Hydrochloric Acid → 4-[4-(3-Cyclopentylpropyl)-5-Tetrazolon-1-Yl]-Benzenesulfonyl Chloride

HRID 863803Notes

Reaction equation

HRID 863803 reaction equation
[ClH:1].N[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[N:9]1[C:13](=[O:14])[N:12]([CH2:15][CH2:16][CH2:17][CH:18]2[CH2:22][CH2:21][CH2:20][CH2:19]2)[N:11]=[N:10]1.N([O-])=O.[Na+].[S:27](=[O:29])=[O:28]>O.[Cu]Cl.C(O)(=O)C>[CH:18]1([CH2:17][CH2:16][CH2:15][N:12]2[C:13](=[O:14])[N:9]([C:4]3[CH:5]=[CH:6][C:7]([S:27]([Cl:1])(=[O:29])=[O:28])=[CH:8][CH:3]=3)[N:10]=[N:11]2)[CH2:22][CH2:21][CH2:20][CH2:19]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 19420721HCID 19420721, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 109267824-[4-(3-Cyclopentylpropyl)-5-Tetrazolon-1-Yl]-Benzenesulfonyl Chloride

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

To a solution of 32 mL of concentrated hydrochloric acid and 8 mL of glacial acetic acid at -20° C. was added 5.42 g of powdered 1-(4-aminophenyl)-4-(3-cyclopentylpropyl)-5-tetrazolone from Step D. The mixture was stirred for 5 min before a solution of 1.6 g of sodium nitrite in 10 mL of water was added at a rate which kept the temperature from rising above -10° C. The diazonium salt mixture was stirred an additional 40 min at -20° C. and then added in one portion to a solution of 32 mL of glacial acetic acid containing 690 mg of copper (I) chloride saturated with sulfur dioxide at 0° C. The resultant reaction mixture instantly changed in color from a dark green with nitrogen evolution to a lime green slurry as time progressed. The reaction mixture was allowed to warm from 0° C. to room temperature over 50 min. The mixture was then poured into ice-water and extracted with ethyl acetate. The combined organic extracts were washed once with cold water, dried over magnesium sulfate, filtered, and concentrated in vacuo to remove acetic acid. The crude sulfonyl chloride was purified by flash chromatography (silica gel, dichloromethane) to yield 3.4 g of the title compound as a white solid: 1H NMR (CDCl3) δ8.37 (d, 2H, J=9.1 Hz), 8.20 (d, 2H, J=8.6 Hz), 4.06 (t, 2H, J=7.1 Hz), 1.93 (m, 3H), 1.81 (m, 2H), 1.62 (m, 2H), 1.55 (m, 2H), 1.41 (m, 2H), 1.11 (m, 2H).

Workup

  1. additionwas added at a rate which
  2. customfrom rising above -10° C
  3. customThe resultant reaction mixture
  4. temperatureto warm from 0° C. to room temperature over 50 min
  5. extractionextracted with ethyl acetate
  6. washThe combined organic extracts were washed once with cold water
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto remove acetic acid
  11. customThe crude sulfonyl chloride was purified by flash chromatography (silica gel, dichloromethane)

Sources & evidence

ORD record
ord-cf14f5ad8e824a31ae4158f55945702d
Source dataset
uspto-grants-1996_10
Patent number
US05561142

Reaction notes

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