Diethyl Malonate → HCID 57222703, compound

HRID 1284875Notes

Reaction equation

HRID 1284875 reaction equation
[CH3:1]C(C)([O-])C.[K+].[C:7]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[F:18][C:19]([F:52])([CH2:29][C@H:30]([C@@H:32]1[C@:49]2([CH3:50])[C@H:35]([C@H:36]3[C@H:46]([CH2:47][CH2:48]2)[C@:44]2([CH3:45])[C:39]([CH2:40][C@@H:41]([OH:51])[CH2:42][CH2:43]2)=[CH:38][CH2:37]3)[CH2:34][CH2:33]1)[CH3:31])[CH2:20]OS(C(F)(F)F)(=O)=O.[CH2:53]1[CH2:57][O:56][CH2:55][CH2:54]1>CN(P(N(C)C)(N(C)C)=O)C>[CH2:16]([O:15][C:7](=[O:14])[CH:8]([CH2:20][C:19]([F:18])([F:52])[CH2:29][C@H:30]([C@@H:32]1[C@:49]2([CH3:50])[C@H:35]([C@H:36]3[C@H:46]([CH2:47][CH2:48]2)[C@:44]2([CH3:45])[C:39]([CH2:40][C@@H:41]([O:51][CH:55]4[CH2:54][CH2:1][CH2:53][CH2:57][O:56]4)[CH2:42][CH2:43]2)=[CH:38][CH2:37]3)[CH2:34][CH2:33]1)[CH3:31])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:17]

Participants

6

Reactant 4

HCID 7761Diethyl MalonateHCID 8028Tetrahydrofuran2×HCID 23665647Potassium tert-butoxideHCID 57067061HCID 57067061, compound

Product 1

HCID 57222703HCID 57222703, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Procedure

A mixture potassium tert-butoxide (1.1 g, 9.6 mmol) and diethyl malonate (3.8 g, 24 mmol) in THF (25 ml) and HMPA (8 ml) was stirred at room temperature under argon atmosphere for 1 hr. To this solution the triflate (8) (1.47 g, 2.4 mmol) in THF (20 ml) was added and the mixture was stirred at room temperature for 26 hr. The usual work-up (ether for extraction) gave a crude product, which was applied to a column of silica gel (100 g). Elution with n-hexane-ether (5:1) provided the diester (9) (1.20 g, 81%), mp 79°-80° C. (ethanol). IR γmaxKBr cm-1 : 1750, 1740. 1H-NMR δ: 0.73 (3H, s, 18-H3), 1.00 (3H, s, 19-H3), 1.10 (3H, d, J=6 Hz, 21-H3), 1.27 (6 H, t, J=7 Hz, --CO2CH2CH3), 3.46 (2H, m, THP), 3.62 (1H, t, J=6 Hz, 25-H), 3.80 (1H,m, 3-H), 4.14 (4H,q,J=JHz, --COCH2CH3), 4.64 (1H,m,THP), 5.30 (1H m, 6-H). MS m/z: 538 (M+ -DHP), 520, 505. Anal. Calcd for C36H56O6F2 : C, 69.40; H, 9.06; F, 6.10. Found: C, 69.19; H, 9.11; F, 5.85.

Workup

  1. extractionThe usual work-up (ether for extraction)
  2. customgave a crude product, which
  3. washElution with n-hexane-ether (5:1)

Sources & evidence

ORD record
ord-9c9fdc488a9c4106b576062a69b6436b
Source dataset
uspto-grants-1986_01
Patent number
US04564474

Reaction notes

Loading…