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18th July 2013 @ 10:47

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Compound

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Identifiers

*Chemical Name rac-((3aS,6aS)-Octahydro-2,2-bis(methoxymethyl)pentalen-5-yl)-dimethyl(phenyl)silane and rac-((3aS,6aR)-octahydro-2,2-bis(methoxymethyl)pentalen-5-yl)-dimethyl(phenyl)silane
Common Name  
Synonym  

Spectra

  *#Spectrum jcamp file *Spectrum Type Comments OpenData Image or PDF
Spectrum 1
HNMR.jdx
 
HNMR 

1H NMR (400 MHz, CDCl3): δ (ppm) = 7.547 – 7.496 (4H, m, Ho-Ph major + minor), 7.368 – 7.336 (6H, m, Hm- + p-Ph major + minor), 3.360 (3H, s, H1/2 minor), 3.357 (3H, s, H1/2 minor), 3.352 (3H, s, H1/2 major), 3.344 (3H, s, H1/2 major), 3.280 (1H, d, J = 8.8 Hz, H3/4 major), 3.276 (1H, d, J = 8.8 Hz, H3/4 major), 3.244 (1H, d, J = 8.8 Hz, H3/4 major), 3.218 (1H, d, J = 8.8 Hz, H3/4 major), 3.291 – 3.208 (4H, m, H3 + 4 minor), 1.936 (1H, dddd, J = 12.0, 10.5, 8.3, 3.8 Hz, Hmajor), 1.790 (1H, m, Hmajor), 1.696 (1H, ddd, J = 11.3, 8.0, 5.5 Hz, Hmajor), 1.605 – 1.479 (12H, m, Hmajor + minor), 1.387 – 1.290 (2H, m, Hmajor + minor), 1.049 – 0.867 (5H, m, Hmajor + minor), 0.342 (3H, s, H13/13’ minor), 0.340 (3H, s, H13/13’ minor), 0.260 (3H, s, H13/13’ major), 0.250 (3H, s, H13/13’ major).

HNMR.pdf
Spectrum 2   CNMR 

13C NMR (100.5 MHz, CDCl3): δ (ppm) = 139.27 (2CSi-i-Ph major + minor), 133.82 (4CHSi-p-Ph major + minor), 128.69 (2CHSi-p-Ph major + minor), 127.60 (4CHSi-m-Ph major + minor), 78.02 (CH23/4 minor), 78.02 (2CH23/4 major + minor), 77.99 (CH23/4 major), 59.20 (CH31/2 major), 59.17 (CH31/2 major), 58.06 (2CH31 + 2 minor), 54.95 (C5 major), 54.24 (C5 minor), 53.49 (CH8/9 major), 52.96 (CH8/9 major), 52.53 (2CH8 + 9 minor), 34.28 (CH26/7 major), 33.97 (CH26/7 major), 31.57 (2CH26 + 7 minor), 29.35 (CH210/11 major), 29.11 (2CH212 major + minor), 27.27 (CH210/11 major), 26.32 (2CH210 + 11 minor), –3.12 (CH313/13’ minor), –3.20 (CH313/13’ minor), –4.56 (CH313/13’ major),  –4.71 (CH313/13’ major). 

 
Spectrum 3   Electron Impact 

HRMS (EI): Sample submitted for experiment. 

HRMS3.35a,b.JPG
 
Spectrum 4   Chemical Ionization +ve  LRMS (CI): m/z: 254 ([M – Ph], 1%), 222 ([M – MeOH], 2%), 190 ([M – 2MeOH], 2%), 135 ([M – 2MeOH – SiMe2Ph], 100 %). 
LRMS3.35a,b.JPG
 
Spectrum 5   Infrared  IR (thin film): = 2952 (m), 2922 (m), 2869 (m), 2820 (m), 1452 (w), 1421 (w), 1251 (m), 1202 (m), 1107 (s), 813 (s), 775 (s), 722 (s), 695 (s) cm–1.
IR3.35a,b.JPG
 
Spectrum 6          
Spectrum 7          
Spectrum 8          
Spectrum 9          
Spectrum 10          

Properties

Experimental Physico-chemical Properties

Property Value Unit Comments
Experimental Boiling Point      
Experimental Flash Point      
Experimental Freezing Point      
Experimental Gravity      
Experimental Ionization Potent      
Experimental LogP      
Experimental Melting Point      
Experimental Optical Rotation      
Experimental Refraction Index      
Experimental Solubility      
Experimental Vapor Pressure      
Non Water Solubility      
Non Water Solubility      

Spectroscopy

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Lambda Max      

Miscellaneous

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Appearance Yellow Oil    
Bio Activity      
Chemical Class      
Compound Source      
Drug Status      
Exposure Limits      
Exposure Limits Niosh Rel      
Exposure Routes      
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Incompatability      
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Attached Files
18th July 2013 @ 10:32

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Compound

ChemSpider ID  
*#Name of Compound mol file
Compound.mol
 

Description and Tags

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Identifiers

*Chemical Name rac-(3aS,8aR)-2-Hexyl-1,2,3,3a,8,8a-hexahydro-2-(1-phenylvinyl)-cyclopenta[a]indene and rac-(3aR,8aR)-2-hexyl-1,2,3,3a,8,8a-hexahydro-2-(1-phenylvinyl)-cyclopenta[a]indene
Common Name  
Synonym  

Spectra

  *#Spectrum jcamp file *Spectrum Type Comments OpenData Image or PDF
Spectrum 1
HNMR.jdx
HNMR 

1H NMR (400 MHz, BENZENE-D6): δ (ppm) = 7.311 – 7.249 (4H, m, Ho-Ph), 7.194 – 7.070 (14H, m, HAr), 5.211 (1H, d, J = 1.3 Hz, H10 major), 5.146 (1H, d, J = 1.3 Hz, H10 minor), 5.068 (1H, d, J = 1.3 Hz, H10 major), 5.029 (1H, d, J = 1.3 Hz, H10 minor), 2.952 (1H, td, J = 12.3, 5.8 Hz, H5b major), 2.891 (1H, td, J = 11.8, 6.3 Hz, H5b minor), 2.665 (1H, dd, J = 13.8, 5.8 Hz, H3a major), 2.635 (1H, dd, J = 13.8, 5.8 Hz, H3a minor), 2.550 (1H, dd, J = 12.3, 6.0 Hz, H7a major), 2.329 (1H, ddt, J = 13.8, 11.5, 1.3 Hz, H3b major), 2.316 (1H, t, J = 13.8 Hz, H3b minor), 2.252 (1H, dd, J = 12.2, 5.7 Hz, H7a minor), 2.157 – 1.940 (3H, m, 2H4 + H6 minor), 1.885 (1H, t, J = 11.3 Hz, H6b major), 1.753 – 1.622 (2H, m, H6 minor + H), 1.740 (1H, dd, J = 11.3, 5.8 Hz, H6a major), 1.538 – 1.129 (19H, m), 1.412 (1H, t, J = 12.3 Hz, H7b major), 1.324 (1H, t, J = 12.2 Hz, H7b minor), 0.897 (3H, t, J = 7.0 Hz, H16 minor), 0.875 (3H, t, J = 7.0 Hz, H16 major). 

HNMR.pdf
 
Spectrum 2
CNMR.jdx
 
CNMR 

13C NMR (100.5 MHz, CDCl3): δ (ppm) = 158.49 (C9 major ), 158.40 (C9 minor ), 149.66 (Ci-Ph, major), 149.63 (Ci-Ph, minor), 145.60 (C1/2 major), 145.56 (C1/2 minor), 144.68 (C1/2 minor), 144.63 (C1/2 major), 128.99 (4CHAr), 128.68 (2CHAr), 128.40 (2CHAr), 127.30 (CHAr), 127.27 (CHAr), 126.73 (CHAr), 126.70 (CHAr), 126.44  (2CHAr), 125.65 (CHAr), 125.61 (CHAr), 122.93 (CHAr), 122.88 (CHAr), 114.10 (CH210 minor), 113.99 (CH210 major), 58.10 (C8 major), 58.05 (C8 minor), 56.97 (CH4/5 major), 56.61 (CH4/5 minor), 55.40 (CH4/5 minor), 55.04  (CH4/5 major), 43.40 (CH2 major), 43.28 (CH2 minor), 42.67 (CH2 major), 41.24 (CH2 minor), 39.54 (CH2 minor),  38.09 (CH2 major), 35.00 (2CHmajor + minor), 32.54 (CH2 minor), 32.49 (CH2 major), 30.58 (CH2 minor), 30.53 (CH2 major),  25.74 (CH2 minor), 25.63 (CH2 major), 23.40 (2CH2 major + minor), 14.67 (2CH316 major + minor).

CNMR.pdf
Spectrum 3   Electron Impact 

HRMS (EI): Found: [M]+, 344.2505. C26H32 requires: 344.2504. 

HRMS3.39a,b.JPG
 
Spectrum 4   Chemical Ionization +ve 

LRMS (CI): m/z: 345 ([M + H], 61%), 260 ([M – Hex + H], 14%), 130 (100%).

LRMS3.39a,b.JPG
 
Spectrum 5
DEPT135.jdx
 
CNMR  DEPT-135 
DEPT135.pdf
 
Spectrum 6  

2D NMR 1H-1H COSY

 
COSY 1H-1H 
COSY.pdf
 
Spectrum 7   Infrared

IR (thin film): = 2933 (m), 2858 (m), 1622 (w), 1489 (w), 1459 (m), 900 (m), 775 (m), 741 (s), 699 (s) cm–1. 

 
IR3.39a,b.JPG
 
Spectrum 8          
Spectrum 9          
Spectrum 10          

Properties

Experimental Physico-chemical Properties

Property Value Unit Comments
Experimental Boiling Point      
Experimental Flash Point      
Experimental Freezing Point      
Experimental Gravity      
Experimental Ionization Potent      
Experimental LogP      
Experimental Melting Point      
Experimental Optical Rotation      
Experimental Refraction Index      
Experimental Solubility      
Experimental Vapor Pressure      
Non Water Solubility      
Non Water Solubility      

Spectroscopy

Property Value Unit Comments
Lambda Max      

Miscellaneous

Property Value Unit Comments
Appearance Pale Yellow Oil    
Bio Activity      
Chemical Class      
Compound Source      
Drug Status      
Exposure Limits      
Exposure Limits Niosh Rel      
Exposure Routes      
First-Aid      
Incompatability      
Personal Protection      
Safety      
Stability      
Symptoms      
Target Organs      
Therapeutical Effect      
Toxicity      
Attached Files
18th July 2013 @ 10:18

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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 Jozef Stec   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton Conceiver
Author 4          

TEXT

*Procedure or Transformation Insertion of lithiated 1,1-dibromoheptane and phenyl acetylide into zirconacycle
*Compound(s) being made rac-(3aS,8aR)-2-Hexyl-1,2,3,3a,8,8a-hexahydro-2-(1-phenylvinyl)-cyclopenta[a]indene and rac-(3aR,8aR)-2-hexyl-1,2,3,3a,8,8a-hexahydro-2-(1-phenylvinyl)-cyclopenta[a]indene
*Chemicals used (delimited by semicolons ;) Cp2ZrCl2THFn-BuLi; Hexanes; 1-allyl-2-vinyllbenzene1,1-dibromoheptaneLDAPhenylacetylene; MeOHNaHCO3H2OEt2O; Brine; MgSO4.
*Procedure

To a solution of Cp2ZrCl2 (0.293 g, 1.0 mmol) in dry THF (5 mL) cooled to  –78 °C was added n-BuLi (0.80 mL of a 2.5 M solution in hexanes, 2.0 mmol) dropwise over 3 minutes. After 25 min at the same temperature, a solution of 1-allyl-2-vinyllbenzene (0.144 g, 1.0 mmol) in dry THF (3 mL) was added dropwise. After 30 min at –78 °C the reaction mixture was allowed to warm to room temperature and stirred for 2 h. After cooling the reaction to –78 °C, a solution of 1,1-dibromoheptane (0.271 g, 1.05 mmol) in dry THF (1 mL) was added followed by dropwise addition of LDA (0.61 mL of a 1.8 M solution, 1.1 mmol). After stirring the reaction mixture for 15 min at –78 °C, lithium phenylacetylide was added dropwise, [prepared from phenylacetylene (0.33 mL, 3.0 mmol) in dry THF (3 mL) and n-BuLi (1.2 mL of a 2.5 M solution in hexanes, 3.0 mmol) at –5 oC over 15 min]. The stirring was continued for 1.5 h during which the reaction mixture was allowed to warm to –30 °C before addition of MeOH (5 mL) and a saturated aqueous solution of NaHCO3 (6 mL). The whole mixture was allowed to warm to room temperature and left stirring overnight. The mixture then was poured onto H2O (100 mL), the products extracted with Et2O (3 × 50 mL). The combined organic phases were washed with H2O (3 × 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 hexanes as the eluent gave the title compound as an inseparable mixture of isomers in NMR ratio of 1.4 : 1 and combined yield of 0.165g (48%, pale yellow oil). 

*Authors Comments Further insertion of lithiated 1,1-dibromoheptane and phenyl acetylide, however, occurred exclusively into the trans ring junction zirconacycle to give the title compounds as an inseparable mixture of two diastereoisomers in the ratio of 1.4 : 1.
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, BENZENE-D6); 13C NMR (100.5 MHz, CDCl3); HRMS (EI); LRMS (CI); IR (thin film).

#Data file 1  http://blogs.chem.soton.ac.uk/data/33254.html
#Data file 2  http://blogs.chem.soton.ac.uk/data/33244.html
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
ReactionScheme.cdx
 
*#Image file (GIF or PNG)
ReactionScheme.png
 

Keywords

Compounds Keywords Alkanes; Alkenes; Aromatics/Arenes 
Reactions Keywords Insertion
Other Keywords  
Attached Files
18th July 2013 @ 09:55

This post is compatible for submission to ChemSpider SyntheticPages.

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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 Jozef Stec   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton Conceiver
Author 4          

TEXT

*Procedure or Transformation Insertion of alkyl carbenoids and acetylides into unsubstituted zirconacyclopentanes
*Compound(s) being made rac-((3aS,6aS)-Octahydro-2,2-bis(methoxymethyl)pentalen-5-yl)-dimethyl(phenyl)silane and rac-((3aS,6aR)-octahydro-2,2-bis(methoxymethyl)pentalen-5-yl)-dimethyl(phenyl)silane
*Chemicals used (delimited by semicolons ;) Cp2ZrCl2; THF; n-BuLi; Hexanes; bis(methoxymethyl)hepta-1,6-diene(dichloromethyl)dimethyl(phenyl)silane; LDA; HMPA; Phenylacetylene; MeOH; NaHCO3; H2O; Et2O; Brine; MgSO4
*Procedure

To a solution of Cp2ZrCl2 (0.293 g, 1.0 mmol) in dry THF (5 mL) cooled to –78 °C was added n-BuLi (0.80 mL of a 2.5 M solution in hexanes, 2.0 mmol) dropwise over 3 minutes. After 25 min at the same temperature, a solution of bis(methoxymethyl)hepta-1,6-diene (0.184 g, 1.0 mmol) in dry THF (3 mL) was added dropwise. After 30 min at –78 °C the reaction mixture was allowed to warm to room temperature and stirred for 2 h. After cooling the reaction mixture to –78 °C, a solution of (dichloromethyl)dimethyl(phenyl)silane (0.285 g, 1.3 mmol) in dry THF (1 mL) was added followed by dropwise addition of LDA (0.85 mL of a 1.8 M solution, 1.5 mmol). The reaction mixture was stirred for 0.5 h during which was allowed to warm to –60 °C before dropwise addition of lithium phenyl acetylide pre-mixed with HMPA. [Lithium phenyl acetylide was freshly prepared from phenylacetylene (0.33 mL, 3.0 mmol) in dry THF (3 mL) and n-BuLi (1.2 mL of a 2.5 M solution in hexanes, 3.0 mmol) at 0 oC over 10 min, then HMPA (0.52 mL, 3.0 mmol) was added and the stirring was continued at the same temperature for further 15 min]. The stirring was continued for 3 h during which time the reaction mixture was allowed to warm to –15 °C before addition of MeOH (5 mL) and a saturated aqueous solution of NaHCO3 (6 mL). The whole mixture was allowed to warm to room temperature and left stirring overnight. The mixture then was poured onto H2O (100 mL), the products extracted with Et2O (3 × 75 mL). The combined organic phases were washed with H2O (3 × 100 mL) and brine (100 mL), dried over MgSO4, filtered and concentrated in vacuo to give the crude product as a red oil.

Purification of the crude material by column chromatography on Al2O3 (basic, grade III) with 5% of Et2O in hexanes as the eluent gave the title compounds as a yellow oil in yield of0.072 g (22%). 

*Authors Comments In this case a higher temperature was required to make the zirconium-alkenylidene rearrangement occur since the resulting anion is stabilized by the adjacent silyl group, therefore the intermediate is less reactive towards the rearrangement. Additionally, the protonated compounds (96 : 4 respectively) were detected by GC in the crude reaction mixture in nearly equimolar amount.
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); HRMS (EI); LRMS (CI); IR (thin film).
#Data file 1  
#Data file 2  
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
ReactionScheme.cdx
 
*#Image file (GIF or PNG)
ReactionScheme.png
 

Keywords

Compounds Keywords Alkenes; Aromatics/Arenes; Ethers 
Reactions Keywords Insertion 
Other Keywords  
Attached Files
31st May 2013 @ 17:05

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