4-(2-[2-Thiocarbonyl-3-carboethoxypyrrolidin-4-yl]ethyl)benzoic acid 2,2-dimethylethyl ester → 4-(2-(2-Thiocarbonyl-3-carboethoxypyrrolidin-4-yl)ethyl)benzoic acid

HRID 1769833Notes

Reaction equation

HRID 1769833 reaction equation
CC(C)C[O:4][C:5](=[O:26])[C:6]1[CH:11]=[CH:10][C:9]([CH2:12][CH2:13][CH:14]2[CH2:18][NH:17][C:16](=[C:19]=[S:20])[CH:15]2[C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:8][CH:7]=1>FC(F)(F)C(O)=O>[C:19](=[C:16]1[CH:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:14]([CH2:13][CH2:12][C:9]2[CH:8]=[CH:7][C:6]([C:5]([OH:26])=[O:4])=[CH:11][CH:10]=2)[CH2:18][NH:17]1)=[S:20]

Participants

3

Reactant 1

HCID 867473244-(2-[2-Thiocarbonyl-3-carboethoxypyrrolidin-4-yl]ethyl)benzoic acid 2,2-dimethylethyl ester

Product 1

HCID 200975214-(2-(2-Thiocarbonyl-3-carboethoxypyrrolidin-4-yl)ethyl)benzoic acidYield 104.6%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

A mixture of 4.17 grams (11.1 mmol) of 4-(2-[2-thiocarbonyl-3-carboethoxypyrrolidin-4-yl]ethyl)benzoic acid 2,2-dimethylethyl ester and 20 ml of trifluoroacetic acid was stirred at room temperature until a clear solution was obtained plus an additional 5 minutes. Next, the resulting mixture was concentrated in a rotary evaporator and the residue therefrom was dissolved in 10 ml of methanol. This new solution was carefully added to a suspension of 2 grams of NaHCO3 in saturated NaHCO3 solution. The pH was adjusted to 5.7 with acetic acid and the resulting mixture extracted with 5×20 ml of ethyl acetate. The combined extracts were dried (MgSO4) and then concentrated to give 3.87 grams (109% crude yield) of 4-(2-(2-thiocarbonyl-3-carboethoxypyrrolidin-4-yl)ethyl)benzoic acid as a foam which was sufficiently pure for use in Example 8. Crystalline 4-(2-(2-thiocarbonyl-3-carboethoxypyrrolidin-4-yl)ethyl)benzoic acid was obtained from chloroform. Selected data: mp 145° -148° C.; 1H NMR (DMSO-d6) δ10.39 (s, 1H), 7.80 (d, J=8.1 Hz, 2H), 7.24 (d, J=8.1 Hz, 2H), 4.06 (q, J=7.1 Hz, 2H), 3.64 (dd, J =10.9, 8.9 Hz, 1H), 3.46 (d, J=8.5 Hz, 1H), 3.20 (dd, J =10.9, 8.0 Hz, 1H), 2.64 (q, J=8.0 Hz, 1H), 2.54 (t, J=7.4 Hz, 2H), 1.70 (m, 2H), 1.12 (t, J=7.1 Hz, 3H); 13C NMR (DMSO-d6) δ198.6, 169.5, 167.0, 146.2, 129.1, 128.6, 128.1, 65.0, 60.4, 52.9, 40.8, 33.5, 32.6, 13.7; IR (CHCl3) 3410, 2985, 1732, 1694, 1517 cm-1 ; UV (EtOH) 236 nm (ε14 900), 271 (15 600); MS(FD) m/z 321 (M+). Anal. Calcd for C16H19NO4S: C, 59.79; H, 5.96; N, 4.36. Found: C, 59.77; H, 6.00; N, 4.37.

Workup

  1. customwas obtained plus an additional 5 minutes
  2. concentrationNext, the resulting mixture was concentrated in a rotary evaporator
  3. dissolutionthe residue therefrom was dissolved in 10 ml of methanol
  4. additionThis new solution was carefully added to a suspension of 2 grams of NaHCO3 in saturated NaHCO3 solution
  5. extractionthe resulting mixture extracted with 5×20 ml of ethyl acetate
  6. dry with materialThe combined extracts were dried (MgSO4)
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-7aaf418171a04f63ae389a74abde988e
Source dataset
uspto-grants-1995_01
Patent number
US05382668

Reaction notes

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