Characterization Template - Proton NMR
ChemSpider compound and associated data template
ChemSpider Reactions template
ChemSpider SyntheticPages style reaction template
- August 2013 (212)
- July 2013 (495)
- June 2013 (331)
- May 2013 (2)
- April 2013 (9)
- 1 (6)
- A.Henderson (226)
- L. Sayer (48)
- Templates (5)
- D. Owen (249)
- D.Macfarlane (91)
- F. Giustiniano (148)
- ForChemSpider (70)
- ForCSSP (35)
- G. Saluste (54)
- Help (7)
- J. Stec (110)
This post is compatible for submission to ChemSpider SyntheticPages.
See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.
SOURCE
Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").
*First name | *Last name | 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 ;) | Cp2ZrCl2; n-BuLi; bis(methoxymethyl)hepta-1,6-diene; 1,1-dibromoheptane; 2,2,6,6-tetramethylpiperidine; THF; phenylacetylene; MeOH; NaHCO3; SiO2; Et2O |
*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 |
This post is compatible for submission to ChemSpider.
See ChemSpider compound and associated data template - help and further information for help when using it.
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 |
This post is compatible for submission to ChemSpider SyntheticPages.
See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.
SOURCE
Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").
*First name | *Last name | 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 ;) | Cp2ZrCl2; n-BuLi; 3-(1-methoxy-2-(methoxymethyl)pent-4-en-2-yl)cyclohex-1-ene; 1,1-dibromoheptane; 2,2,6,6-tetramethylpiperidine; THF; phenylacetylene; MeOH; NaHCO3; SiO2; Et2O |
*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 |
This post is compatible for submission to ChemSpider SyntheticPages.
See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.
SOURCE
Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").
*First name | *Last name | 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 ;) | Cp2ZrCl2; n-BuLi; 1,2-diallylbenzene; 1,1-dibromoheptane; 2,2,6,6-tetramethylpiperidine; THF; phenylacetylene; MeOH; NaHCO3; SiO2; Et2O |
*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 |
This post is compatible for submission to ChemSpider SyntheticPages.
See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.
SOURCE
Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").
*First name | *Last name | 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; NaHCO3; SiO2; Et2O |
*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 |