Hydrochloric Acid → N-But-2-en-1-ylglycine

HRID 1931145Notes

Reaction equation

HRID 1931145 reaction equation
C(O[N:19]1[C:24](=O)[CH2:23][CH2:22][C:20]1=O)(OCC1C2C(=CC=CC=2)C2C1=CC=CC=2)=O.Cl.N[C@@H:28](CC=CC)[C:29]([OH:31])=[O:30].C([O-])(O)=O.[Na+].Cl>CC(C)=O.O>[CH2:24]([NH:19][CH2:28][C:29]([OH:31])=[O:30])[CH:23]=[CH:22][CH3:20]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 134122N-(9-Fluorenylmethoxycarbonyloxy)succinimideHCID 516892Sodium BicarbonateHCID 131727453(2s)-2-Aminohex-4-enoic acid hydrochloride salt

Product 1

HCID 53407996N-But-2-en-1-ylglycineYield 211.3%

Reagents, catalysts & solvents 1

HCID 18366337Propan-2-one--water (1/1)Solvent

Procedure

2-N-Fluorenylmethoxycarbonylaminohex-4-enoic acid 100 was prepared according to the procedure described by Paquet.230 Fmoc-OSu (2.36 g, 7.00 mmol) was added to a stirred suspension of L-crotylglycine HCl 101 (1.16 g, 7.03 mmol) and NaHCO3 (2.95 g, 35.0 mmol) in a mixture of acetone:water (1:1, 30 mL). The resultant suspension was stirred at room temperature for 15 h. The reaction mixture was then acidified with concentrated HCl (pH 2) and the acetone was removed under reduced pressure. The resultant suspension was extracted into DCM (3×25 mL) and the combined organic extract was washed with dilute HCl solution (1 M, 2×25 mL), water (2×25 mL), dried (MgSO4) and evaporated under reduced pressure to afford the titled Fmoc-amino acid 100 as colourless solid (1.91 g, 78%), m.p. 119-121° C. νmax (KBr): 3390bm, 3033m, 2961s, 2357w, 1730s, 1651w, 1505w, 1450w, 1395w, 850w cm−1. 1H n.m.r. (300 MHz, CDCl3): δ 1.67 (d, J=6.2 Hz, 3H, H6), 2.37-2.69 (m, 2H, H3), 4.23 (t, J=6.8 Hz, 1H, H9′), 4.42-4.48 (m, 3H, CH2O, H2), 5.30-5.37 (m, 2H, H5, NH), 5.61 (m, 1H, H4), 7.31 (td, J=7.2, 1.3 Hz, 2H, H2′, 7′), 7.34 (td, J=7.4, 1.5 Hz, 2H, H3′, 6′), 7.60 (d, J=7.3 Hz, 2H, H1′, 8′), 7.74 (d, J=7.0 Hz, 2H, H4′, 5′), one exchangeable proton (OH) not observed. 13C n.m.r. (75 MHz, CDCl3): δ 16.7 (C6), 34.1 (C3), 46.2 (C9′), 52.3 (C2), 66.2 (CH2O), 118.9 (C5), 123.0 (C2′, 7′), 124.6 (C3′, 6′), 125.2 (C1′, 8′), 127.5 (C4′, 5′), 129.7 (C4), 140.3 (C8′a, 9′a), 142.7 (C4′a, 4′b), 154.9 (OCONH), 175.0 (C1). Mass Spectrum (ESI+, MeOH): m/z 352.1 (M+H)+, C21H22NO4 requires 352.2. Spectroscopic data were in agreement with those reported in the literature.146

Workup

  1. custom2-N-Fluorenylmethoxycarbonylaminohex-4-enoic acid 100 was prepared
  2. customthe acetone was removed under reduced pressure
  3. extractionThe resultant suspension was extracted into DCM (3×25 mL)
  4. extractionthe combined organic extract
  5. washwas washed with dilute HCl solution (1 M, 2×25 mL), water (2×25 mL)
  6. dry with materialdried (MgSO4)
  7. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-073759d9d4df4e12be738e93fec1274f
Source dataset
uspto-grants-2012_05
Patent number
US08188217B2

Reaction notes

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