Acetic Acid → Benzyl 3-benzyloxy-5-aminobenzoate

HRID 2266944Notes

Reaction equation

C(O)(=O)C.[CH2:5]([O:12][C:13]1[CH:14]=[C:15]([CH:26]=[C:27]([N+:29]([O-])=O)[CH:28]=1)[C:16]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:17])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>C(Cl)Cl.[Zn]>[CH2:5]([O:12][C:13]1[CH:14]=[C:15]([CH:26]=[C:27]([NH2:29])[CH:28]=1)[C:16]([O:18][CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)=[O:17])[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

Conditions

Temperature: 0 °C

Procedure

2.52 g (38.5 mmol) Zn were suspended in 6 mL methylene chloride (dry, distilled), 0.9 mL (15.7 mmol) acetic acid were added and the suspension was cooled to 0° C. A solution of 0.7 g (1.93 mmol) nitrobenzoate 12 in 2 mL methylene chloride was added by syringe. After 2 h of stirring, TLC (hexanes/ethyl acetate, 7:3, Rf=0.4) indicated complete conversion of starting material. Zn was filtered off and the filtrate was concentrated, taken up in ethyl acetate and washed with aqueous NaHCO3 three times, then with brine. After drying with MgSO4 and evaporation, an orange-brown oil was obtained, which was purified by column chromatography (hexanes/ethyl acetate, 7:3) to afford 310 mg (48%) of a yellow oil. 1H NMR (CDCl3) δ 7.50-7.27 (m, 10H), 7.12 (dd, J1=1.3 Hz, J2=2.2 Hz, 1H), 7.02 (dd, J1=1.3 Hz, J2=2.2 Hz, 1H), 6.49 (t, J1=2.2 Hz, J2=2.2 Hz, 1H), 5.38 (s, 2H, PhCH2), 5.03 (s, 2H), 3.69 (s, 2H, PhCH2).

Workup

filtrationZn was filtered off
concentrationthe filtrate was concentrated
washwashed with aqueous NaHCO3 three times
dry with materialAfter drying with MgSO4 and evaporation
customan orange-brown oil was obtained
customwhich was purified by column chromatography (hexanes/ethyl acetate, 7:3)

Sources & evidence

ORD record: ord-4d8058f1ed6b4b8080fa33ed5b8b1299
Source dataset: uspto-grants-2010_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07858737B2

Reaction notes

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