4-Toluenesulfonyl chloride → 2-(2-Bromophenyl)ethyl 4-methylbenzene-1-sulfonate

HRID 992678Notes

Reaction equation

HRID 992678 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[CH2:4][CH2:5][OH:6].[CH3:11][C:12]1[CH:17]=[CH:16][C:15]([S:18](Cl)(=[O:20])=[O:19])=[CH:14][CH:13]=1.[OH-].[K+]>C(OCC)C.O.N1C=CC=CC=1>[CH3:11][C:12]1[CH:17]=[CH:16][C:15]([S:18]([O:6][CH2:5][CH2:4][C:3]2[CH:7]=[CH:8][CH:9]=[CH:10][C:2]=2[Br:1])(=[O:20])=[O:19])=[CH:14][CH:13]=1

Participants

7

Reactant 3

HCID 73974-Toluenesulfonyl chloride2×HCID 14797Potassium HydroxideHCID 27340892-(2-Bromophenyl)ethan-1-ol

Product 1

HCID 109152412-(2-Bromophenyl)ethyl 4-methylbenzene-1-sulfonateYield 98%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
18 °C

Procedure

A magnetically stirred solution of 2-bromophenethyl alcohol (5.00 g, 24.9 mmol, ex ALDRICH) and 4-methylbenzenesulfonyl chloride (11.20 g, 59.7 mmol) in diethyl ether (50 ml) was cooled to 0° C. (ice-bath) then treated with powdered KOH (3.2 g, 2.4 mole equiv.). The reaction mixture thus obtained was allowed to warm to 18° C., stirred at this temperature for 2.0 h then diluted with water (100 ml). The separated organic phase was washed with water (1×100 ml) then dried (MgSO4), filtered and concentrated under reduced pressure to give a white solid. Since this material contained residual 4-methylbenzenesulfonyl chloride it was dissolved in pyridine (75 ml) and the resulting solution stirred at 18° C. for 0.16 h then diluted with water (500 ml) and extracted with diethyl ether (1×500 ml). The separated organic phase was washed with HCl (1×250 ml of a 5 M aqueous solution) then sodium hydrogen carbonate (1×250 ml of a 0.5 M aqueous solution) before being dried (MgSO4), filtered and concentrated under reduced pressure to give the title compound (8.66 g, 98%) as white crystalline masses, m.p. 39-39.5° C. (Found: C, 50.9; H, 4.2; Br, 22.6; S, 8.8. C15H15BrO3S requires C, 50.7; H, 4.3; Br, 22.5; S, 9.0%). nmax (KBr) 1356, 1177, 1021, 980, 962, 895, 812, 769, 752, 665, 557 cm−1. 1H n.m.r. d 7.68, d, J 8.3 Hz, 2H; 7.45, d, J 7.7 Hz, 1H; 7.27, d, J 8.3 Hz, 2H; 7.17, m, 2H; 7.07, m, 1H; 4.25, t, J 7.0 Hz, 2H; 3.09, t, J 7.0 Hz, 2H; 2.43, s, 3H. 13C n.m.r. d 144.5 (C), 135.3 (C), 132.7 (CH), 132.8 (C), 131.3 (CH), 129.7 (CH), 128.5 (CH), 127.6 (CH), 127.4 (CH), 124.2 (C), 68.6 (CH2), 35.5 (CH2), 21.5 (CH3). Mass spectrum m/z 356 (0.7%) 354 (0.7) (M+.); 184 (98) 182 (100) [M—H3CC6H4SO3H)+.]; 171 (49) 169 (51); 155 (45); 103 (32); 91 (80) (C7H7+).

Workup

  1. customThe reaction mixture thus obtained
  2. washThe separated organic phase was washed with water (1×100 ml)
  3. dry with materialthen dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customto give a white solid
  7. stirringthe resulting solution stirred at 18° C. for 0.16 h
  8. extractionextracted with diethyl ether (1×500 ml)
  9. washThe separated organic phase was washed with HCl (1×250 ml of a 5 M aqueous solution) then sodium hydrogen carbonate (1×250 ml of a 0.5 M aqueous solution)
  10. dry with materialbefore being dried (MgSO4)
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-d83740c687bb45dc845c71761cb831e6
Source dataset
uspto-grants-2002_10
Patent number
US06469171B1

Reaction notes

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