Aluminium lithium hydride → 2,12-Bis-(4-isobutylphenyl)-2,12-dimethyl-7-([1,3]dithianyl)-tridecane-1,13-diol

HRID 969023Notes

Reaction equation

HRID 969023 reaction equation
C([O:3][C:4](=O)[C:5]([C:39]1[CH:44]=[CH:43][C:42]([CH2:45][CH:46]([CH3:48])[CH3:47])=[CH:41][CH:40]=1)([CH3:38])[CH2:6][CH2:7][CH2:8][CH2:9][CH:10]([CH:32]1[S:37][CH2:36][CH2:35][CH2:34][S:33]1)[CH2:11][CH2:12][CH2:13][CH2:14][C:15]([C:22]1[CH:27]=[CH:26][C:25]([CH2:28][CH:29]([CH3:31])[CH3:30])=[CH:24][CH:23]=1)([CH3:21])[C:16](OCC)=[O:17])C.[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[CH2:45]([C:42]1[CH:43]=[CH:44][C:39]([C:5]([CH3:38])([CH2:6][CH2:7][CH2:8][CH2:9][CH:10]([CH:32]2[S:33][CH2:34][CH2:35][CH2:36][S:37]2)[CH2:11][CH2:12][CH2:13][CH2:14][C:15]([C:22]2[CH:27]=[CH:26][C:25]([CH2:28][CH:29]([CH3:31])[CH3:30])=[CH:24][CH:23]=2)([CH3:21])[CH2:16][OH:17])[CH2:4][OH:3])=[CH:40][CH:41]=1)[CH:46]([CH3:48])[CH3:47]

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 865877332,12-Bis-(4 isobutylphenyl)-2,12-dimethyl-7-([1,3]dithianyl)-tridecanedioic acid diethyl ester

Product 1

HCID 234314492,12-Bis-(4-isobutylphenyl)-2,12-dimethyl-7-([1,3]dithianyl)-tridecane-1,13-diolYield 94%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 212f (5.81 g, 8.33 mmol) in freshly distilled THF (50 mL) was added dropwise to a suspension of LiAlH4 (1.0 g, 26.4 mmol) in THF (50 mL) at −78° C. under a nitrogen atmosphere. The solution was warmed to room temperature over 4 h, then cooled back to −78° C., and quenched with ethyl acetate (5.0 mL). After warming to room temperature, water (100 mL) was added and the product was extracted with Et2O (2×100 mL). The ether extracts were combined, dried with sodium sulfate, filtered, and concentrated. After drying under high vacuum for 4 h, 213f (4.80 g, 94%) was obtained as a colorless oil. 1H NMR (CDCl3): δ 7.20 (d, 4H, J=8.0), 7.09 (d, 4H, J=8.0), 3.64 (d, 2H, J=10.7), 3.48 (d, 2H, J=10.7), 2.71 (t, 4H, J=5.1), 2.50-2.35 (m br., 2H), 2.43 (d, 4H, J=7.0), 1.90-1.80 (m, 4H), 1.80-1.68 (m, 6H), 1.58-1.42 (m, 2H), 1.38-1.25 (m, 4H), 1.30 (s, 6H), 1.26-1.10 (m, 2H), 1.10-0.95 (m, 2H), 0.89 (d, 12H, J=6.6). 13C NMR (CDCl3): δ 141.94, 139.39, 129.20, 126.44, 72.48, 53.30, 44.97, 43.09, 38.45, 38.18, 30.21, 26.01, 25.64, 24.84, 24.09, 22.55, 21.64. HRMS (LSIMS, nba): Calcd for C38H61O2S2 (MH+): 613.4113, found: 613.4075. HPLC: 97.6% pure.

Workup

  1. temperaturecooled back to −78° C.
  2. customquenched with ethyl acetate (5.0 mL)
  3. temperatureAfter warming to room temperature
  4. additionwater (100 mL) was added
  5. extractionthe product was extracted with Et2O (2×100 mL)
  6. dry with materialdried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customAfter drying under high vacuum for 4 h

Sources & evidence

ORD record
ord-341ec1388a084e598e3e351c2a0d30f6
Source dataset
uspto-grants-2007_12
Patent number
US07304093B2

Reaction notes

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