Trisodium Phosphate → HCID 86735948, compound

HRID 2419625Notes

Reaction equation

HRID 2419625 reaction equation
[CH3:1][CH2:2][O:3][C:4](/[CH:6]=[CH:7]/[CH2:8]P(OCC)(OCC)=O)=[O:5].C([Li])CCC.[C:22]([O:25][C@@H:26]1[CH2:48][CH2:47][C@@:46]2([CH3:49])[CH:28]([CH2:29][CH2:30][C@@H:31]3[C@@H:45]2[CH2:44][C@H:43]([O:50][C:51](=[O:53])[CH3:52])[C@@:42]2([CH3:54])[C@H:32]3[CH2:33][CH2:34][C@@H:35]2[C@H:36]([CH3:41])[CH2:37][CH2:38][CH:39]=O)[CH2:27]1)(=[O:24])[CH3:23].P([O-])([O-])([O-])=O.[Na+].[Na+].[Na+]>C(COC)OC.CCCCCC>[CH2:2]([O:3][C:4](=[O:5])/[CH:6]=[CH:7]/[CH:8]=[CH:39]/[CH2:38][CH2:37][CH:36]([C@@H:35]1[C@:42]2([CH3:54])[C@H:32]([C@H:31]3[C@H:45]([CH2:44][C@@H:43]2[O:50][C:51](=[O:53])[CH3:52])[C@:46]2([CH3:49])[C@@H:28]([CH2:27][C@H:26]([O:25][C:22](=[O:24])[CH3:23])[CH2:48][CH2:47]2)[CH2:29][CH2:30]3)[CH2:33][CH2:34]1)[CH3:41])[CH3:1]

Participants

7

Reactant 4

HCID 24243Trisodium PhosphateHCID 5365783Triethyl 4-phosphonocrotonate, mixture of isomersHCID 53897611HCID 53897611, compoundHCID 178418339Butyllithium

Product 1

HCID 86735948HCID 86735948, compound

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

To a solution of 19.6 g of freshly distilled triethyl 4-phosphonocrotonate in 50 ml of dry glyme was added (at -70° ) 50 ml of a 1.6 M solution of butyl lithium in hexane. After 15 min the temperature was brought to -10° and 30 g of 3α,12α-diacetoxycholan-24-al was dissolved in 200 ml of dry glyme was added dropwise. After stirring for 20 min at this temperature the reaction mixture was allowed to warm to room temperature and stirred for 0.5 hr. The reaction mixture was then poured into 2 liters of a 5% monobasic sodium phosphate solution and the mixture extracted with ether. The ether solution was washed with a saturated aqueous sodium chloride solution and dried (MgSO4). The solvent was removed under reduced pressure and the residue after being dissolved in a minimum amount of benzene was washed through 300 g of silica gel. The column was eluted with 4 liters of benzene and then 4 liters of 0.5% ethyl acetate-benzene solution, and the solids obtained therefrom were combined to give 20.7 g of crude 7-(3α,12α-diacetoxy-5β-pregnane-20-yl)-trans,trans- 2,4-heptadienoic acid ethyl ester. Trituration with petroleum ether afforded 13.1 g of 7-(3α,12α-diacetoxy-5β-pregnane-20-yl)-trans,trans-2,4-heptadienoic acid ethyl ester, mp 129°-131°, plus a second crop of 2.4 g, mp 128°-130°. Crystallization from methanol afforded the analytical sample, mp 130°-132°.

Workup

  1. additionwas added dropwise
  2. stirringstirred for 0.5 hr
  3. extractionthe mixture extracted with ether
  4. washThe ether solution was washed with a saturated aqueous sodium chloride solution
  5. dry with materialdried (MgSO4)
  6. customThe solvent was removed under reduced pressure
  7. dissolutionthe residue after being dissolved in a minimum amount of benzene
  8. washwas washed through 300 g of silica gel
  9. washThe column was eluted with 4 liters of benzene
  10. custom4 liters of 0.5% ethyl acetate-benzene solution, and the solids obtained

Sources & evidence

ORD record
ord-70e35d6b584748af911390ee26b47c57
Source dataset
uspto-grants-1978_08
Patent number
US04107188

Reaction notes

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