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17th July 2013 @ 15:49

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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 Synthesis of rac-(3aS,6aS)-Octahydro-2,2-bis(methoxymethyl)-5-(3-phenylpropa1,2-dienyl)pentalene and rac-(3aS,6aS)-octahydro-2,2-bis(methoxymethyl)-5-(3-phenylprop-2-ynyl)pentalene
*Compound(s) being made Rac-(3aS,6aS)-Octahydro-2,2-bis(methoxymethyl)-5-(3-phenylpropa1,2-dienyl)pentalene and rac-(3aS,6aS)-octahydro-2,2-bis(methoxymethyl)-5-(3-phenylprop-2-ynyl)pentalene
*Chemicals used (delimited by semicolons ;)  Cp2ZrCl2n-BuLi; bis(methoxymethyl)hepta-1,6-diene1,1-dibromoheptane2,2,6,6-tetramethylpiperidineTHFphenylacetyleneMeOHNaHCO3SiO2Et2O
*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 12 h. After cooling the reaction to –78 °C, 1,1-dichloromethane (0.064 mL, 1.0 mmol) was added followed by dropwise addition of freshly prepared LiTMP, [prepared from freshly distilled 2,2,6,6-tetramethylpiperidine (0.20 mL, 1.2 mmol) in dry THF (2 mL) and n-BuLi (0.48 mL of a 2.5 M solution in hexanes, 1.15 mmol) at 0 °C over 20 min]. The reaction mixture was stirred for 1 h during which was allowed to warm to –65 °C before re-cooling to –78 °C and dropwise addition of lithium phenyl acetylide, [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 15 min]. The stirring was continued for 3 h during which time the reaction mixture was allowed to warm to –35 °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 for 18 h. The mixture then was poured onto H2O (100 mL), the products were 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 brown oil.

Purification of the crude material by column chromatography on SiO2 (230 – 400 mesh) with 5% of Et2O in hexanes gave the title compounds as an inseparable mixture of compounds in the following ratio: 3.80a/b : 3.80b/a, 1 : 1.8 and 3.80 : 3.81, 1 : 2, as a pale yellow oil in combined yield of 0.033 g (10%).

*Authors Comments  

Further acetylide insertion allows for incorporation of the alkynyl moiety into the molecule to provide intermediate 3.79, which after protonolysis gives three products: 3.80a, b and 3.81 as an inseparable mixture of compounds in 10% combined yield and following ratio: 3.80a/b : 3.80b/a, 1.8 : 1 and 3.80 : 3.81, 1 : 2 by NMR. Despite considerable optimization undertaken, the reaction proved to be low yielding and the purification of the final product difficult due to many unidentifiable products. 

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  
HNMR.pdf
#Data file 2  
CNMR.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
FINAL_Scheme_3.80.mol
 
*#Image file (GIF or PNG)  
FINAL_Scheme_3.80.gif

Keywords

Compounds Keywords arenes, carbocyclic compounds, alkenes, alkynes 
Reactions Keywords addition, substitution
Other Keywords  
Attached Files
17th July 2013 @ 15:45

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Compound

ChemSpider ID  
*#Name of Compound mol file
Structure_3.80.mol
 

Description and Tags

Description Mixture 3.80/3.81 in J.Stec's thesis
Tags (separated by comma)  zirconocene chemistry

Identifiers

*Chemical Name Rac-(3aS,6aS)-Octahydro-2,2-bis(methoxymethyl)-5-(3-phenylpropa1,2-dienyl)pentalene and rac-(3aS,6aS)-octahydro-2,2-bis(methoxymethyl)-5-(3-phenylprop-2-ynyl)pentalene
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) = 7.393 – 7.145 (15H, m, HAr), 6.162 (1H, dd, J = 6.3, 3.0 Hz, H17a/b), 6.160 (1H, dd, J = 6.3, 2.9 Hz, H17a/b), 5.685 (2H, td, J = 6.5, 3.5 Hz, H15), 3.334 – 3.218 (30H, m), 2.723 – 2.650 (2H, m, H14), 2.433 (2H, d, J = 7.0 Hz, H10), 1.989 – 1.348 (27H, m), 1.319 – 0.841 (14H, m).

Y  
HNMR.pdf
Spectrum 2  
CNMR.jdx
CNMR  

13C NMR (100.5 MHz, CDCl3): δ (ppm) = 203.46 (C16a/b), 203.40 (C16a/b), 135.18 (2Ci-Ph B), 131.54 (2CHo-Ph A), 128.53 (4CHm-Ph B), 128.14 (2CHm-Ph A), 127.40 (CHp-Ph A), 126.59 (2CHo-Ph B), 126.54 (2CHp-Ph B), 126.49 (2CHo-Ph B), 124.15 (Ci-Ph A), 101.81  (CH17a/b), 101.76 (CH17a/b), 95.73 (2CH15a + b), 89.90 (C12), 80.45 (C13), 78.17 (2CH22), 78.10 (4CH22), 59.20 (6CH31), 54.42 (2C3), 54.34 (C3), 52.33 (3CH6/7), 50.90 (2CH6/7), 50.76 (CH6/7), 43.33 (CH 10), 42.92 (2CH 14), 34.72 (2CH2), 34.40 (CH2), 34.33 (2CH2), 34.25 (2CH2), 34.20 (2CH2), 33.61 (2CH2), 32.51 (CH2), 26.99 (CH2).

Y  
CNMR.pdf
Spectrum 3  
CDEPTNMR.jdx
CNMR   Y  
CDEPTNMR.pdf
Spectrum 4   Chemical Ionization +ve  

LRMS (CI): m/z: 313 ([M + H], 9%), 268 ([M – MeOH + H], 6%), 267 ([M – Et2O + H], 4%), 249 ([M – 2MeOH + H], 9%), 235 ([M – Ph], 7%), 115 ([C9H7], 34%).

 

 Y  
Spectrum 5          
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

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
17th July 2013 @ 15:29

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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 Synthesis of Rac-(2aR,4[E/Z],4aR,7aS,7bR)-1,1-Bis(methoxymethyl)-4-hexylidenedecahydro-1H-cyclopenta[cd]indene
*Compound(s) being made Rac-(2aR,4[E/Z],4aR,7aS,7bR)-1,1-Bis(methoxymethyl)-4-hexylidenedecahydro-1H-cyclopenta[cd]indene
*Chemicals used (delimited by semicolons ;)  Cp2ZrCl2n-BuLi; 3-(1-methoxy-2-(methoxymethyl)pent-4-en-2-yl)cyclohex-1-ene1,1-dibromoheptane2,2,6,6-tetramethylpiperidineTHFphenylacetyleneMeOHNaHCO3SiO2Et2O
*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 3-(1-methoxy-2-(methoxymethyl)pent-4-en-2-yl)cyclohex-1-ene (0.224 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 –90 °C, a solution of 1,1-dibromoheptane (0.284 g, 1.1 mmol) in dry THF (1 mL) was added followed by dropwise addition of freshly prepared LiTMP, [prepared from freshly distilled 2,2,6,6-tetramethylpiperidine (0.196 mL, 1.15 mmol) in dry THF (2 mL) and n-BuLi (0.46 mL of a 2.5 M solution in hexanes, 1.15 mmol) at 0 °C over 20 min]. The reaction mixture was stirred for 20 min during which was allowed to warm to –78 °C before dropwise addition of lithium phenyl acetylide. [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 15 min]. The stirring was continued for 2 h during which time the reaction mixture was allowed to warm to RT 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 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 5% of Et2O in hexanes and Kugelrohr distillation (200 °C, 1.0 mmHg) gave the title compounds as an inseparable mixture 3 : 1 of E : Z isomers as a pale yellow oil in yield of 0.029 g (9%).

*Authors Comments  The insertion of lithiated 1,1-dibromoheptane occurred very poorly and was followed by β-hydride elimination to provide an inseparable mixture of 3 : 1 (by 13C NMR), E : Z isomers of 3.70 and 9% combined yield
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  
HNMR.pdf
#Data file 2  
CNMR.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
FINAL_Scheme_3.70.cdx
 
*#Image file (GIF or PNG)  
FINAL_Scheme_3.70.gif

Keywords

Compounds Keywords carbocyclic compounds, alkenes 
Reactions Keywords  insertion
Other Keywords  
Attached Files
17th July 2013 @ 14:30

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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 Synthesis of mixture 3.65/3.66/3.67
*Compound(s) being made Rac-(3aR,9aS)-1-Hexyl-3a,4,9,9a-tetrahydro-1H-cyclopentanaphtalene, rac-(3aS,9aR)-2-hexylidene-2,3,3a,4,9,9a-hexahydro-1H-cyclopentanaphtalene and rac-(3aS,9aR)-2-hexyl-2,3,3a,4,9,9a-hexahydro-1H-cyclopentanaphtalene
*Chemicals used (delimited by semicolons ;)  Cp2ZrCl2n-BuLi1,2-diallylbenzene1,1-dibromoheptane2,2,6,6-tetramethylpiperidineTHFphenylacetyleneMeOHNaHCO3SiO2Et2O
*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 1,2-diallylbenzene (0.158 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 2.5 h. After cooling the reaction to –85 °C, a solution of 1,1-dibromoheptane (0.335 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). After 15 min a dropwise addition of lithium phenyl acetylide followed, [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 h during which time the reaction mixture was allowed to warm to –55 °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 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 compounds as colourless oil in yield of 0.083 g (33%) as an inseparable mixture of compounds with the ratios 3.65:65%, 3.66:31% and 3.67:4% 

*Authors Comments These compounds were obtained simultaneously with compound 3.64
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  
HNMR.pdf
#Data file 2  
CNMR.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
FINAL_Sheme_3.65etc.cdx
 
*#Image file (GIF or PNG)  
FINAL_Sheme_3.65etc.gif

Keywords

Compounds Keywords carbocyclic compounds, alkenes
Reactions Keywords addition, substitution
Other Keywords  
Attached Files
17th July 2013 @ 12:32

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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  Synthesis of Rac-(3aR,7a[S/R])-2-Hexyl-octahydro-2-(1-phenylvinyl)-1-H-indene 
*Compound(s) being made  Rac-(3aR,7a[S/R])-2-Hexyl-octahydro-2-(1-phenylvinyl)-1-H-indene 
*Chemicals used (delimited by semicolons ;) Cp2ZrCl2; n-BuLi; 1,7-octadiene; 1,1-dibromoheptane; 2,2,6,6-tetramethylpiperidine; THF; phenylacetylene; NaHCO3SiO2Et2O
*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 1,7-octadiene (0.110 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 (0.335 g, 1.30 mmol) in dry THF (1 mL) was added followed by dropwise addition of LDA (0.83 mL of a 1.8 M solution, 1.50 mmol). The reaction mixture was stirred at –78 °C for 15 min before dropwise addition of lithium phenyl acetylide, [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 30 min during which time the reaction mixture was allowed to warm to –50 °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 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 an orange oil.

Purification of the crude material by column chromatography on SiO2 (230 – 400 mesh) with hexanes as the eluant gave the title compounds as a pale yellow oil in combined yield of 0.165 g (53%).

*Authors Comments  Rac-(3aS,7aR)-2-Hexylidene-octahydro-1-H-indene was also obtained (simultaneously) from this reaction.
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  
HNMR.pdf
#Data file 2  
CNMR.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
FINAL_Scheme_3.59.cdx
 
*#Image file (GIF or PNG)  
FINAL_Scheme_3.59.gif

Keywords

Compounds Keywords  alkenes, carbocyclic compounds, arenes
Reactions Keywords  insertion
Other Keywords  
Attached Files