Difference between revisions of "9-Borabicyclononane"

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{{wrongtitle|title=9-Borabicyclo[3.3.1]nonane}}
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{{bracketed|title=9-Borabicyclo[3.3.1]nonane}}
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{{chembox
 
{{chembox
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| Name = 9-Borabicyclo[3.3.1]nonane
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| IUPACName = 9-Borabicyclo[3.3.1]nonane
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|  OtherNames = Borabicyclononane
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| Section1 = {{Chembox Identifiers
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|  Abbreviations = 9-BBN
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|  CASNo = 280-64-8
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|  EINECS = 206-000-9
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|  ChemSpiderID = 71299
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|  PubChem =
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|  SMILES = C1(B2)CCCC2CCC1
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|  InChI = 1/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2
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|  StdInChI = 1S/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2
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|  InChIKey = FEJUGLKDZJDVFY-UHFFFAOYAE
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|  StdInChIKey = FEJUGLKDZJDVFY-UHFFFAOYSA-N
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  }}
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| Section2 = {{Chembox Properties
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|  Formula = C<sub>8</sub>H<sub>15</sub>B
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|  MolarMass = 122.02 g/mol
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  }}
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}}
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{{chembox
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| Name = 9-Borabicyclo[3.3.1]nonane dimer
 
| ImageFileL1 = 9-BBN dimer structure.svg
 
| ImageFileL1 = 9-BBN dimer structure.svg
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| ImageSizeL1 = 80 px
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|   ImageSizeL1 = 80 px
 
| ImageFileR1 = 9-BBN-dimer-xtal-3D-sticks-skeletal.png
 
| ImageFileR1 = 9-BBN-dimer-xtal-3D-sticks-skeletal.png
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| ImageSizeR1 = 120px
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|   ImageSizeR1 = 120px
 
| ImageFile2 = BBN_Crystals.jpg
 
| ImageFile2 = BBN_Crystals.jpg
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| IUPACName = 9-Borabicyclo[3.3.1]nonane
 
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| OtherNames = Borabicyclononane
 
 
| Section1 = {{Chembox Identifiers
 
| Section1 = {{Chembox Identifiers
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| Abbreviations = 9-BBN
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|   Abbreviations = 9-BBN
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| CASNo = 280-64-8
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|   CASNo = 21205-91-4
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| EINECS = 206-000-9
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|   EINECS =  
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| ChemSpiderID = 4885947
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|   ChemSpiderID = 21241191
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| PubChem =
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|   PubChem =
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| SMILES = C1(B2)CCCC2CCC1
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|   SMILES = [H]1[B@]5([H][B@@]13C2CCCC3CCC2)C4CCCC5CCC4
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| InChI = 1/C8H14B/c1-3-7-5-2-6-8(4-1)9-7/h7-8H,1-6H2
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|   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}}
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| InChIKey = AMKGKYQBASDDJB-UHFFFAOYAO
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|  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}}
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| StdInChIKey = AMKGKYQBASDDJB-UHFFFAOYSA-N
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|   InChIKey = QQDDHBYRUTZKSX-UHFFFAOYAH
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| RTECS =
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|   StdInChIKey = QQDDHBYRUTZKSX-UHFFFAOYSA-N
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| MeSHName =
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|   RTECS =
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| ChEBI =
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  }}
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| KEGG =
 
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| ATCCode_prefix =
 
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| ATCCode_suffix =
 
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| ATC_Supplemental =}}
 
 
| Section2 = {{Chembox Properties
 
| Section2 = {{Chembox Properties
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| Formula = C<sub>16</sub>H<sub>26</sub>B<sub>2</sub>
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|   Formula = C<sub>16</sub>H<sub>26</sub>B<sub>2</sub>
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| MolarMass = 244.04 g/mol
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|   MolarMass = 244.04 g/mol
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| Appearance =
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|   Appearance = white solid
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| Density = 0.894 g/cm<sup>3</sup>
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|   Density = 0.894 g/cm<sup>3</sup>
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| MeltingPt = 153-155 °C
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|   MeltingPt = 153–155 °C
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| Melting_notes =
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|   Melting_notes =
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| BoilingPt =
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|   BoilingPt =
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| Boiling_notes =
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|   Boiling_notes =
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| Solubility = Reacts
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|   Solubility = reacts
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| SolubleOther =
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  }}
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| Solvent =
 
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| pKa =
 
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| pKb = }}
 
 
| Section7 = {{Chembox Hazards
 
| Section7 = {{Chembox Hazards
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| EUClass =
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|   EUIndex = not listed
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| EUIndex =
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|   GHSPictograms =  
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| MainHazards =
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|   GHSSignalWord =  
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| NFPA-H =
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|   HPhrases =  
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| NFPA-F =
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|   FlashPt =
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| NFPA-R =
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|   Autoignition =
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| NFPA-O =
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|   ExploLimits =
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| RPhrases = {{R11}} {{R14/15}} {{R36/37/38}}
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|   PEL =  
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| SPhrases = {{S7/9}} {{S16}} {{S33}} {{S7/8}} {{S26}} {{S37/39}}  
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  }}
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| FlashPt =
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| Autoignition =
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{{chembox
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| ExploLimits =
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| Name = 9-Borabicyclo[3.3.1]nonane—tetrahydrofuran
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| PEL = }}
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| Section1 = {{Chembox Identifiers
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|  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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  }}
 
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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>
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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&#91;3.3.1&#93;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&#91;3.3.1&#93;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.
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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.
  
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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]]. The compound exists as a hydride-bridged dimer, which easily cleaves in the presence of reducible substrates.<ref>Brown, H. C. “Organic Syntheses via Boranes” John Wiley & Sons, Inc. New York: 1975.  ISBN 0-471-11280-1.</ref> Like other organoboron compounds, 9-BBN is [[pyrophoric]].
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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&#91;3.3.1&#93;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]].
  
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9-BBN is prepared by the reaction of [[1,5-cyclooctadiene]] and [[borane]] usually in etherial solvents.<ref>{{cite journal | title = <nowiki>Simple, remarkably efficient route to high purity, crystalline 9-borabicyclo[3.3.1]nonane (9-BBN) dimer</nowiki> | author = John A. Soderquist, [[Herbert C. Brown]] | journal = [[J. Org. Chem.]] | year = 1981 | volume = 46 | issue = 22 | pages = 4599–4600 | doi = 10.1021/jo00335a067}}</ref> The compound is commercially available as a solution in [[tetrahydrofuran]] and as a solid. 9-BBN is especially useful in [[Suzuki reaction]]s.<ref>{{OrgSynth | author = Tatsuo Ishiyama, Norio Miyaura, and Akira Suzuki | title = <nowiki>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 </nowiki> | collvol = 9 | collvolpages = 107 | prep = cv9p0107}}</ref>
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== Spectroscopic data ==
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From Soderquist & Negron (1992):<ref name="OrgSynthPrepn"/>
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*<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.  
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*<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)
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*<sup>11</sup>B-NMR (96 MHz, C<sub>6</sub>D<sub>6</sub>): ''δ''<sub>B</sub> = 28
  
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Its highly stereoselective addition on olefins allows the preparation of terminal alcohols by subsequent oxidative cleavage with H<sub>2</sub>O<sub>2</sub> in aq. KOH. The steric demand of 9-BBN greatly suppresses the formation of the 2-substituted isomer compared to the use of borane.
 
 
== References ==
 
== References ==
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{{Reflist}}
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{{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.
9-Borabicyclo[3.3.1]nonane
IUPAC name 9-Borabicyclo[3.3.1]nonane
Other names Borabicyclononane
Identifiers
Abbreviations 9-BBN
InChI InChI=1/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2
InChIKey FEJUGLKDZJDVFY-UHFFFAOYAE
Standard InChI InChI=1S/C8H15B/c1-3-7-5-2-6-8(4-1)9-7/h7-9H,1-6H2
Standard InChIKey FEJUGLKDZJDVFY-UHFFFAOYSA-N
CAS number [280-64-8]
EC number 206-000-9
ChemSpider 71299
SMILES
Properties
Chemical formula C8H15B
Molar mass 122.02 g/mol
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
9-Borabicyclo[3.3.1]nonane dimer
9-BBN dimer structure.svg
9-BBN-dimer-xtal-3D-sticks-skeletal.png
BBN Crystals.jpg
Identifiers
Abbreviations 9-BBN
InChI InChI=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
InChIKey QQDDHBYRUTZKSX-UHFFFAOYAH
Standard InChI InChI=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
Standard InChIKey QQDDHBYRUTZKSX-UHFFFAOYSA-N
CAS number [21205-91-4]
ChemSpider 21241191
SMILES
Properties
Chemical formula C16H26B2
Molar mass 244.04 g/mol
Appearance white solid
Density 0.894 g/cm3
Melting point

153–155 °C

Solubility in water reacts
Hazards
EU index number not listed
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
9-Borabicyclo[3.3.1]nonane—tetrahydrofuran
Identifiers
InChI InChI=1/C12H23BO/c1-2-10-14(9- 1)13-11-5-3-6-12(13)8-4-7-11/h 11-13H,1-10H2
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)

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. ↑ 1.0 1.1 Brown, H. C. Organic Syntheses via Boranes; Wiley: New York, 1975. ISBN 0-471-11280-1.
  2. ↑ Köster, R. Cyclische Alkyldiborane. Angew. Chem. 1960, 72 (17), 626–27. DOI: 10.1002/ange.19600721705.
  3. ↑ 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. ↑ 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.
  5. ↑ 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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