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{{short description|Chemical compound}} |
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{{correct title|reason=bracket|Propellane}} |
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{{correct title|reason=bracket|edit=omission|Propellane}} |
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{{Chembox |
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{{Chembox |
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| verifiedrevid = 406641218 |
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|Watchedfields = changed |
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| Name=Propellane |
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|verifiedrevid = 418039735 |
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| ImageFileL1 = 2.2.2-propellane.svg |
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|Name=Propellane |
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| ImageSizeL1 = 100px |
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| ImageFileR1 = 2.2.2-propellane.png |
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|ImageFileL1 = 2.2.2-propellane.svg |
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|ImageFileR1 = 2.2.2-propellane.png |
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| ImageSizeR1 = 150px |
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|ImageSizeR1 = 150px |
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| IUPACName = Tricyclooctane |
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|PIN = Tricyclooctane |
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| OtherNames = |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 36120-88-4 |
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|CASNo = 36120-88-4 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo_Ref = {{cascite|correct|??}} |
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| PubChem = |
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|PubChem = 564666 |
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|ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| SMILES = C1C23C(CC2)(CC3)C1}} |
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|ChemSpiderID = 490864 |
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| Section2 = {{Chembox Properties |
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|SMILES = C1C23C(CC2)(CC3)C1 |
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| C=8 | H=12 |
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|InChI = 1/C8H12/c1-2-8-5-3-7(1,8)4-6-8/h1-6H2 |
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| Appearance = |
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|InChIKey = GPMHXZWOEIWUPW-UHFFFAOYAI |
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| Density = |
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|StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| MeltingPt = |
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|StdInChI = 1S/C8H12/c1-2-8-5-3-7(1,8)4-6-8/h1-6H2 |
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| BoilingPt = |
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|StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| Solubility = }} |
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|StdInChIKey = GPMHXZWOEIWUPW-UHFFFAOYSA-N}} |
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| Section3 = {{Chembox Hazards |
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|Section2={{Chembox Properties |
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| MainHazards = |
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|C=8 | H=12 |
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| Autoignition = }} |
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'''Propellane''', formally '''tricyclooctane''' is an ], a member of the ] family. It is a ] with formula C<sub>8</sub>H<sub>12</sub>, or C<sub>2</sub>(=C<sub>2</sub>H<sub>4</sub>)<sub>3</sub>. Its molecule has three rings with four ] atoms each, sharing one C-C bond. |
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'''Propellane''', formally '''tricyclooctane''' is an ], a member of the ] family. It is a ] with formula C<sub>8</sub>H<sub>12</sub>, or C<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>)<sub>3</sub>. Its molecule has three rings with four ] atoms each, sharing one C–C bond. |
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This compound is unstable (although not as much as propellane]]). The bond angles on the shared carbons are considerably strained: three of them are close to 90 degrees, the other three to 120 degrees. The ] is estimated to be 93 kcal/mol (390 kJ/mol). |
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This compound is unstable (although not as much as propellane]]; however it is less persistent than propellane<ref>{{Cite web|url=https://www.thieme.de/shop/Houben-Weyl--SoS/de-Meijere-Butenschoen-Chow-Fitjer-Haufe-Houben-Weyl-Methods-of-Organic-Chemistry-9783131819840/p/000000009583004404|archive-url=https://web.archive.org/web/20171022033632/https://www.thieme.de/shop/Houben-Weyl--SoS/de-Meijere-Butenschoen-Chow-Fitjer-Haufe-Houben-Weyl-Methods-of-Organic-Chemistry-9783131819840/p/000000009583004404|url-status=dead|archive-date=October 22, 2017|title=Houben-Weyl Methods of Organic Chemistry Vol. E 17e, 4th Edition Supplement (E-Book PDF) - Thieme.de - Thieme Webshop - Armin de Meijere, Holger Butenschön, Hak-Fun Chow, Lutz Fitjer, Günter Haufe|website=Thieme Webshop|language=de|access-date=2017-10-21}}</ref>). The bond angles on the shared carbons are considerably strained: three of them are close to 90°, the other three to 120°. The ] is estimated to be 93 kcal/mol (390 kJ/mol). |
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==Synthesis== |
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==Synthesis== |
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Propellane was first ] in 1973 by the group of ] (who had earlier obtained ]),<ref> |
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Propellane was first ] in 1973 by the group of ] (who had earlier obtained ]),<ref>{{cite journal|first1=Philip E.|last1=Eaton|first2=George H.|last2=Temme|authorlink=Philip Eaton|date=1973|title=Propellane system|journal=]|volume=95|issue=22|pages=7508–7510|doi=10.1021/ja00803a052}}</ref> according to the following scheme: |
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Philip E. Eaton and George H. Temme (1973), ''Propellane system'' ], volume 95 issue 22, pp. 7508–7510; {{DOI|10.1021/ja00803a052}} |
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</ref> according to the following scheme: |
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:propellane skeleton.]] |
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:propellane skeleton.]] |
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The synthesis begins with ] ] of ] on the ] derivative '''1''' to produce the ] '''2''', followed by ] with ] of ] to cyclobutene '''3''', followed by another cycloaddition with ethylene to '''4'''. This compound is converted to the ] ketone '''5''' by deprotonation (using ] and ]) and reaction with ]. The ketone then undergoes ] to ] '''6'''. ] forms the ] '''7''', another diazotation yields the ketene '''8''', which undergoes Wolff rearrangement again to the ketene '''9'''. Reaction with ] affords the propellane backbone with a ] substituent '''10'''. |
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The synthesis begins with ] ] of ] on the ] derivative '''1''' to produce the ] '''2''', followed by ] with ] of ] to cyclobutene '''3''', followed by another cycloaddition with ethylene to '''4'''. This compound is converted to the ] ketone '''5''' by deprotonation (using ] and ]) and reaction with ]. The ketone then undergoes ] to ] '''6'''. ] forms the ] '''7''', another diazotation yields the ] ketone '''8''', which undergoes Wolff rearrangement again to the ketene '''9'''. Reaction with ] affords the propellane backbone with a ] substituent '''10'''. |
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The final product '''10''' was found to spontaneously ] in solution to the ] ] '''11''', with a ] of 28 minutes at room temperature. |
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The final product '''10''' was found to spontaneously ] in solution to the ] ] '''11''', with a ] of 28 minutes at room temperature. |
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==Derivatives== |
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==Derivatives== |
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A highly fluorinated propellane was also synthesized by the group of David Lemal <ref>Zhang, Y.; Smith, J.R.; Lemal, D.M. (1996) "Octafluorobicyclohex-1(4)-ene: A Greatly Strained Alkene with Novel Reactivity" ''J. Amer. Chem. Soc.'', volume 39, page 9454. {{doi|10.1021/ja961656o}}</ref>. |
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A highly fluorinated propellane was also synthesized by the group of David Lemal.<ref>{{cite journal|last1=Zhang|first1=Y.|last2=Smith|first2=J.R.|last3=Lemal|first3=D.M.|date=1996|title=Octafluorobicyclohex-1(4)-ene: A Greatly Strained Alkene with Novel Reactivity|journal=]|volume=118|issue=39 |page=9454|doi=10.1021/ja961656o}}</ref> |
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== See also == |
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== See also == |
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* -Propellane]] |
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* Propellane]] |
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* -Propellane]] |
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== References == |
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== References == |
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{{DEFAULTSORT:Propellane, 2.2.2}} |
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{{DEFAULTSORT:Propellane, 2.2.2}} |
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