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[ CAS No. 144072-29-7 ]

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2D
Chemical Structure| 144072-29-7
Chemical Structure| 144072-29-7
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Product Details of [ 144072-29-7 ]

CAS No. :144072-29-7MDL No. :MFCD04974271
Formula : C12H17NO3 Boiling Point : 310.049°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :223.27Pubchem ID :10242688
Synonyms :

Computed Properties of [ 144072-29-7 ]

TPSA : 58.6 H-Bond Acceptor Count : 3
XLogP3 : 1.6 H-Bond Donor Count : 2
SP3 : 0.42 Rotatable Bond Count : 4

Safety of [ 144072-29-7 ]

Signal Word:WarningClassN/A
Precautionary Statements:P261-P305 P351 P338UN#:N/A
Hazard Statements:H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 144072-29-7 ]

  • Upstream synthesis route of [ 144072-29-7 ]
  • Downstream synthetic route of [ 144072-29-7 ]

[ 144072-29-7 ] Synthesis Path-Upstream   1~7

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YieldReaction ConditionsOperation in experiment
100% With N-ethyl-N,N-diisopropylamine In tetrahydrofuranHeating / reflux To a solution of p-amino-benzylalcohol (1 g, 8.12 mmol, 1 eq) in 80 mL of anhydrous THF were added DIEA (1.4 mL, 8.12 mmol, 1 eq) and BoC2O (1.9 mL, 8.12 mmol, 1 eq). The mixture was heated to reflux overnight, then cooled down and evaporated under vacuum. The residue was dissolved in EtOAc. The organic layer was washed with a 0.1 N HCl solution, dried over MgSO4, filtered and evaporated under vacuum. The crude product was purified by <n="74"/>column chromatography on silica gel (Hex-EtOAc, 1:1, v/v) to give 1.85 g of product (quantitative yield): 1H NMR δ 0.1.49 (9H, s), 2.17 (IH, s), 4.53 (2H5 s), 6.83 (IH, s), 7.19 (2H, d, J = 8.5 Hz), 7.28 (2H, d, J = 8.2 Hz); 13 C NMR δ 28.28, 64.54, 80.37, 118.49, 127.59, 135.31, 137.46, 152.72.
98% for 18.00 h; To a 250 mL round bottom flask was added (4-amino-phenyl)-methanol (4.13 g, 33.6 mmol), dichloromethane (50 mL) followed by di-tert-butyl dicarbonate (8.5 g, 36.9 mmol). The mixture was allowed to stir for 18 h under a nitrogen atmosphere. By TLC, a small amount of starting amine remained, which reacted during concentration by rotary evaporation. The product was purified by column chromatography (ethyl acetate : hexanes, 1:1) to yield (4- hydroxymethyl-phenyl)-carbamic acid tert-butyl ester (7.36 g, 33.0 mmol, 98 percent) as a white solid.
98% at 80℃; for 0.17 h; Green chemistry General procedure: The reactions were carried out in a 50 mL RB flask under reduced pressure for 10 min at 80°C unless reported differently. In a typical experiment, 5 mmol of amine was added to 5 mmol of BOC anhydride, and the reaction was allowed to proceed for 10 min. The desired product was obtained in a rotary evaporator under vacuum conditions.
87% With sodium hydroxide In 1,4-dioxane; water at 0 - 20℃; for 1.50 h; PREPARATION 15; Preparationof teri-buty\\ 4-(chloromethyl)phenylcarbamate; A. To a stirred solution of 4-aminobenzyl alcohol ( 1.50 g. 12.18 mmol) in 1.4-dioxane (30 mL) was added sodium hydroxide (0.49 g. 12.2 mmol) in water (30 mL). The mixture was cooled to 0 0C. and di-/1H NMR (300 MHz. CDCl3) δ 7.37-7.26 (m. 4H). 6.52 (br s. I H). 4.63 (s, 2H). 1.52 (s. 9H); MS (ES+) m/z 246.3 (M + 23).
83% With triethylamine In tetrahydrofuran at 20 - 50℃; A i00-mL, three-necked, round-bottomed flask, was equipped with a magnetic stimng bar, a retlux condenser, and a pressure-equalizing dropping funnel that was connected to a nitrogen flow line and charged with a solution of 97percent di-tert-butyl dicarbonate (4.04 g, 18.5 nimol) in tetralydrofuran (30 mid). Amino benzyi alcohol (2.5 g, 20.3 mmol) was placed in the flask and suspended in tetrahydrofuran (65 mL) and 99percent triethylamine (3.1 mL, 22 mmoi). The resultmg white suspension was cooled with an ice-water bath and the solution of di-tert-butyl dicarbonate was added dropwise over a period of 30 minutes. After 10 mm of additional stirring, the ice-water bath was removed and the suspension was stirred overnight at room temperature, then warmed at 50°C for a further 3 hours. T he solvent was removed tinder reduced pressure and the residue partitioned between EtOAc (50 mL) and saturated aqueous bicarbonate solution (50 mL). The aqueous phase was extracted with three 50-ni. portions of EtOAc. The combined organic phases were dried with anhydrous MgSO4 and concentrated under reduced pressure to give 3.72 g (83percent yield) of the product as a brown oil that was used without further purification. ‘H NMR (as rotamers) (400 MHz, CDCh) 6 9.26 (s, I H), 8.64 (s, iH), 7.39 (.4H), 7.20 (4H), 5,75 (s, 1H), 5.05 (2H), 4.49 —4.35 (m, 4H), i.47 (s, 9H), 1.40 (s, 1H).
82% With triethylamine In 1,4-dioxane at 20℃; Intermediate 10: tert-butyl 4-(hydroxymethyl)phenylcarbamateTo a solution of p-aminobenzyl alcohol (38,2 mmol) in 100 ml dioxane were added triethylamine (114 mmol) and di-tert-butyldicarbonate (42,0 mmol) was added in portions. The mixture was stirred overnight at room temperature. The solvent was evaporated. EtOAc was added and washed with 2N HCI, saturated NaHCO3 and brine solution. The organic layer was dried over Na2SO4 and evaporated to yield a brown oil.Yield: 82 percent, MS (ESI) m/z 224.3 [M+H]1H-NMR (ODd3, 400 MHz) 51.54 (s, 9H), 4.65 (s, 2H), 6.54 (s, 1H), 7.22-7.43 (m, 4H).
74% With acetic acid In tetrahydrofuran; water at 20℃; for 18.00 h; Inert atmosphere tert-Butyl (4-(hydroxymethyl)phenyl)carbamate 19. To a solution of ra-aminobenzyl alcohol (0.123 g, 0.0999 mmol) in AcOH (10percent in water, 8 mL) was added a solution of di-feri-butyl dicarbonate in THF (1 M, 1.05 mL, 1 .05 mmol), and the reaction was stirred for 18 h at ambient temperature. Water (30 mL) was added, and the mixture was basified with a NaOH solution (2 M) to pH 14. The resulting mixture was extracted with Et20 (3 χ 30 mL). The combined organic layer was washed with water (2 x 1 5 mL), dried over Na2S04, filtered, and concentrated under reduced pressure to afford boc-protected aminobenzyl alcohol 19 (0.166 g, 0.743 mmol, 74percent yield) as a light yellow solid. [000219] NMR (600 MHz, CDC13) δ 7.34 (2H, d, J = 8.0 Hz), 7.28 (2H, d, J = 8.4 Hz), 4.62 (2H, s), 1 .52 (9H, s). [000220] 13C NMR (150 MHz, CDC13) δ 152.9, 138.0, 135.6, 128.0, 1 18.7, 65.1 , 31.3, 28.5. [000221] HRMS: Obsvd 246.1 102 [M + Na]+, Calcd for C12H17NNa03: 246.1 101.
59% With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; To a solution of (4-aminophenyl)methanol (30, 8.0 g, 65.0 mmol) in THF (50 mL) were added Boc2O (21.3 g, 97.5 mmol) and DIEA (16.8 g, 130.0 mmol) at rt, and the resulting mixture was refluxed overnight. The reaction mixture was concentrated and purified by column chromatography (silica gel, eluted with 1:10 MeOH/DCM) to yield 31 (8.6 g, 59percent) as a yellow solid. 1H NMR (400 MHz, CD3OD) δ 1.53 (9H, s), 4.54 (2H, s), 7.26 (2H, d, J = 8.4 Hz), 7.38 (2H, d, J = 8.4 Hz). MS (API): m/z 206.0 (M + H - H2O)+.

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