Hydrochloric Acid → HCID 54476339, compound

HRID 1109084Notes

Reaction equation

HRID 1109084 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([F:21])([F:20])[F:19])[CH:13]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.C([Li])CCC.Cl[CH2:28]/[C:29](/[CH3:54])=[CH:30]/[CH2:31][CH2:32][C:33]1([CH3:53])[CH2:38][CH2:37][C:36]2[CH:39]=[C:40]([O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47])[C:41]([CH3:44])=[C:42]([CH3:43])[C:35]=2[O:34]1.Cl>C1COCC1.CN(P(N(C)C)(N(C)C)=O)C>[CH3:52][C:49]([Si:46]([CH3:47])([CH3:48])[O:45][C:40]1[C:41]([CH3:44])=[C:42]([CH3:43])[C:35]2[O:34][C:33]([CH2:32][CH2:31][CH:30]=[C:29]([CH3:28])[CH2:54][CH:11]([S:8]([C:5]3[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][CH:6]=3)(=[O:9])=[O:10])[C:12]3[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([F:21])([F:19])[F:20])[CH:13]=3)([CH3:53])[CH2:38][CH2:37][C:36]=2[CH:39]=1)([CH3:50])[CH3:51]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 19021851HCID 19021851, compoundHCID 19955619HCID 19955619, compoundHCID 178418339Butyllithium

Product 1

HCID 54476339HCID 54476339, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

4-Methyl-1-[[[3-(trifluoromethyl)phenyl]methyl]sulfonyl]benzene (30 mmole) was dissolved in 100 mL of dry THF. The mixture was cooled to about -78° under nitrogen, and n-butyllithium (30 mmole) was added dropwise giving rise to a colored anion [yellowish-orange]. The solution was stirred for about 1 hour at about -78° before the addition of HMPA (5 mL) and [2-(5-chloro-4-methyl-3(E)-pentenyl)]-3,4-dihydro-6-[(1,1- dimethylethyl)dimethyl silyloxy]-2,7,8-trimethyl-2H-1-benzopyran (25 mmole). The mixture was stirred for about 1 hour at about -78°, then warmed to about -5° for about 12 hours, and poured into 1N HCl. The mixture was extracted with fresh ether. The combined organic fractions were washed With water and dried (brine, MgSO4). Concentration in vacuo gave a crude material that was purified by flash chromatography (gradient 10:1 to 2:1 hexanes:ether) to give the coupled product as colorless oil: IR (film) 2930, 1472, 1450, 1424, 1330, 1166, 1146, 1130, 1088 cm-1 ; 1H NMR (CDCl3) δ 0.16 (s, 6H), 1.00 (s, 9H), 1.09, 1.10 (s, 3H), 1.28 (m, 2H), 1.41, 1.39 (s, 3H), 1.60 (m, 2H), 1.91 (m, 2H), 2.02 (s, 3H), 2.07 (s, 3H), 2.39 (s, 3H), 2.56 (m, 2H), 2.74 (t, J=13.9 Hz, 1H), 3.09 (d, J=11.9 Hz, 1H), 4.22 (d of t, J=12.1, 4.0 Hz, 1H), 5.06 (m, 1H), 6.30 (s, 1H), 7.10 (s, 1H), 7.18 (d, J=8.5 Hz, 2H), 7.36 (m, 4H), 7.48 (d, J=6.5 Hz, 1H); MS m/e 701 (MH+).

Workup

  1. temperatureThe mixture was cooled to about -78° under nitrogen
  2. customgiving rise to a colored anion [yellowish-orange]
  3. temperaturewarmed to about -5° for about 12 hours
  4. extractionThe mixture was extracted with fresh ether
  5. washThe combined organic fractions were washed With water
  6. dry with materialdried (brine, MgSO4)
  7. concentrationConcentration in vacuo
  8. customgave a crude material that
  9. customwas purified by flash chromatography (gradient 10:1 to 2:1 hexanes:ether)

Sources & evidence

ORD record
ord-c968e7104ae0404f83266bc5a4774720
Source dataset
uspto-grants-1994_06
Patent number
US05318993

Reaction notes

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