p-Toluenesulfonic acid → HCID 68607104, compound

HRID 2267597Notes

Reaction equation

HRID 2267597 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8][CH:9]([C:26]1[CH:31]=[C:30]([F:32])[CH:29]=[CH:28][C:27]=1[F:33])[C@@H:10]([C:22]([O:24]C)=O)[NH:11][C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13].C1(C)C=CC(S(O)(=O)=O)=CC=1>>[F:33][C:27]1[CH:28]=[CH:29][C:30]([F:32])=[CH:31][C:26]=1[C@H:9]1[C@@H:10]([NH:11][C:12](=[O:13])[O:14][CH2:15][C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:22](=[O:24])[NH:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=2[S:8]1

Participants

3

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 68607971HCID 68607971, compound

Product 1

HCID 68607104HCID 68607104, compoundYield 60%

Procedure

A suspension of methyl β-[(2-aminophenyl)thio]-N-[(benzyloxy)carbonyl]-2,5-difluorophenylalaninate (4:1, Z:E) (4.3 g) and p-toluenesulfonic acid (catalytic) in xylenes (100 mL) was heated to reflux for 2 h, using a Dean-Stark apparatus to remove water. The mixture was then cooled, resulting in precipitation of the crude product as a white solid (3.3 g, 4:1, cis:trans). This was recrystallized from ethyl acetate/ether to afford the title compound (2.4 g, 60%). 1H NMR (300 MHz, d6-DMSO) δ 4.63 (t, 1H), 4.96 (s, 2H), 5.47 (d, 1H), 7.00 (d, 1H), 7.23-7.34 (m, 9H), 7.49-7.53 (m, 2H), 7.70 (d, 1H), 10.57 (s, 1H). MS APCI, m/z=441 (M+1). LC/MS: 2.74 min.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 2 h
  3. customto remove water
  4. temperatureThe mixture was then cooled
  5. customresulting in precipitation of the crude product as a white solid (3.3 g, 4:1, cis:trans)
  6. customThis was recrystallized from ethyl acetate/ether

Sources & evidence

ORD record
ord-c526a3b96cfc42c2a2db77e9f29fc862
Source dataset
uspto-grants-2010_12
Patent number
US07858776B2

Reaction notes

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