| Revision as of 17:39, 27 April 2011 editR'n'B (talk | contribs)Administrators421,571 editsm Unlinked: C6H6← Previous edit |
Latest revision as of 17:25, 28 December 2022 edit undoAntandBee (talk | contribs)20 editsm corrected the initials of the first two authors of reference 2 |
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{{chembox |
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| verifiedrevid = 426240665 |
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| ImageFile = Bicycloprop-2-enyl.svg |
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| ImageFile = Bicycloprop-2-enyl.svg |
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| ImageSize = 100px |
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| ImageFile1 = 3,3'-bicyclopropenyl-from-xtal-1993-Mercury-3D-balls.png |
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| IUPACName = Bicycloprop-2-enyl |
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| PIN = -1,1′-diene |
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| OtherNames = 3,3'-bicyclopropenyl |
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| OtherNames = 1,1′-Bi(cycloprop-2-en-1-yl)<br />3,3'-Bicyclopropenyl |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CAS = |
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| CASNo_Ref = {{cascite|changed|??}} |
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| PubChem = |
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| CASNo = 62595-44-2 |
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| PubChem = 143919 |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| InChI = |
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| ChemSpiderID = 126965 |
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| SMILES = C\1=C\C/1C\2/C=C/2 |
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| InChI = 1/C6H6/c1-2-5(1)6-3-4-6/h1-6H |
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| InChIKey = HVWGZGIZCKXHJV-UHFFFAOYAR |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 1S/C6H6/c1-2-5(1)6-3-4-6/h1-6H |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = HVWGZGIZCKXHJV-UHFFFAOYSA-N |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| Section2 = {{Chembox Properties |
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| Formula = C<sub>6</sub>H<sub>6</sub> |
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| Formula = C<sub>6</sub>H<sub>6</sub> |
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| MolarMass = 78.1 g/mol |
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| MolarMass = 78.1 g/mol |
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| MeltingPt = 198 K |
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| MeltingPtK = 198 |
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| Section3 = {{Chembox Hazards |
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'''Bicyclopropenyl''' (bicycloprop-2-enyl, C<sub>6</sub>H<sub>6</sub>) is an ] and one of several ]s of ]. The molecule can be described as two coupled ] units. The positions of the ] groups can vary and therefore two other isomers are known: bicycloprop-1,2-enyl and bicyclopropen-1-yl. |
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'''Bicyclopropenyl''' (bicycloprop-2-enyl, C<sub>6</sub>H<sub>6</sub>) is an ] and one of several ]s of ]. The molecule can be described as two coupled ] units. The positions of the ] groups can vary and therefore two other isomers are known: bicycloprop-1,2-enyl and bicyclopropen-1-yl. |
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The synthesis of all three isomers was reported in 1989 By Billups and Haley.<ref>{{cite DOI|10.1002/anie.198917111}}</ref><ref>{{cite DOI|10.1016/S0040-4020(01)89261-9}}</ref> The 3,3 isomer was formed in two steps by reaction of ''1,4-bis(trimethylsilyl)buta-1,3-diene'' with ] and ], introducing two cyclopropane rings into the molecule. The bis(2-chloro-3-(trimethylsilyl)cyclopropan-1-yl) formed is reacted with ]. In this latter reaction fluoride couples to the trimethylsilyl group, in the process forming the double bond and forcing the chlorine atom to leave as chloride. In presence of ] ions bicycloprop-2-enyl rearranges to ]. The compound can also be trapped by ]. Above -10 °C it decomposes with ]. |
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The synthesis of all three isomers was reported in 1989 By Billups and Haley.<ref>{{Cite journal| doi = 10.1002/anie.198917111| title = Bicycloprop-2-enyl (C6H6)| year = 1989| last1 = Billups | first1 = W. E.| last2 = Haley | first2 = M. M.| journal = Angewandte Chemie International Edition in English| volume = 28| issue = 12| pages = 1711 }}</ref><ref>{{Cite journal| doi = 10.1016/S0040-4020(01)89261-9| title = Synthesis of the bicyclopropenyls | year = 1994| first4 = D.| last4 = Bläser | first3 = R.| last3 = Boese | first2 = M. M.| last2 = Haley| last1 = Billups | first1 = W. E.| journal = Tetrahedron| volume = 50| issue = 36| pages = 10693–10700 }}</ref> The 3,3 isomer was formed in two steps by reaction of ''1,4-bis(trimethylsilyl)buta-1,3-diene'' with ] and ], introducing two cyclopropane rings into the molecule. The bis(2-chloro-3-(trimethylsilyl)cyclopropan-1-yl) formed is reacted with ]. In this latter reaction fluoride couples to the trimethylsilyl group, in the process forming the double bond and forcing the chlorine atom to leave as chloride. In presence of ] ions bicycloprop-2-enyl rearranges to ]. The compound can also be trapped by ]. Above -10 °C it decomposes with ]. |
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An ] has been reported <ref>{{cite DOI|10.1021/ja00055a052}}</ref>. The ] for the central bond is short by 1.503 ] (150.3 ]). |
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An ] has been reported.<ref>{{Cite journal| doi = 10.1021/ja00055a052| title = Structure and photoelectron spectrum of 3,3'-bicyclopropenyl| year = 1993| last1 = Boese | first1 = R.| last2 = Blaeser | first2 = D.| last3 = Gleiter | first3 = R.| last4 = Pfeifer | first4 = K. H.| last5 = Billups | first5 = W. E.| last6 = Haley | first6 = M. M.| journal = Journal of the American Chemical Society| volume = 115| issue = 2| pages = 743 }}</ref> The ] for the central bond is short by 1.503 ] (150.3 ]). |
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The other two isomers are increasingly unstable. Bicycloprop-1-enyl can only be detected in trapping experiments. |
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The other two isomers are increasingly unstable. Bicycloprop-1-enyl can only be detected in trapping experiments. |
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!colspan="3" | Properties benzene valence isomers |
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!colspan="3" | Properties benzene valence isomers |
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! Compound || Calc. ] <ref name=cheung>{{cite DOI|10.1016/S0166-1280(98)00189-4}}</ref><ref name=chueng_details>G2 level, isodesmic bond separation scheme</ref>|| Calc. Heat of formation <ref name=cheung/><ref name=chueng_details/> |
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! Compound || Calc. ]<ref name=cheung>{{Cite journal| doi = 10.1016/S0166-1280(98)00189-4| title = Ab initio calculations of the heats of formation for (CH)6 isomers| year = 1998| last1 = Cheung | first1 = Y.| journal = Journal of Molecular Structure: THEOCHEM| volume = 454| pages = 17–20 }}</ref><ref name=chueng_details>G2 level, isodesmic bond separation scheme</ref>|| Calc. Heat of formation <ref name=cheung/><ref name=chueng_details/> |
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! || 0 K (KJ/mole) || 298 K (KJ/mole) |
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! || 0 K (KJ/mole) || 298 K (KJ/mole) |
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| ] || 100.5 || 82.0 |
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| ] || 100.5 || 82.0 |
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| ] || 397.5 || 378.1 |
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| ] || 397.5 || 378.1 |
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| ] || 567.2 || 547.0 |
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| ] || 567.2 || 547.0 |
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| Bicycloprop-2-enyl || 593.6 || 578.8 |
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| Bicycloprop-2-enyl || 593.6 || 578.8 |
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Derivatives can be much more stable, for example perfluorohexamethylbicyclopropenyl that must be heated to 360 °C to be as unstable.<ref>{{Cite journal|last=Billups|first=W. E.|last2=M. Haley|first2=Michael|last3=Boese|first3=Roland|last4=Bläser|first4=Dieter|date=1994-01-01|title=Synthesis of the bicyclopropenyls|journal=Tetrahedron|series=The International Journal for the Rapid Publication of Critical|volume=50|issue=36|pages=10693–10700|doi=10.1016/S0040-4020(01)89261-9}}</ref> |
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==References== |
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==References== |
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