Triethylamine → Ethyl [({[4-(acetyloxy)-3-methoxybenzyl]oxy}carbonyl)amino]acetate

HRID 1798425Notes

Reaction equation

HRID 1798425 reaction equation
S=C1N([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([O:17][C:18](=[O:20])[CH3:19])=[C:13]([O:21][CH3:22])[CH:12]=2)=[O:8])CCS1.[NH2:23][CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26].C(N(C(C)C)CC)(C)C.C(N(CC)CC)C>C1COCC1.C(Cl)(Cl)Cl.C(Cl)Cl>[C:18]([O:17][C:14]1[CH:15]=[CH:16][C:11]([CH2:10][O:9][C:7]([NH:23][CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])=[O:8])=[CH:12][C:13]=1[O:21][CH3:22])(=[O:20])[CH3:19]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 12176Glycine ethyl esterHCID 81531DiisopropylethylamineHCID 568478684-(Acetyloxy)-3-methoxybenzyl 2-thioxo-1,3-thiazolidine-3-carboxylate

Product 1

HCID 66597863Ethyl [({[4-(acetyloxy)-3-methoxybenzyl]oxy}carbonyl)amino]acetateYield 60.2%

Reagents, catalysts & solvents 3

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Thiazolide VII (266.8 mg, 0.781 mmol) was dissolved in anhydrous THF (3 mL), and the resulting solution was added to a previously prepared solution of ethyl glycinate (130 mg, 1.19×0.781 mmol) and diisopropylethylamine (120 mg, 162 μL, 1.19×0.781 mmol) in chloroform (3 mL). To the resulting solution was added triethylamine (72.6 mg, 100 μL, 0.72 mmol) at which point a slight cloudiness developed. The mixture was stirred overnight at room temperature. The reaction mixture was diluted with CH2Cl2 and extracted with 1N HCl and saturated NaCl. The organic layer was dried over anhydrous MgSO4, filtered and concentrated. The product was purified by column chromatography on silica gel using a gradient of CH2Cl2/ethyl acetate (94:6-9:1, v/v) to yield 152.9 mg (60%) of a white solid 19: mp=62-64° C. (uncorrected); Rf=0.27 (CH2Cl2/EtOAc, 96:4, v/v); 1HNMR (CDCl3) δ 6.99 (d, 3J=8 Hz, 1H), 6.96 (bs, 1H), 6.92 (bd, 3J=8 Hz, 1H), 5.22 (bs, 1H), 5.08 (bs, 2H), 4.20 (q, 3J=7.15 Hz, 2H), 3.96 (d, 3J=5.55 Hz, 2H), 3.82 (s, 3H), 2.29 (s, 3H) and 1.27 (t, 3J=7.15 Hz, 3H). Exact mass (ESI) calculated for C15H20NO7 [M+H]=326.1234. found 326.1245.

Workup

  1. extractionextracted with 1N HCl and saturated NaCl
  2. dry with materialThe organic layer was dried over anhydrous MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe product was purified by column chromatography on silica gel using a gradient of CH2Cl2/ethyl acetate (94:6-9:1

Sources & evidence

ORD record
ord-9470aea2190c4b8b82fc3b6dd2aec1a8
Source dataset
uspto-grants-2013_01
Patent number
US08343971B2

Reaction notes

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