Basketane is a polycyclicalkane with the chemical formula C10H12. The name is taken from its structural similarity to a basket shape. Basketane was first synthesized in 1966, independently[1] by Masamune[2] and Dauben and Whalen.[3] A patent application published in 1988 used basketane, which is a hydrocarbon, as a source material in doping thin diamond layers because of the molecule's high vapor pressure, carbon ring structure, and fewer hydrogen-to-carbon bond ratio.[4]
In the year 1989 and before the synthesis of basketane, historic chemists were intrigued by the structural make-up of molecules, specifically those in objects seen in everyday life.[5] Using supramolecular chemistry, molecules such as cubane and basketane were named according to their corresponding shape and historically revealed certain characteristics and personal motives of chemists at that time.[5] Naming these uniquely shaped molecules were also done considering chemical nomenclature such as adding "-anes" for single carbon-carbon bonds and "-enes" for double carbon-carbon bonds to the end of the appropriate molecules.[6]
Synthesis
The synthesis of basketane reported by Masamune begins with a Diels–Alder reaction between cyclooctatetraene (1) and maleic anhydride (2), giving the polycyclic anhydride 3, which photoisomerizes in acetone via an intramolecular cyclization to give 4 at a 40% yield. Hydrolysis of the anhydride followed by treatment with lead tetraacetate affords the unsaturated basketene (5), which is then hydrogenated to basketane (6).[2]
An alternative synthetic route with better overall yield uses 1,4-benzoquinone and cyclohexa-1,3-diene as starting materials. 1,4-Benzoquinone (1) is first converted to 2,5-dibromo-1,4-benzoquinone (2), which reacts in a Diels–Alder reaction with cyclohexa-1,3-diene (3) to form the polycyclic diketone 4. This diketone photoisomerizes to 1,6-dibromopentacyclo[6.4.0.03,6.04,12.05,9]dodeca-2,7-dione (5), which undergoes a pseudo-Favorskii rearrangement in a 25% aqueous solution of sodium hydroxide, giving the dicarboxylic acid 6. The acid is decarboxylated with a modified Hunsdiecker reaction to a dibromide 7, which is reductively debrominated with tributyltin hydride to basketane (8) at a 11% yield relative to the starting material cyclohexa-1,3-diene.[7]
A 1994 synthesis by Binmore starts with homocubanone, a cubane derivative, forming basketane via the basketyl radical. The synthesis functions by forcing cubane rings to be opened up via structural strain to create the chemical bonds necessary for this rigid molecule.[8] This method is known as ring expansion where one part of two conjoined ringed are opened and rearranged to remove barriers between the two ring systems.[9]Cyclobutylmethyl radicals that rearrange and open into structures such as basketane and cubane are favorable rearrangements with free energy barriers around 0.3 kcal/mol.[10]
Properties
Basketane and other polycyclic, cage-like molecules do not conform to simple carbon-carbon bonds with angles of 109.5 degrees due to their strained system.[11] The strain energy causes thermodynamic instability resulting in higher combustion and heat release.[11] When taking a mass analysis, the mass spectrum graph for basketane has a distinct tall peak at 39 m/z distinguishing a clear cyclic structure.[12]
Transition metals catalyze the valence isomerization of basketane and substituted derivatives. Silver perchlorate catalyzes its isomerization to the compound snoutane.
Using other transition metals for this reaction affords a mixture of snoutane or the corresponding snoutane derivative with a tricyclic diene. The ratio of the products depends on the nature of the catalyst used and the substitutions on the basketane.[13]
In the hydrogenation of basketane with palladium on carbon, it absorbs an equivalent amount of hydrogen gas. The initial assumption by Masamune was that the bond between C4 and C5 opens to give the symmetric hydrocarbon tetracyclo[4.4.0.02,9.05,8]decane, but Musso later showed that it is the bond between C3 and C4 (or equivalently C4 and C7) that breaks, giving the dihydrobasketane tetracyclo[4.4.0.02,5.03,8]decane.[14] Further hydrogenation breaks the C5-C6 bond to give the hydrocarbon twistane.[15]
^Marchand, A. P. (1989). "Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes". Chem. Rev.89 (5): 1011–1033. doi:10.1021/cr00095a004.
^ abMasamune, S.; Cuts, H.; Hogben, M. G. (1966). "Strained systems. VII. Pentacyclo[4.2.2.02,5.03,8.04,7]deca-9-ene, basketene". Tetrahedron Lett.7 (10): 1017–1021. doi:10.1016/S0040-4039(00)70232-2.
^Dauben, W. G.; Whalen, D. L. (1966). "Pentacyclo[4.4.0.02,5.03,8.04,7]decane and pentacyclo[4.3.0.02,5.03,8.04,7]nonane". Tetrahedron Lett. 7 (31): 3743–3750. doi:10.1016/S0040-4039(01)99958-7.
^WO 1988002792, Pastor, Ricardo C., "Process for depositing layers of diamond", published 1988-04-21, assigned to Hughes Aircraft Co., since withdrawn.
^ abVicens, Jacques (2007-07-26). "Aesthetics in chemistry". Journal of Inclusion Phenomena and Macrocyclic Chemistry. 58 (3–4): 327–328. doi:10.1007/s10847-006-9161-7. ISSN 0923-0750. S2CID 94479873.
^Gassman, Paul G.; Yamaguchi, Ryohei (1978). "1,8-Bishomocubane". The Journal of Organic Chemistry. 43 (24): 4654–4656. doi:10.1021/jo00418a028. ISSN 0022-3263.
^Binmore, Gavin T.; Della, Ernest W.; Elsey, Gordon M.; Head, Nicholas J.; Walton, John C. (April 1994). "Homolytic Reactions of Homocubane and Basketane: Rearrangement of the 9-Basketyl Radical by Multiple .beta.-Scissions". Journal of the American Chemical Society. 116 (7): 2759–2766. doi:10.1021/ja00086a009. ISSN 0002-7863.
^"Ring Opening versus Ring Expansion in Rearrangement of Bicyclic Cyclobutylcarbinyl Radicals". dx.doi.org. doi:10.1021/jo702164r.s002. Retrieved 2021-03-16.
^Shi, Jing; Chong, Sha-Sha; Fu, Yao; Guo, Qing-Xiang; Liu, Lei (2008-02-01). "Ring Opening versus Ring Expansion in Rearrangement of Bicyclic Cyclobutylcarbinyl Radicals". The Journal of Organic Chemistry. 73 (3): 974–982. doi:10.1021/jo702164r. ISSN 0022-3263. PMID 18179235.
^ abMarchand, Alan P. (1989-07-01). "Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes". Chemical Reviews. 89 (5): 1011–1033. doi:10.1021/cr00095a004. ISSN 0009-2665.
^"Basketane - MS - Spectrum - SpectraBase". spectrabase.com. Retrieved 2021-03-16.
^Paquette, Leo A.; Boggs, Roger A.; Farnham, William B.; Beckley, Ronald S. (1975). "Silver(I) ion catalyzed rearrangements of strained .sigma. bonds. XXIX. Influence of structural features on the course of transition metal catalyzed 1,8-bishomocubane rearrangements". Journal of the American Chemical Society. 97 (5): 1112–1118. doi:10.1021/ja00838a026. ISSN 0002-7863.
^Andre Sasaki, N.; Zunker, Reinhard; Musso, Hans (1973). "Welche C–C‐Bindung wird bei der Hydrierung von Basketanderivaten geöffnet?". Chemische Berichte. 106 (9): 2992–3000. doi:10.1002/cber.19731060930. ISSN 0009-2940.
^Musso, Hans (1975). "Hydrogenolyse kleiner Kohlenstoffringe, II. Über die Hydrierung von Basketan‐ und Snoutanderivaten". Chemische Berichte. 108 (1): 337–356. doi:10.1002/cber.19751080143. ISSN 0009-2940.
Further reading
Binmore, Gavin T.; Della, Ernest W.; Elsey, G. M.; Head, N. J.; Walton, J. C. (1994). "Homolytic Reactions of Homocubane and Basketane: Rearrangement of the 9-Basketyl Radical by Multiple β-Scissions". J. Am. Chem. Soc.116 (7): 2759–2766. doi:10.1021/ja00086a009.
This article about a hydrocarbon is a stub. You can help Wikipedia by expanding it.
basketane, polycyclic, alkane, with, chemical, formula, c10h12, name, taken, from, structural, similarity, basket, shape, first, synthesized, 1966, independently, masamune, dauben, whalen, patent, application, published, 1988, used, basketane, which, hydrocarb. Basketane is a polycyclic alkane with the chemical formula C10H12 The name is taken from its structural similarity to a basket shape Basketane was first synthesized in 1966 independently 1 by Masamune 2 and Dauben and Whalen 3 A patent application published in 1988 used basketane which is a hydrocarbon as a source material in doping thin diamond layers because of the molecule s high vapor pressure carbon ring structure and fewer hydrogen to carbon bond ratio 4 Basketane NamesPreferred IUPAC name Pentacyclo 4 4 0 02 5 03 8 04 7 decaneIdentifiersCAS Number 5603 27 03D model JSmol Interactive imageChemSpider 16736517PubChem CID 12496332CompTox Dashboard EPA DTXSID70891942InChI InChI 1S C10H12 c1 2 4 7 5 3 1 6 8 4 10 7 9 5 6 h3 10H 1 2H2Key QKWLQWFMFQOKET UHFFFAOYSA NInChI 1 C10H12 c1 2 4 7 5 3 1 6 8 4 10 7 9 5 6 h3 10H 1 2H2Key QKWLQWFMFQOKET UHFFFAOYABSMILES C2CC5C1C4C3C1C2C3C45PropertiesChemical formula C 10H 12Molar mass 132 206 g mol 1Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Chemical nomenclature 2 Synthesis 3 Properties 4 See also 5 References 6 Further readingChemical nomenclature EditIn the year 1989 and before the synthesis of basketane historic chemists were intrigued by the structural make up of molecules specifically those in objects seen in everyday life 5 Using supramolecular chemistry molecules such as cubane and basketane were named according to their corresponding shape and historically revealed certain characteristics and personal motives of chemists at that time 5 Naming these uniquely shaped molecules were also done considering chemical nomenclature such as adding anes for single carbon carbon bonds and enes for double carbon carbon bonds to the end of the appropriate molecules 6 Synthesis EditThe synthesis of basketane reported by Masamune begins with a Diels Alder reaction between cyclooctatetraene 1 and maleic anhydride 2 giving the polycyclic anhydride 3 which photoisomerizes in acetone via an intramolecular cyclization to give 4 at a 40 yield Hydrolysis of the anhydride followed by treatment with lead tetraacetate affords the unsaturated basketene 5 which is then hydrogenated to basketane 6 2 An alternative synthetic route with better overall yield uses 1 4 benzoquinone and cyclohexa 1 3 diene as starting materials 1 4 Benzoquinone 1 is first converted to 2 5 dibromo 1 4 benzoquinone 2 which reacts in a Diels Alder reaction with cyclohexa 1 3 diene 3 to form the polycyclic diketone 4 This diketone photoisomerizes to 1 6 dibromopentacyclo 6 4 0 03 6 04 12 05 9 dodeca 2 7 dione 5 which undergoes a pseudo Favorskii rearrangement in a 25 aqueous solution of sodium hydroxide giving the dicarboxylic acid 6 The acid is decarboxylated with a modified Hunsdiecker reaction to a dibromide 7 which is reductively debrominated with tributyltin hydride to basketane 8 at a 11 yield relative to the starting material cyclohexa 1 3 diene 7 A 1994 synthesis by Binmore starts with homocubanone a cubane derivative forming basketane via the basketyl radical The synthesis functions by forcing cubane rings to be opened up via structural strain to create the chemical bonds necessary for this rigid molecule 8 This method is known as ring expansion where one part of two conjoined ringed are opened and rearranged to remove barriers between the two ring systems 9 Cyclobutylmethyl radicals that rearrange and open into structures such as basketane and cubane are favorable rearrangements with free energy barriers around 0 3 kcal mol 10 Properties EditBasketane and other polycyclic cage like molecules do not conform to simple carbon carbon bonds with angles of 109 5 degrees due to their strained system 11 The strain energy causes thermodynamic instability resulting in higher combustion and heat release 11 When taking a mass analysis the mass spectrum graph for basketane has a distinct tall peak at 39 m z distinguishing a clear cyclic structure 12 Transition metals catalyze the valence isomerization of basketane and substituted derivatives Silver perchlorate catalyzes its isomerization to the compound snoutane Using other transition metals for this reaction affords a mixture of snoutane or the corresponding snoutane derivative with a tricyclic diene The ratio of the products depends on the nature of the catalyst used and the substitutions on the basketane 13 In the hydrogenation of basketane with palladium on carbon it absorbs an equivalent amount of hydrogen gas The initial assumption by Masamune was that the bond between C4 and C5 opens to give the symmetric hydrocarbon tetracyclo 4 4 0 02 9 05 8 decane but Musso later showed that it is the bond between C3 and C4 or equivalently C4 and C7 that breaks giving the dihydrobasketane tetracyclo 4 4 0 02 5 03 8 decane 14 Further hydrogenation breaks the C5 C6 bond to give the hydrocarbon twistane 15 See also EditCubane List of chemical compounds with unusual namesReferences Edit Marchand A P 1989 Synthesis and chemistry of homocubanes bishomocubanes and trishomocubanes Chem Rev 89 5 1011 1033 doi 10 1021 cr00095a004 a b Masamune S Cuts H Hogben M G 1966 Strained systems VII Pentacyclo 4 2 2 02 5 03 8 04 7 deca 9 ene basketene Tetrahedron Lett 7 10 1017 1021 doi 10 1016 S0040 4039 00 70232 2 Dauben W G Whalen D L 1966 Pentacyclo 4 4 0 02 5 03 8 04 7 decane and pentacyclo 4 3 0 02 5 03 8 04 7 nonane Tetrahedron Lett 7 31 3743 3750 doi 10 1016 S0040 4039 01 99958 7 WO 1988002792 Pastor Ricardo C Process for depositing layers of diamond published 1988 04 21 assigned to Hughes Aircraft Co since withdrawn a b Vicens Jacques 2007 07 26 Aesthetics in chemistry Journal of Inclusion Phenomena and Macrocyclic Chemistry 58 3 4 327 328 doi 10 1007 s10847 006 9161 7 ISSN 0923 0750 S2CID 94479873 2 3 2 www nanomedicine com Retrieved 2021 02 23 Gassman Paul G Yamaguchi Ryohei 1978 1 8 Bishomocubane The Journal of Organic Chemistry 43 24 4654 4656 doi 10 1021 jo00418a028 ISSN 0022 3263 Binmore Gavin T Della Ernest W Elsey Gordon M Head Nicholas J Walton John C April 1994 Homolytic Reactions of Homocubane and Basketane Rearrangement of the 9 Basketyl Radical by Multiple beta Scissions Journal of the American Chemical Society 116 7 2759 2766 doi 10 1021 ja00086a009 ISSN 0002 7863 Ring Opening versus Ring Expansion in Rearrangement of Bicyclic Cyclobutylcarbinyl Radicals dx doi org doi 10 1021 jo702164r s002 Retrieved 2021 03 16 Shi Jing Chong Sha Sha Fu Yao Guo Qing Xiang Liu Lei 2008 02 01 Ring Opening versus Ring Expansion in Rearrangement of Bicyclic Cyclobutylcarbinyl Radicals The Journal of Organic Chemistry 73 3 974 982 doi 10 1021 jo702164r ISSN 0022 3263 PMID 18179235 a b Marchand Alan P 1989 07 01 Synthesis and chemistry of homocubanes bishomocubanes and trishomocubanes Chemical Reviews 89 5 1011 1033 doi 10 1021 cr00095a004 ISSN 0009 2665 Basketane MS Spectrum SpectraBase spectrabase com Retrieved 2021 03 16 Paquette Leo A Boggs Roger A Farnham William B Beckley Ronald S 1975 Silver I ion catalyzed rearrangements of strained sigma bonds XXIX Influence of structural features on the course of transition metal catalyzed 1 8 bishomocubane rearrangements Journal of the American Chemical Society 97 5 1112 1118 doi 10 1021 ja00838a026 ISSN 0002 7863 Andre Sasaki N Zunker Reinhard Musso Hans 1973 Welche C C Bindung wird bei der Hydrierung von Basketanderivaten geoffnet Chemische Berichte 106 9 2992 3000 doi 10 1002 cber 19731060930 ISSN 0009 2940 Musso Hans 1975 Hydrogenolyse kleiner Kohlenstoffringe II Uber die Hydrierung von Basketan und Snoutanderivaten Chemische Berichte 108 1 337 356 doi 10 1002 cber 19751080143 ISSN 0009 2940 Further reading EditBinmore Gavin T Della Ernest W Elsey G M Head N J Walton J C 1994 Homolytic Reactions of Homocubane and Basketane Rearrangement of the 9 Basketyl Radical by Multiple b Scissions J Am Chem Soc 116 7 2759 2766 doi 10 1021 ja00086a009 This article about a hydrocarbon is a stub You can help Wikipedia by expanding it vte Retrieved from https en wikipedia org w index php title Basketane amp oldid 1136351140, wikipedia, wiki, book, books, library,
