Diisobutylaluminum hydride → HCID 69270444, compound

HRID 2221111Notes

Reaction equation

HRID 2221111 reaction equation
C[O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([S:11]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)(=[O:13])=[O:12])[C:9]=1[CH3:10])=O.CC(C[AlH]CC(C)C)C>O1CCCC1.C(Cl)Cl>[Cl:20][C:17]1[CH:16]=[CH:15][C:14]([S:11]([C:8]2[C:9]([CH3:10])=[C:5]([CH2:3][OH:2])[S:6][CH:7]=2)(=[O:13])=[O:12])=[CH:19][CH:18]=1

Participants

5

Reactant 2

HCID 14487Diisobutylaluminum hydride2×HCID 2778437Methyl 4-(4-chlorobenzene-1-sulfonyl)-3-methylthiophene-2-carboxylate

Product 1

HCID 69270444HCID 69270444, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 4-(4-Chloro-benzenesulfonyl)-3-methyl-thiophene-2-carboxylic acid methyl ester (992 mg, 3.00 mmol) in dry tetrahydrofuran (20 mL) and dry CH2Cl2 (10 mL) was cooled to 0° C. under N2, and DIBAL-H (9.0 mL, 9.0 mmol, 1 M solution in toluene) was added. After 3 hours, another portion of DIBAL-H (4.5 mL, 4.5 mmol) was added, and stirring was continued for another 2 hours. The reaction was quenched by the addition of saturated Rochelle salt solution (30 mL), and the mixture was stirred for 1 hour at room temperature. The phases were separated, the aqueous phase was extracted with EtOAc (2×50 mL) and the pooled organic layers were dried over Na2SO4 and evaporated in vacuo. The product was purified by chromatography on silica gel on a FlashMaster system using as eluent heptane/ethyl acetate (linear gradient elution from 1:0 to 6:4). Fractions containing the product were pooled and evaporated in vacuo to yield the desired compound (788 mg, 87%). LC-MS: (m/z)=285.2 (M−H2O+H+), calcd for C12H10ClO2S2: 284.9805, tR=2.45 min. 1H NMR (CDCl3): 1.84 (t, J=5.7 Hz, 1 H), 2.20 (s, 3 H), 4.73 (d, J=5.7 Hz, 2 H), 7.49 (d, J=8.5 Hz, 2 H), 7.84 (d, J=8.5 Hz, 2 H), 8.18 (s, 1 H).

Workup

  1. waitwas continued for another 2 hours
  2. customThe reaction was quenched by the addition of saturated Rochelle salt solution (30 mL)
  3. stirringthe mixture was stirred for 1 hour at room temperature
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted with EtOAc (2×50 mL)
  6. dry with materialthe pooled organic layers were dried over Na2SO4
  7. customevaporated in vacuo
  8. customThe product was purified by chromatography on silica gel on a FlashMaster system
  9. additionFractions containing the product
  10. customevaporated in vacuo

Sources & evidence

ORD record
ord-a07da0f56e244b46b44d0a7ad475423b
Source dataset
uspto-grants-2008_05
Patent number
US07368472B2

Reaction notes

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