Hydrochloric Acid → (E)-4-(Benzo[d]thiazol-2-ylthio)-2-methylbut-2-en-1-ol

HRID 2202772Notes

Reaction equation

HRID 2202772 reaction equation
C1[O:6][CH:2]1[C:3](=[CH2:5])[CH3:4].[CH3:7]N(C=O)C.[SH:12][C:13]1[S:14][C:15]2[CH:21]=[CH:20][CH:19]=[CH:18][C:16]=2[N:17]=1.Cl>C(Cl)Cl.[Cu]I.CCOC(C)=O.CCCCCC>[S:14]1[C:15]2[CH:21]=[CH:20][CH:19]=[CH:18][C:16]=2[N:17]=[C:13]1[S:12][CH2:7]/[CH:5]=[C:3](\[CH3:4])/[CH2:2][OH:6]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 1549093,4-Epoxy-2-methyl-1-buteneHCID 178418395HCID 178418395, compound

Product 1

HCID 118599150(E)-4-(Benzo[d]thiazol-2-ylthio)-2-methylbut-2-en-1-olYield 9%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent3×

Procedure

Isoprene monoxide (2.64 g, 31.40 mmol) of Chemical Formula 2 was mixed with DMF (30 mL) and stirred, and the resulting stirred solution was added with 2-mercaptobenzothiazole (5.25 g, 31.40 mmol) and CuI (299 mg, 1.57 mmol). The reaction mixture was stirred at room temperature for 21 hr, and added with a 1 M HCl solution to terminate the reaction, and the resulting reaction product was diluted with CH2Cl2. The unreacted yellow starting material was removed using a porous glass funnel filter, and the filtrate was washed with a 1 M NaOH solution and H2O, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure, thus obtaining a crude product. The crude product was analyzed with 1H-NMR, yielding a 1,2-addition product (0.68 g, 2.71 mmol, 9% yield, Rf=0.31/1:4 EtOAc/hexane), a 1,4-addition product (Z-configuration, 0.85 g, 3.38 mmol, 11% yield, Rf=0.24/1:4 EtOAc/hexane), and a 1,4-addition product (E-configuration, Chemical Formula 3, 3.40 g, 13.53 mmol, 43% yield, Rf=0.15/1:4 EtOAc/hexane) at a ratio of 1:1.25:5 from the sulfide.

Workup

  1. stirringthe resulting stirred solution
  2. stirringThe reaction mixture was stirred at room temperature for 21 hr
  3. customto terminate
  4. customthe reaction
  5. customthe resulting reaction product
  6. customwas removed
  7. filtrationfilter
  8. washthe filtrate was washed with a 1 M NaOH solution and H2O
  9. dry with materialdried over anhydrous Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customthus obtaining a crude product

Sources & evidence

ORD record
ord-2e706c75b1bc48f6bc926b559dba1247
Source dataset
uspto-grants-2016_06
Patent number
US09365561B2

Reaction notes

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