Tin tetrachloride → HCID 15895032, compound

HRID 1871286Notes

Reaction equation

HRID 1871286 reaction equation
[CH:1]([C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([CH:15]([CH3:17])[CH3:16])[C:12]=1[O:13][CH3:14])[C:7]([OH:9])=O)([CH3:3])[CH3:2].C(Cl)(=O)C(Cl)=O.[Sn](Cl)(Cl)(Cl)Cl.[CH2:29]([C:36]1[O:37][C:38]([CH3:42])=[C:39]([CH3:41])[CH:40]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>C(Cl)Cl.CN(C)C=O>[CH2:29]([C:36]1[O:37][C:38]([CH3:42])=[C:39]([CH3:41])[C:40]=1[C:7]([C:6]1[CH:10]=[C:11]([CH:15]([CH3:17])[CH3:16])[C:12]([O:13][CH3:14])=[C:4]([CH:1]([CH3:2])[CH3:3])[CH:5]=1)=[O:9])[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

7

Reactant 4

HCID 24287Tin tetrachlorideHCID 65578Oxalyl chlorideHCID 15895030HCID 15895030, compoundHCID 15895031HCID 15895031, compound

Product 1

HCID 15895032HCID 15895032, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

At ambient temperature, to a stirred suspension containing 3,5-diisopropyl-p-anisic acid (1.95 g, 8.23 mmol, RN-117439-59-5) and oxalyl chloride (0.8 mL, 9.20 mmol) in CH2Cl2 (22.5 mL) was added N,N-dimethylformamide (2 drops). After 2 h, the reaction was cooled to -78° C. To the reaction was added tin (IV) chloride (1.05 mL) followed by a solution of 2-benzyl-4,5-dimethylfuran (1.8 g, 9.68 mmol) in CH2Cl2 (10.0 mL). After the additions were complete, the reaction was allowed to warm to ambient temperature and stirred for 24 h. The reaction was quenched into crushed ice (100 g), diluted with sat. aq. KH2PO4 (100 mL) and extracted with ether. The combined ethereal extracts were washed with sat aq. NaHCO3 (2×60 mL), with brine (1×60 mL), dried (Na2SO4) and concentrated. The crude product was purified on Biotage KP-Sil eluting with 1% EtOAc/pet. ether to give 2.07 g, (62%) of the title compound as an oil; 1H NMR (DMSO-d6) δ 1.17 (d, 12 H), 1.81 (s, 3 H), 2.19 (s, 3 H), 3.29 (septet, 2 H), 3.74 (s, 3 H), 3.84 (s, 2 H), 7.01-7.03 (m, 2 H), 7.16-7.25 (m, 3 H), 7.47 (s, 2 H). mass spectrum (EI), m/z 404 (M+). Anal. Calcd. for C27H32O3.0.6H2O: C, 78.07; H, 8.06; N, 0.00. Found: C, 78.04; H, 7.93; N, -0.02.

Workup

  1. temperatureto warm to ambient temperature
  2. customThe reaction was quenched
  3. custominto crushed ice (100 g)
  4. additiondiluted with sat. aq. KH2PO4 (100 mL)
  5. extractionextracted with ether
  6. washThe combined ethereal extracts were washed with sat aq. NaHCO3 (2×60 mL), with brine (1×60 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. customThe crude product was purified on Biotage
  10. washKP-Sil eluting with 1% EtOAc/pet. ether

Sources & evidence

ORD record
ord-59ac38616b634f8db96a90896404491e
Source dataset
uspto-grants-2000_08
Patent number
US06103708

Reaction notes

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