Triethylamine → HCID 86753000, compound

HRID 481812Notes

Reaction equation

HRID 481812 reaction equation
[CH3:1][Si:2]([CH3:39])([O:9][C@H:10]1[CH2:28][C@H:27]([O:29][Si:30]([CH2:35][CH3:36])([CH2:33][CH3:34])[CH2:31][CH3:32])[C@@:26]2([CH3:37])[C:12](=[CH:13][CH:14]=[C:15]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:38])[C@H:16]3[CH2:17][CH2:18]/[C:19]/2=[CH:20]/[CH3:21])[CH2:11]1)[C:3]([CH3:8])([CH3:7])[CH:4]([CH3:6])[CH3:5].[CH3:40][C:41]([Si:44]([CH3:54])([CH3:53])[O:45][C:46]([CH3:52])([CH3:51])[C:47]#[C:48][CH:49]=[O:50])([CH3:43])[CH3:42].[Cl-].C[Al+]C.C(N(CC)CC)C.[OH-].[NH4+]>CCCCCC>[CH3:43][C:41]([Si:44]([CH3:54])([CH3:53])[O:45][C:46]([C:47]#[C:48][CH:49]([OH:50])[C@H:20]([C:19]1[C@:22]2([CH3:38])[C@H:16]([C:15]3[C@H:25]([CH2:24][CH2:23]2)[C@:26]2([CH3:37])[C:12]([CH2:11][C@@H:10]([O:9][Si:2]([CH3:1])([CH3:39])[C:3]([CH3:7])([CH3:8])[CH:4]([CH3:6])[CH3:5])[CH2:28][C@@H:27]2[O:29][Si:30]([CH2:35][CH3:36])([CH2:31][CH3:32])[CH2:33][CH3:34])=[CH:13][CH:14]=3)[CH2:17][CH:18]=1)[CH3:21])([CH3:52])[CH3:51])([CH3:40])[CH3:42]

Participants

7

Reactant 5

HCID 8471TriethylamineHCID 14923Ammonium HydroxideHCID 108896204-((Tert-butyldimethylsilyl)oxy)-4-methylpent-2-ynalHCID 16686359Dimethylalumanylium chlorideHCID 86752999(1alpha,3beta,17Z)-dimethyl[[1-[(triethylsilyl)oxy]pregna-5,7,17(20)-trien-3-yl]oxy](1,1,2-trimethylpropyl)silane

Product 1

HCID 86753000HCID 86753000, compound

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent2×

Conditions

Temperature
-75 °C

Procedure

A 3-L three-necked flask equipped with a mechanical stirrer, thermometer, addition funnel, and Ar-inlet tube was charged with 91.9 g (160 mmol) of (1α,3β,17Z)-dimethyl[[1-[(triethylsilyl)oxy]pregna-5,7,17(20)-trien-3-yl]oxy](1,1,2-trimethylpropyl)silane, 62.8 mL (240 mmol) of 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy-4-methyl-2-pentynal, and 480 mL of hexane. After cooling to -75° C., 480 mL (480 mmol) of a 1M dimethylaluminum chloride solution in hexane was added over 1 hr. After stirring at -75° C. for 1.5 hr., 66.9 mL (480 mmol) of triethylamine was added followed by 147 mL of ammonium hydroxide over 5 min. After 5 min, the cold-bath was removed, and the mixture was stirred for 2 hr (Gas evolved). Then, 147 g of powder Na2SO4 was added, and the stirring was continued for 30 min. The solid was removed by filtration and washed with a total of 720 mL of hexane. The combined hexane solutions were washed with 480 mL of 95% methanol. The methanol layer was extracted with 240 mL of hexane. The combined hexane solutions were dried over Na2SO4 and concentrated. The residue was then dried under high vacuum overnight to give 153 g (overweight) of crude (1α,3β)-25-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-3-[[dimethyl(1,1,2-trimethylpropyl)silyl]oxy]-1-[(triethylsilyl)oxy]cholesta-5,7,16-trien-23-yn-22-ol as a brown viscous oil.

Workup

  1. customA 3-L three-necked flask equipped with a mechanical stirrer
  2. additionthermometer, addition funnel
  3. waitAfter 5 min
  4. customthe cold-bath was removed
  5. stirringthe mixture was stirred for 2 hr (Gas evolved)
  6. additionThen, 147 g of powder Na2SO4 was added
  7. waitthe stirring was continued for 30 min
  8. customThe solid was removed by filtration
  9. washwashed with a total of 720 mL of hexane
  10. washThe combined hexane solutions were washed with 480 mL of 95% methanol
  11. extractionThe methanol layer was extracted with 240 mL of hexane
  12. dry with materialThe combined hexane solutions were dried over Na2SO4
  13. concentrationconcentrated
  14. customThe residue was then dried under high vacuum overnight

Sources & evidence

ORD record
ord-5a91709175fe495bb8bae4488183861f
Source dataset
uspto-grants-1998_08
Patent number
US05789607

Reaction notes

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