Toluene → HCID 22311850, compound

HRID 966542Notes

Reaction equation

HRID 966542 reaction equation
[C:1]([O:5][C:6](=[O:17])[NH:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([NH2:16])=[CH:12][CH:11]=1)([CH3:4])([CH3:3])[CH3:2].[C:18]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)(=[O:23])[CH2:19][C:20]([CH3:22])=O.[C:32]1(C)C=CC=CC=1>C1(C)C(S(O)(=O)=O)=CC=CC=1>[CH2:25]([O:24][C:18](=[O:23])/[CH:19]=[C:20](/[NH:16][C:13]1[CH:14]=[CH:15][C:10]([CH2:9][CH2:8][NH:7][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:17])=[CH:11][C:12]=1[CH3:32])\[CH3:22])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

5

Reactant 3

HCID 1140TolueneHCID 142266Benzyl acetoacetateHCID 382207Tert-butyl 4-aminophenethylcarbamate

Product 1

HCID 22311850HCID 22311850, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 69252-Methylbenzenesulfonic acidCatalyst

Procedure

[2-(4-Amino-phenyl)-ethyl]-carbamic acid tert-butyl ester (1.0 g, 2.76 mmol), benzyl acetoacetate (0.796 g, 4.14 mmol) and toluenesulfonic acid (0.026 g, 0.138 mmol) were refluxed in toluene at 125° C. 3 hours. The reaction was then cooled, evaporated to dryness, the crude redissolved in EtOAc and dried over anhydrous Na2SO4. Filtration under vacuum followed by purification on SiO2 (30% EtOAc/hexane) gave 1.055 g (71%) of the desired (E)-3-[4-(2-tert-butoxycarbonylamino-ethyl)-2-methyl-phenylamino]-but-2-enoicacid benzyl ester. 1HNMR (400 MHz, DMSO): δ 1.32 (s, 9H), 1.81 (s, 3H, olefineCH3),2.63 (t, J=2.96 Hz, 2H), 3.12 (q, J=6.03 Hz, 2H), 4.77 (s, 1H, olefineH), 5.07 (s, 2H), 6.83 (b, ArH), 7.20-7.35 (m, 6H, ArH), 7.70 (s, 1H, ArH), 10.05 (s, ArNH). MS(APCI−) m/z 535.2(M−1).

Workup

  1. custom3 hours
  2. temperatureThe reaction was then cooled
  3. customevaporated to dryness
  4. dissolutionthe crude redissolved in EtOAc
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationFiltration under vacuum
  7. customfollowed by purification on SiO2 (30% EtOAc/hexane)

Sources & evidence

ORD record
ord-4dcf0b4718e04cf9ba3f206df718c5f2
Source dataset
uspto-grants-2005_10
Patent number
US06951848B2

Reaction notes

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