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30th May 2013 @ 14:00

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SOURCE

Author 1 is the author of this LabTrove post  (and has contributor role of "Abstracter").

  *First name *Last name Email Organization Role
Author 2 Józef Stec   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton  Conceiver
Author 4          

TEXT

*Procedure or Transformation Insertion of allenyl carbenoid into organochlorozirconocenes with the potential for asymmetric synthesis: rac-3-Hexyl-2-methyltridec-4-yn-2-ol
*Compound(s) being made Characterisation of rac-3-Hexyl-2-methyltridec-4-yn-2-ol (4.82d)
*Chemicals used (delimited by semicolons ;) 1-octene; Cp2ZrHCl; non-1-yn-3-yl benzensulfonate; LiTMP; Me2CO; MeOH; NaHCO3
*Procedure To a stirred suspension of Cp2ZrHCl (0.258 g, 1.0 mmol) in dry THF (10 mL) at RT was added neat 1-octene (0.125 mL, 0.8 mmol) dropwise over 3 minutes. After stirring the yellow solution for 1 h at RT, the reaction mixture was cooled to –78 C and a solution of the non-1-yn-3-yl benzensulfonate (0.294 g, 1.0 mmol) in dry THF (1 mL) was added dropwise followed by dropwise addition of freshly prepared LiTMP, [prepared from freshly distilled 2,2,6,6-tetramethylpiperidine (0.17 mL, 1.0 mmol) in dry THF (2 mL) and n-BuLi (0.4 mL of a 2.5 M solution in hexanes, 1.0 mmol) at –5 C over 15 min]. The stirring was continued for a further 1.5 h during which time the reaction mixture was allowed to warm to RT. The reaction mixture was re-cooled to –78 C and a solution of acetone (0.22 mL 3.0 mmol) in dry THF (1 mL) was added, the reaction mixture warmed gradually to RT. The reaction mixture was then refluxing for 20 h before cooling to RT and quenching with MeOH (5 mL) and a saturated aqueous solution of NaHCO3 (6 mL), the mixture left stirring overnight. The mixture was poured onto H2O (100 mL), the products extracted with Et2O (3 × 75 mL). The combined organic phases were washed with H2O (2 × 100 mL) and brine (100 mL), dried over MgSO4, filtered and concentrated in vacuo to give the crude product as a yellow oil. Purification of the crude material by column chromatography on SiO2 (230 – 400 mesh) with hexane : EtOAc (10 : 1) as the eluent to yield the title compound as a yellow oil in yield of 0.118 g (50%, contained 10% of unidentified by-products).
*Authors Comments -
Lead Reference J. Stec, 2009, "Tandem Reaction Sequences on a Zirconocene Template",PhD thesis, University of Southampton
Other References  
Multimedia Content  
*Data 1H NMR (400 MHz, CDCl3); 13C NMR (100.5 MHz, CDCl3)
#Data file 1
nv1707jst2.010.001.jdx
#Data file 2
nv1707jst2.011.001.jdx
#Data file 3  
#Data file 4  
#Data file 5  

Chemicals Used/Produced

Compound Information Amounts Other information
Name: 1-octene
ChemSpider ID:7833
Formula: C8H16
MW: 112.21
image from chemspider
User ID:
Source:
Ratio: 1
Amount: 0.8mmol
Purity: 100%
Volume: 0.125mL*
Role: Reactant
Comments:
Safety Information:
Name: Cp2ZrHCl
ChemSpider ID:28605366
Formula: C10H11ClZrC
MW: 257.87
image from chemspider
User ID:
Source:
Ratio: 1.25*
Purity: 100%*
Amount: 1mmol
Mass: 0.258g
Role: Reactant
Comments:
Safety Information:
Name: non-1-yn-3-yl benzensulfonate
Formula: C11H12O3S
MW: 224.276
User ID:
Source:
Ratio: 1.25*
Purity: 100%*
Amount: 1mmol
Mass: 0.294g
Role: Reactant
Comments:
Safety Information:
Name: 2,2,6,6-tetramethylpiperidine
ChemSpider ID:12493
Formula: C9H19N
MW: 141.25
image from chemspider
User ID:
Source:
Ratio: 1.25*
Purity: 100%*
Amount: 1mmol
Volume: 0.17mL
Role: Reactant
Comments:
Safety Information:
Name: n-BuLi
ChemSpider ID:10254339
Formula: C4H9Li
MW: 64.06
image from chemspider
User ID:
Source:
Ratio: 1.25*
Purity: 100%*
Amount: 1mmol
Volume: 0.4mL
Role: Reactant
Comments:
Safety Information:
Name: Me2CO
ChemSpider ID:175
Formula: C3H6O
MW: 58.08
image from chemspider
User ID:
Source:
Ratio: 3.75*
Purity: 100%*
Amount: 3mmol
Volume: 0.22mL
Role: Reactant
Comments:
Safety Information:
Name: Characterisation of rac-3-Hexyl-2-methyltridec-4-yn-2-ol (4.82d)
ChemSpider ID: 28605365
Formula: C20H38O
MW: 290.48
image from chemspider
User ID: 4.82d
Source:
Planned Amount: 0.8mmol
Planned Mass: 0.232g
Actual Mass: 0.118g*
Purity:90%*
Yield: 50%
Role: Product
Comments:yellow oil
Safety Information:

(* indicates entered value)

SCHEME

*#Name of Structure file (ChemDraw, ChemSketch or RXN file)
CSSP verscheme for 4_82.cdx
 
*#Name of Image file (GIF or PNG)
CSSP verscheme for 4_82.gif

 

Linked Posts
Attached Files
JS Thesis 10_08.12.09 Final VI_pp99-100.pdf
JS Thesis 10_08.12.09 Final VI_pp240-241.pdf
CSSP verscheme for 4_82.cdx
CSSP verscheme for 4_82.gif