p-Toluenesulfonic acid → HCID 20334531, compound

HRID 1111785Notes

Reaction equation

HRID 1111785 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([S:18](=[O:21])(=[O:20])[NH2:19])[C:10]=1[O:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:5]([OH:7])=[O:6].Br[CH2:23][CH2:24][CH:25]=[CH2:26].C1(C)C=CC(S(O)(=O)=O)=CC=1>C(O)CC=C>[CH2:26]([NH:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([S:18](=[O:21])(=[O:20])[NH2:19])[C:10]=1[O:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:5]([OH:7])=[O:6])[CH2:25][CH:24]=[CH2:23]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 21241Homoallyl bromideHCID 1199273-Amino-4-phenoxy-5-sulfamoylbenzoic acid

Product 1

HCID 20334531HCID 20334531, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 693893-Buten-1-olSolvent

Procedure

A solution of 3-amino-4-phenoxy-5-sulfamylbenzoic acid (7.5 g), 4-bromo-1-butene (12 ml), and p-toluenesulfonic acid (500 mg) in 3-buten-1-ol (35 ml) was heated under reflux for 6 days. Most of the solvent was recovered by distillation. The concentrated solution was diluted with pet. ether and stirred for 1/2 hour. The ester of the product was collected (3.9 g) and hydrolyzed in 10% by weight methanolic KOH at room temperature. A second crop of 4.0 g was a mixture of the esters of starting material and product. These were not separated. The 3.9 g crop afforded 3.1 g (35%) of 3-(but-3-enylamino)-4-phenoxy-5-sulfamylbenzoic acid which was clean by tlc. Recrystallization from ether/pet. ether gave colorless crystals. The analytical sample was sublimed in vacuum. The product had mp 228°-32° (dec); ir (Nujol) 3350, 3200, 2600 (broad), 1680, 1610, 1585, 1540 and 1515 cm-1 ; nmr (CDCl3 /d6 -DMSO/D2O-washed) 2.17 (q, 2H), 3.13 (t, 2H), 3.13 (t, 2H), 4.6-6.0 (m, 3H, vinyl), 6.8-7.5 (m, C6H5), 7.55 (d, J=2, CH), and 7.95 ppm (d, CH); mass spectrum m/e 321 (100%) and 363 (M+).

Workup

  1. temperatureunder reflux for 6 days
  2. distillationMost of the solvent was recovered by distillation
  3. additionThe concentrated solution was diluted with pet. ether
  4. customThe ester of the product was collected (3.9 g)
  5. customat room temperature
  6. additiona mixture of the esters of starting material and product
  7. customThese were not separated

Sources & evidence

ORD record
ord-34a6968b550d4b7e935c2f4829d72da5
Source dataset
uspto-grants-1978_10
Patent number
US04118587

Reaction notes

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