Difference between revisions of "9-Borabicyclononane"
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{{bracketed|title=9-Borabicyclo[3.3.1]nonane}} | {{bracketed|title=9-Borabicyclo[3.3.1]nonane}} | ||
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{{chembox | {{chembox | ||
| Name = 9-Borabicyclo[3.3.1]nonane | | Name = 9-Borabicyclo[3.3.1]nonane | ||
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| 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 |
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}} | }} | ||
| 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 |
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{{chembox | {{chembox | ||
| Name = 9-Borabicyclo[3.3.1]nonane dimer | | Name = 9-Borabicyclo[3.3.1]nonane dimer | ||
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| 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 | ||
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}} | }} | ||
}} | }} | ||
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| + | | 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}} | ||
| + | }} | ||
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| + | '''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 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, 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]]. | |
| − | + | == 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 == | ||
| − | {{ | + | {{reflist}} |
== External links == | == External links == | ||
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.
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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
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