry. p. 184.

[6] Chin, Clinton G.; Cuts, Harold W.; Masamune, Satoru (1966). "Strained systems: cubane". Chemical Communications (London) (23): 880. doi:10.1039/c19660000880. ISSN 0009-241X.

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