Difference between revisions of "9-Borabicyclononane"
Physchim62 (talk | contribs) |
Physchim62 (talk | contribs) |
||
| (2 intermediate revisions by the same user not shown) | |||
| Line 9: | Line 9: | ||
| CASNo = 280-64-8 | | CASNo = 280-64-8 | ||
| EINECS = 206-000-9 | | EINECS = 206-000-9 | ||
| − | | ChemSpiderID = | + | | ChemSpiderID = 71299 |
| PubChem = | | PubChem = | ||
| SMILES = C1(B2)CCCC2CCC1 | | SMILES = C1(B2)CCCC2CCC1 | ||
| − | | InChI = 1/ | + | | InChI = 1/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2 |
| − | | StdInChI = 1S/ | + | | StdInChI = 1S/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2 |
| − | | InChIKey = | + | | InChIKey = FEJUGLKDZJDVFY-UHFFFAOYAE |
| − | | StdInChIKey = | + | | StdInChIKey = FEJUGLKDZJDVFY-UHFFFAOYSA-N |
| − | |||
}} | }} | ||
| Section2 = {{Chembox Properties | | Section2 = {{Chembox Properties | ||
| − | | Formula = C<sub> | + | | Formula = C<sub>8</sub>H<sub>15</sub>B |
| − | | MolarMass = | + | | MolarMass = 122.02 g/mol |
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
| − | |||
}} | }} | ||
}} | }} | ||
| Line 58: | Line 37: | ||
| PubChem = | | PubChem = | ||
| SMILES = [H]1[B@]5([H][B@@]13C2CCCC3CCC2)C4CCCC5CCC4 | | SMILES = [H]1[B@]5([H][B@@]13C2CCCC3CCC2)C4CCCC5CCC4 | ||
| − | | InChI = 1/C16H30B2/c1-5-13-7-2-8-14(6-1)17(13)19-18(20-17)15-9-3- | + | | InChI = {{InChIwrap|1/C16H30B2/c1-5-13-7-2-8 -14(6-1)17(13)19-18(20-17)15-9 -3-10-16(18)12-4-11-15/h13-16H ,1-12H2}} |
| − | | StdInChI = 1S/C16H30B2/c1-5-13-7-2-8-14(6-1)17(13)19-18(20-17)15-9-3- | + | | StdInChI = {{InChIwrap|1S/C16H30B2/c1-5-13-7-2- 8-14(6-1)17(13)19-18(20-17)15- 9-3-10-16(18)12-4-11-15/h13-16 H,1-12H2}} |
| InChIKey = QQDDHBYRUTZKSX-UHFFFAOYAH | | InChIKey = QQDDHBYRUTZKSX-UHFFFAOYAH | ||
| StdInChIKey = QQDDHBYRUTZKSX-UHFFFAOYSA-N | | StdInChIKey = QQDDHBYRUTZKSX-UHFFFAOYSA-N | ||
| Line 84: | Line 63: | ||
| ExploLimits = | | ExploLimits = | ||
| PEL = | | PEL = | ||
| + | }} | ||
| + | }} | ||
| + | {{FixBunching|mid}} | ||
| + | {{chembox | ||
| + | | Name = 9-Borabicyclo[3.3.1]nonane—tetrahydrofuran | ||
| + | | Section1 = {{Chembox Identifiers | ||
| + | | InChI={{InChIwrap|1/C12H23BO/c1-2-10-14(9- 1)13-11-5-3-6-12(13)8-4-7-11/h 11-13H,1-10H2}} | ||
}} | }} | ||
}} | }} | ||
{{FixBunching|end}} | {{FixBunching|end}} | ||
| − | '''9-Borabicyclo[3.3.1]nonane''' or '''9-BBN''' is an [[organoborane]] compound. This colourless solid is used in [[organic chemistry]] as a [[hydroboration]] [[reagent]] | + | '''9-Borabicyclo[3.3.1]nonane''' or '''9-BBN''' is an [[organoborane]] compound. This colourless solid is used in [[organic chemistry]] as a [[hydroboration]] [[reagent]].<ref name="BrownBook">{{citation | last = Brown | first = H. C. | authorlink = Herbert C. Brown | title = Organic Syntheses via Boranes | publisher = Wiley | location = New York | year = 1975 | isbn = 0-471-11280-1}}.</ref> |
| − | 9-BBN is prepared by the reaction of [[1,5-cyclooctadiene]] and [[borane]] adducts, usually in etherial solvents.<ref name="BrownJOC">{{citation | title = Simple, remarkably efficient route to high purity, crystalline 9-borabicyclo[3.3.1]nonane (9-BBN) dimer | first1 = John A. | last1 = Soderquist | first2 = Herbert C. |last2 = Brown | authorlink2 = Herbert C. Brown | journal = J. Org. Chem. | year = 1981 | volume = 46 | issue = 22 | pages = 4599–4600 | doi = 10.1021/jo00335a067}}.</ref><ref name="OrgSynthPrepn">{{OrgSynth | first1 = John A. | last1 = Soderquist | first2 = Alvin |last2 = Negron | title = 9-Borabicyclo[3.3.1]nonane Dimer | prep = cv9p0095 | year = 1992 | volume = 70 | pages = 169 | collvol = 9 | collvolpages = 95}}.</ref> The compound is commercially available as a solution in [[tetrahydrofuran]] and as a solid. | + | 9-BBN was first prepared by the thermal redistribution of 9-propyl-9-BBN,<ref>{{citation | last = Köster | first = R. | title = Cyclische Alkyldiborane | journal = Angew. Chem. | year = 1960 | volume = 72 | issue = 17 | page = 626–27 | doi = 10.1002/ange.19600721705}}.</ref> but it is more usually prepared by the reaction of [[1,5-cyclooctadiene]] and [[borane]] adducts, usually in etherial solvents.<ref name="BrownJOC">{{citation | title = Simple, remarkably efficient route to high purity, crystalline 9-borabicyclo[3.3.1]nonane (9-BBN) dimer | first1 = John A. | last1 = Soderquist | first2 = Herbert C. | last2 = Brown | authorlink2 = Herbert C. Brown | journal = J. Org. Chem. | year = 1981 | volume = 46 | issue = 22 | pages = 4599–4600 | doi = 10.1021/jo00335a067}}.</ref><ref name="OrgSynthPrepn">{{OrgSynth | first1 = John A. | last1 = Soderquist | first2 = Alvin | last2 = Negron | title = 9-Borabicyclo[3.3.1]nonane Dimer | prep = cv9p0095 | year = 1992 | volume = 70 | pages = 169 | collvol = 9 | collvolpages = 95}}.</ref> The compound is commercially available as a solution in [[tetrahydrofuran]] and as a solid. |
| − | The solid is a hydride-bridged dimer:<ref name="BrownBook"/> solutions in THF and other donor solvents contain monomeric adducts with a solvent molecule, eg 9-BBN·THF. | + | The solid is a hydride-bridged dimer:<ref name="BrownBook"/> solutions in THF and other donor solvents contain monomeric adducts with a solvent molecule, eg 9-BBN·THF, although dimer (without solvent molecules) can be [[Recrystallization|recrystallized]] from [[1,2-dimethoxyethane]] (DME).<ref name="OrgSynthPrepn"/> The solid is relatively stable to air compared with other dialkylboranes, although it should be stored under an inert atmosphere. It may be handled for short periods in air, and a sample stored in air for one month showed only limited decomposition.<ref name="OrgSynthPrepn"/> Solutions of 9-BBN are handled using normal [[air-free technique]]s, eg [[Schlenk line]] and [[cannula]]s. |
9-BBN is especially useful in [[Suzuki reaction]]s.<ref>{{OrgSynth | first1 = Tatsuo | last1 = Ishiyama | first2 = Norio | last2 = Miyaura | first3 = Akira | last3 = Suzuki | title = Palladium(0)-catalyzed reaction of 9-alkyl-9-borabicyclo[3.3.1]nonane with 1-bromo-1-phenylthioethene: 4-(3-cyclohexenyl)-2-phenylthio-1-butene | prep = cv9p0107 | year = 1993 | volume = 71 | pages = 89 | collvol = 9 | collvolpages = 107}}.</ref> Its highly stereoselective addition on olefins allows the preparation of terminal alcohols by subsequent oxidative cleavage with [[hydrogen peroxide]] in aqueous [[potassium hydroxide]]. The steric demand of 9-BBN greatly suppresses the formation of the 2-substituted isomer compared to the use of [[borane]]. | 9-BBN is especially useful in [[Suzuki reaction]]s.<ref>{{OrgSynth | first1 = Tatsuo | last1 = Ishiyama | first2 = Norio | last2 = Miyaura | first3 = Akira | last3 = Suzuki | title = Palladium(0)-catalyzed reaction of 9-alkyl-9-borabicyclo[3.3.1]nonane with 1-bromo-1-phenylthioethene: 4-(3-cyclohexenyl)-2-phenylthio-1-butene | prep = cv9p0107 | year = 1993 | volume = 71 | pages = 89 | collvol = 9 | collvolpages = 107}}.</ref> Its highly stereoselective addition on olefins allows the preparation of terminal alcohols by subsequent oxidative cleavage with [[hydrogen peroxide]] in aqueous [[potassium hydroxide]]. The steric demand of 9-BBN greatly suppresses the formation of the 2-substituted isomer compared to the use of [[borane]]. | ||
| + | |||
| + | == Spectroscopic data == | ||
| + | From Soderquist & Negron (1992):<ref name="OrgSynthPrepn"/> | ||
| + | *<sup>1</sup>H-NMR (300 MHz, C<sub>6</sub>D<sub>6</sub>): ''δ''<sub>H</sub> = 1.44–1.57 (m, 4H), 1.58–1.74 (m, 12H), 1.83–2.07 (m, 12H). A [[HETCOR]] experiment revealed that resonances from protons on each of the methylene carbons were superimposed upon one another. | ||
| + | *<sup>13</sup>C-NMR (75 MHz, C<sub>6</sub>D<sub>6</sub>): ''δ''<sub>C</sub> = 20.2 (br, C-1,5), 24.3 (C-3,7), 33.6 (C-2,4,6,8) | ||
| + | *<sup>11</sup>B-NMR (96 MHz, C<sub>6</sub>D<sub>6</sub>): ''δ''<sub>B</sub> = 28 | ||
== References == | == References == | ||
Latest revision as of 11:41, 23 August 2009
- The correct title of this article is 9-Borabicyclo[3.3.1]nonane. The substitution or omission of any < > [ ] { } is due to technical restrictions.
| ||||||||||||||||||||||||||||||||||||||||||||
| ||||||||||||||||||||||||||||||||||||||||||||
| ||||||||||||||||||||||||||||||||||||||||||||
9-Borabicyclo[3.3.1]nonane or 9-BBN is an organoborane compound. This colourless solid is used in organic chemistry as a hydroboration reagent.[1]
9-BBN was first prepared by the thermal redistribution of 9-propyl-9-BBN,[2] but it is more usually prepared by the reaction of 1,5-cyclooctadiene and borane adducts, usually in etherial solvents.[3][4] The compound is commercially available as a solution in tetrahydrofuran and as a solid.
The solid is a hydride-bridged dimer:[1] solutions in THF and other donor solvents contain monomeric adducts with a solvent molecule, eg 9-BBN·THF, although dimer (without solvent molecules) can be recrystallized from 1,2-dimethoxyethane (DME).[4] The solid is relatively stable to air compared with other dialkylboranes, although it should be stored under an inert atmosphere. It may be handled for short periods in air, and a sample stored in air for one month showed only limited decomposition.[4] Solutions of 9-BBN are handled using normal air-free techniques, eg Schlenk line and cannulas.
9-BBN is especially useful in Suzuki reactions.[5] Its highly stereoselective addition on olefins allows the preparation of terminal alcohols by subsequent oxidative cleavage with hydrogen peroxide in aqueous potassium hydroxide. The steric demand of 9-BBN greatly suppresses the formation of the 2-substituted isomer compared to the use of borane.
Spectroscopic data
From Soderquist & Negron (1992):[4]
- 1H-NMR (300 MHz, C6D6): δH = 1.44–1.57 (m, 4H), 1.58–1.74 (m, 12H), 1.83–2.07 (m, 12H). A HETCOR experiment revealed that resonances from protons on each of the methylene carbons were superimposed upon one another.
- 13C-NMR (75 MHz, C6D6): δC = 20.2 (br, C-1,5), 24.3 (C-3,7), 33.6 (C-2,4,6,8)
- 11B-NMR (96 MHz, C6D6): δB = 28
References
- ↑ 1.0 1.1 Brown, H. C. Organic Syntheses via Boranes; Wiley: New York, 1975. ISBN 0-471-11280-1.
- ↑ Köster, R. Cyclische Alkyldiborane. Angew. Chem. 1960, 72 (17), 626–27. DOI: 10.1002/ange.19600721705.
- ↑ Soderquist, John A.; Brown, Herbert C. Simple, remarkably efficient route to high purity, crystalline 9-borabicyclo[3.3.1]nonane (9-BBN) dimer. J. Org. Chem. 1981, 46 (22), 4599–4600. DOI: 10.1021/jo00335a067.
- ↑ 4.0 4.1 4.2 4.3 Soderquist, John A.; Negron, Alvin 9-Borabicyclo[3.3.1]nonane Dimer. Org. Synth. 1992, 70, 169, <http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv9p0095>; Coll. Vol., 9, 95.
- ↑ Ishiyama, Tatsuo; Miyaura, Norio; Suzuki, Akira Palladium(0)-catalyzed reaction of 9-alkyl-9-borabicyclo[3.3.1]nonane with 1-bromo-1-phenylthioethene: 4-(3-cyclohexenyl)-2-phenylthio-1-butene. Org. Synth. 1993, 71, 89, <http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv9p0107>; Coll. Vol., 9, 107.
External links
| Error creating thumbnail: Unable to save thumbnail to destination |  |
This page was originally imported from Wikipedia, specifically this version of the article "9-Borabicyclononane". Please see the history page on Wikipedia for the original authors. This WikiChem article may have been modified since it was imported. It is licensed under the Creative Commons Attribution–Share Alike 3.0 Unported license. |
