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[ CAS No. 1149388-19-1 ]

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Chemical Structure| 1149388-19-1
Chemical Structure| 1149388-19-1
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Product Details of [ 1149388-19-1 ]

CAS No. :1149388-19-1 MDL No. :MFCD26389396
Formula : C9H9BrO3 Boiling Point : 318.2±37.0°C at 760 mmHg
Linear Structure Formula :- InChI Key :-
M.W :245.07 g/mol Pubchem ID :57700291
Synonyms :

Safety of [ 1149388-19-1 ]

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

Application In Synthesis of [ 1149388-19-1 ]

  • Upstream synthesis route of [ 1149388-19-1 ]
  • Downstream synthetic route of [ 1149388-19-1 ]

[ 1149388-19-1 ] Synthesis Path-Upstream   1~2

  • 1
  • [ 55289-05-9 ]
  • [ 1149388-19-1 ]
YieldReaction ConditionsOperation in experiment
33% With bromine; <i>tert</i>-butylamine In dichloromethane at -70 - 20℃; To a solution of iert-butylamine (2.0 g, 27.1 mmol) in DCM (180 mL) at -70 °C was added a solution of Br2 (4.2 g, 27.1 mmol) in DCM (10 mL) dropwise and the mixture was stirred at - 70 °C for 1 hour. A solution of methyl 3-hydroxy-2-methylbenzoate I89 (4.5 g, 27.1 mmol) in DCM (10 mL) was then added dropwise and the resulting mixture allowed to warm to room temperature and stirred overnight. The reaction was quenched by addition of water (30 mL) and the aqueous layer extracted with DCM (3 x 50 mL). The combined organic layers were washed with brine, dried (Na2SO.i) and concentrated. The crude residue obtained was purified by silica gel chromatography (2percent EtOAc in petroleum ether) to give the title compound (2.2 g, 33percent) as a white solid. LCMS-C: RT 2.46 min; m/z 245.0, 247.0 [M+H] \ 1 H NMR (400 MHz, DMSO-cfe) δ 9.38 (s, 1 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.17 (d, J = 8.4 Hz, 1 H), 3.80 (s, 3H), 2.38 (s, 3H)
22% With bromine; <i>tert</i>-butylamine In dichloromethane at -78℃; for 2.5 h; A 500 ml 3-neck round bottom flask was fitted with two dropping funnels. Towas added a solution of the tert-butyl amine (4.4 g, 60.2 mmol) in CH2C12 (140 ml)the tiask was cooled to -78°C. A solution of bromine (9.6 g, 60.2 mmol) in CH2C12ml) was added drop wise over 30 minutes from the dropping funnel. The mixture was stirred at -78°C for another 1 h. A solution of methyl 3-hydroxy-2-methyl benzoate (10.0 g, 60.2 mrnol) in CH2C12 (25 ml) was added from the second dropping funnel during 1 h. (US 2005110979). The reaction mixture was allowed to warm to room temperature and stir for overnight. LCMS showed 3 peaks. Aqueous work up and extraction with DCM followed by flash column chromatography using an ISCO system (2 X 80 g silica gel column, hexane/EtOAc solvent mixture) gave the product (1st peak, fractions 4-5, 3.3 g, 22percent yield). The side products isolated and characterized as dibromo and 5-bromo derivatives. 1H NMR (CDC13): 7.29-7.21 (dd, 2H), 5.64 (s, 1H), 3.81(s, 3H), 2.45(s, 3H).
20% With bromine; <i>tert</i>-butylamine In dichloromethane at -78 - 20℃; A solution of bromine (1.608 mL, 31.29 mmol) in dichloromethane (20 mL) was added was added dropwise over 30 min to a solution of 2-methylpropan-2-amine (3.30 mL, 31.29 mmol) in dichloromethane (100 mL) at -78° C. The solution was stirred for 30 min at -78° C. A solution of methyl 3-hydroxy-2-methylbenzoate (5.2 g, 31.29 mmol) in dichloromethane (30 mL) was added over 30 min. The reaction was allowed to reach room temperature, stirred over night and water was added. The aqueous phase was extracted with dichloromethane and the combined organic phases were washed with water, dried over magnesium sulphate and concentrated in vacuo. Purification by column chromatography, using a gradient of 0 to 10percent ethyl acetate in heptane as the eluent, gave 1.51 g (20percent yield) of the title compound:MS (ESI) m/z 245, 243 [M-1]-
20% With bromine; <i>tert</i>-butylamine In dichloromethane at -78 - 20℃; A solution of bromine (1.608 mL, 31.29 mmol) in dichloromethane (20 mL) was added was added dropwise over 30 min to a solution of 2-methylpropan-2-amine (3.30 mL, 31.29 mmol) in dichloromethane (100 mL) at -780C. The solution was stirred for 30 min at - 780C. A solution of methyl 3-hydroxy-2-methylbenzoate (5.2 g, 31.29 mmol) in dichloromethane (30 mL) was added over 30 min. The reaction was allowed to reach room temperature, stirred over night and water was added. The aqueous phase was extracted with dichloromethane and the combined organic phases were washed with water, dried over magnesium sulphate and concentrated in vacuo. Purification by column chromatography, using a gradient of 0 to 10percent ethyl acetate in heptane as the eluent, gave 1.51 g (20percent yield) of the title compound: MS (ESI) m/z 245, 243 [M-I]"
17% With bromine; <i>tert</i>-butylamine In dichloromethane at -78 - 20℃; for 15.5 h; STEP 2: To a solution of tert-butylamine (1.6 mL, 15 mmol) in dichloromethane (100 mL) at -780C was added drop-wise over 30 minutes a solution of bromine (773 μl, 15 mmol in 15 mL of dichloromethane). The solution was stirred at -780C for 30 minutes. While maintaining the temperature at -780C, a solution of methyl 3-hydroxy-2-methylbenzoate (2.5 g, 15 mmol in 15 mL of dichloromethane) was added to the reaction mixture drop-wise over 30 minutes. The mixture was allowed to warm to room temperature and was stirred for 15 hours. The mixture was washed with 20percent aqueous citric acid then brine and dried over anhydrous sodium sulfate. Filtration and concentration afforded a brown residue that was purified by silica gel column chromatography. Eluting with 10percent diethyl ether in hexane, purified fractions were pooled and concentrated to afford 612 mg, 2.5 mmol (17percent) of methyl 4-bromo-3-hydroxy-2-methylbenzoate as a colorless oil. 1H NMR (400 MHz, CDCl3): 7.37-7.29 (m, 2H), 5.71 (s, IH), 3.81 (s, 3H), 2.53 (s, 3H). MS (EI) for C9H9BrO3: 245 (MH+).

Reference: [1] Patent: WO2016/34673, 2016, A1, . Location in patent: Page/Page column 108
[2] Patent: WO2014/144380, 2014, A1, . Location in patent: Paragraph 0482
[3] Patent: US2009/131468, 2009, A1, . Location in patent: Page/Page column 40-41
[4] Patent: WO2009/64251, 2009, A1, . Location in patent: Page/Page column 78
[5] Patent: WO2009/55077, 2009, A1, . Location in patent: Page/Page column 401
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  • [ 603-80-5 ]
  • [ 1149388-19-1 ]
Reference: [1] Patent: WO2014/144380, 2014, A1,
[2] Patent: WO2016/34673, 2016, A1,
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