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[ CAS No. 1149-26-4 ]

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Chemical Structure| 1149-26-4
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CAS No. :1149-26-4 MDL No. :MFCD00008922
Formula : C13H17NO4 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :251.28 g/mol Pubchem ID :726987
Synonyms :

Safety of [ 1149-26-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302+H312+H332-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1149-26-4 ]

  • Upstream synthesis route of [ 1149-26-4 ]
  • Downstream synthetic route of [ 1149-26-4 ]

[ 1149-26-4 ] Synthesis Path-Upstream   1~11

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YieldReaction ConditionsOperation in experiment
90% With dicyclohexyl-carbodiimide In tetrahydrofuran at 0 - 20℃; for 16 h; Step 1.
To a stirred solution of compound 39-1 (1 g, 4 mmol), compound 39-2 (459 mg, 4 mmol) in THF (20 mL) was added DCC (908 mg, 4.4 mmol) at 0°C. The reaction mixture was stirred at r.t. for 16 h. The mixture was filtered and the filtrate was concentrated to give compound 39-3 (Yield: 90 percent).
85.5 g With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran at 5℃; for 20.75 h; 2-(((benzyloxy)carbonyl)amino)-3-methylbutanoic acid (65g, 259mMol), tetrahydrofuran (450ml) were charged to a flask. N-hydroxy succinimide (33.3g 285mMol) was added to the reaction mass. Reaction mass was stirred for lOmins. Dimethyl amino pyridine (DMAP, lg) was added to the reaction mass. Reaction mass was stirred and temperature of reaction mass was decreased to 5°C. Solution of DCC in THF (42.5percent, 200ml) was added dropwise to the reaction mass over a period of 45 minutes at 5°C. Reaction mass was stirred for 20 hours. Obtained solid was filtered; solvent was stripped off under reduced pressure. Solid was washed with heptane (3x250ml ), to get crude material (2,5- dioxopyrrolidin-l-yl 2-(((benzyloxy)carbonyl)amino)-3-methylbutanoate) with sufficient purity. Yield 85.5 g. (0091) JH NMR (DMSO-D6, 400 MHz): δ 1.02(d,6H), 2.24(m,lH), 2.82(s,4H), 4.37(q,lH), 5.09 (s,2H), 7.34-7.44 (m,5H), 8.09 (d,lH). (0092) 13C NMR (DMSO D6, 100MHz): δ 18.3, 19.3, 25.4, 30.1, 58.1, 65.9, 127.7, 128.4,136.7, 156.3, 168.0, 170.0, 172.8 (0093) FTIR (KBr): 3327, 2933, 2117, 1816, 1784, 1741, 1527, 1204, 893 cm"1 . (0094) MS (EI): Q7H20N2O6 Exact mass: 348.35, observed mass: 366.2 (+ H20).
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Reference: [1] Tetrahedron Letters, 1983, vol. 24, # 41, p. 4451 - 4454
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YieldReaction ConditionsOperation in experiment
98%
Stage #1: With N-ethyl-N,N-diisopropylamine; HATU In N,N-dimethyl-formamide at 0℃; for 0.25 h;
Stage #2: With ammonium chloride In N,N-dimethyl-formamide at 23℃; for 16 h;
[0197] To a stuffed solution of compound I (10 g, 39.84 mmol, 1 eq) in DMF (100 mL) was added DIPEA (19.7 mL, 119.5 mmol, 3 eq) and HATU (18.17 g, 47.8 mmol, 1.2 eq) at 0°C and the resulting mixture was stuffed for 15 mm. To the mixture was added ammonium chloride (10.7 g, 199.2 mmol, 5 eq) and the resulting mixture was allowed to stir at 23°C for another 16 h. The mixture was poured into ice cold water (500 mL), the organic components were extracted with EtOAc (3 x 500 mL) and the combined organic layers were washed with aqueous ammonium chloride solution and brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to dryness. The crude product was recrystallized from ethanol to obtain the title compound (9.8 g, 98percent) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) ö 7.35 (m, 6H), 7.12 (d, 1H, J = 9 Hz), 7.01 (s, 1H), 5.03 (s, 2H), 3.80 (t, 1H, J = 8 Hz), 1.95 (m, 1H), 0.85 (m, 6H). LCMS: mlz = 251.2 [M+Hj , RT = 2.81 minutes, (Program P1, Column Y).
93%
Stage #1: With chloroformic acid ethyl ester; triethylamine In tetrahydrofuran at 0℃; for 0.5 h;
Stage #2: With ammonium chloride In tetrahydrofuran; water at 0℃; for 0.5 h;
General procedure: To a colorless solution of 150mg (0.50mmol) of Cbz-L-Phe-OH 3a in 10mL of THF were added 67μL (0.70mmol, 1.4equiv) of ClCO2Et and 209μL (1.5mmol, 3.0equiv) of Et3N at 0°C.
After stirring for 30min at 0°C, 0.75 ml of a 1.0M aqueous solution of NH4Cl (0.75mmol, 1.5equiv) were added at 0°C to the colorless suspension.
The mixture was stirred for 30min at 0°C and 5mL of H2O was added to the resulted mixture.
The colorless clear solution was extracted with 30mL of EtOAc and the aqueous layer was extracted with 20mL of EtOAc.
The organic layers were combined, washed with 5mL of brine, and dried over anhydrous MgSO4.
The crude product was chromatographed on silica gel with EtOAc to afford 129mg (86percent yield) of Cbz-L-Phe-NH2 4a. 4.3.7
Cbz-l-Val-NH2 4d
117 mg (93percent); >99percent ee; coloress solid; mp: 172-175 °C; [α]D25 = +17.8 (c 0.99, DMSO); 1H NMR (400 MHz, DMSO-d6): δ 0.83 (d, J = 6.8 Hz, 3H, CH3), 0.86 (d, J = 6.8 Hz, 3H, CH3), 1.94 (ddd, J = 6.7, 6.8, 6.8 Hz, 1H, CH(CH3)2), 3.80 (dd, J = 6.7, 8.8 Hz, 1H, CHCO), 5.03 (s, 2H, OCH2C6H5), 7.03 (br, 1H, CONHA), 7.16 (d, J = 8.8 Hz, 1H, NHCH), 7.29-7.39 (m, 6H, CONHB, C6H5); 13C NMR (100 MHz, DMSO-d6): δ 18.0, 19.3, 30.1, 60.0, 65.3, 127.6, 127.7, 128.3, 137.1, 156.1, 173.2; IR (KBr, vmax/cm-1): 3381 (CONH), 3319 (CONH), 3203 (CONH), 1654 (CON); HRMS (ESI-TOF): Calcd for C13H18N2O3Na (M+Na)+: 273.1210, found: 273.1193; The enantiomeric ratio was determined by HPLC (Chiralcel AD: hexane/2-propanol = 90/10): Tr 11.5 min.
63.8%
Stage #1: With chloroformic acid ethyl ester; triethylamine In tetrahydrofuran at -78℃; for 1 h;
Stage #2: With ammonium hydroxide In tetrahydrofuran at 20℃; for 2 h;
Step 1. To a solution of 27-1 (8 g, 31.8 mmol) and Et3N (6.43 g, 63.6 mmol) in dry THF (100 mL) at -78°C was added dropwise a solution of ethyl chloro formate (3.45 g, 31.8 mmol) in THF (10 mL). After the reaction was stirred at -78°C for 1 h, NH3.H20 (5 mL) was added. The reaction was warmed to r.t. over 2 h. White solid was collected by filtration and dried to give 27-2 (5.1 g, 63.8percent).
53.15% With pyridine; di-<i>tert</i>-butyl dicarbonate; ammonium bicarbonate In 1,4-dioxane at 0 - 20℃; To a solution of (S)-2-(benzyloxycarbonylamino)-3-methylbutanoic acid (10.0 g, 39.84 mmol) in 1,4-dioxane (50 mL) was added di-tert-butyl dicarbonate (11.95 g, 51.79mmol) in portions at 0°C. Then pyridine (2 mL, 25.76 mmol) was added drop-wise at 0°C, followed by ammonium bicarbonate (3.94 g, 50.43 mmol) in portions. The reaction was stirred at room temperature overnight. The mixture was poured into ice water and filtered. The filter cake was washed with water and dried under vacuum. The filter cake was then re-crystallized from dioxane/water (80 mL, 9: 1, v/v) to give (S)-benzyl (1-amino-3-methyl-1-oxobutan-2-yl)carbamate(5.3 g, 53.15percent yield) as a white solid. LC-MS (ESI) found: 251 [M+Hf’, ee>99percent, (CHIRALPAK AS-H, 15percent ethanol/ hexane)

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