[ CAS No. 70264-94-7 ]

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CAS No. :70264-94-7MDL No. :MFCD00270115
Formula :C10H11BrO3InChI Key :UXSNXOMMJXTFEG-UHFFFAOYSA-N
M.W :259.10Pubchem ID :2759828
Boiling Point :-
Synonyms :

Computed Properties

TPSA : 35.5 H-Bond Acceptor Count : 3
XLogP3 : 2.3 H-Bond Donor Count : 0
SP3 : 0.30 Rotatable Bond Count : 4

Safety

Signal Word:DangerClass6.1
Precautionary Statements:P273-P280-P305+P351+P338UN#:2811
Hazard Statements:H315-H317-H318-H410Packing Group:
GHS Pictogram:

Application In Synthesis

[ 70264-94-7 ] Synthesis Path-Upstream   1~5

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YieldReaction ConditionsOperation in experiment
97% With N-Bromosuccinimide In tetrachloromethane for 16.00 h; Heating / reflux STEP 1 : A mixture of methyl 4-methyl-3-(methyloxy)benzoate (1.00 g, 5.55 mmol), N-bromosuccinimide (1.09 g, 6.10 mmol) and a catalytic amount of 2,2'- azobis(isobutyronitrile) (AIBN) was refluxed in carbon tetrachloride (40 ml) for 16h.The reaction mixture was filtered and the solution was washed with brine (25 ml), dried over sodium sulfate and concentrated to give methyl 4-(bromomethyl)-3- (methyloxy)benzoate (1.4g, 97percent yield).
94% With tert.-butylhydroperoxide; cetyltrimethylammonim bromide; potassium bromide In water at 120℃; Microwave irradiation General procedure: The reaction mixture was treated in a controlled microwavesynthesizer (Biotage Initiator+SP Wave model, 0–200 W at2.45 GHz, capped at 60 W during steady state) for severalminutes (the reaction attained 120 °C at 1 bar pressure). Thefinal products were isolated by column chromatographyusing an EtOAc–hexane gradient
92% With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In ethyl acetateHeating / reflux Reference Example 49; Methyl 4-(bromomethyl)-3-methoxybenzoate; A mixture of methyl 3-methoxy-4-methylbenzoate (10.0 g, 55.5 mmol), N-bromosuccinimide (10.7 g, 60.9 mmol), 2,2'-azobis(isobutyronitrile)(1.6 mg) and ethyl acetate (200 ml) was heated under reflux overnight. The solvent was evaporated under reduced pressure, and hexane was added to the residue. The precipitate was filtered off, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (9: 1-7:3, v/v) to give the title compound (12.8 g, 92percent) as a colorless oil. 1H-NMR (CDC13) 8: 3. 92 (3H, s) , 3. 95 (3H, s) , 4. 55 (2H, s), 7.38 (1H, d, J=8.1 Hz) , 7.53 (1H, d, J=1.5 Hz) , 7.60 (1H, dd, J=1.5, 8.1 Hz).
82% With N-Bromosuccinimide; azobisisobutyronitrile In tetrachloromethane Part F.
Methyl 4-Bromomethyl-3-methoxybenzoate.
Methyl 3-methoxy-4-methylbenzoate (9.95 g; 55.2 mmol) and 10.81 g (60.7 mmol) of NBS were combined in 250 mL of CCl4 and heated to reflux. AIBN (0.75 g; 5.5 mmol) was added and the resultant mixture was heated at reflux for 8 h.
The mixture was refrigerated, then filtered and concentrated under reduced pressure.
The residue was triturated with hexanes and filtered to give the title compound as white needles (11.7 g; 82percent yield).
1H NMR (CDCl3) δ 7.63 (d, J=7.6 Hz, 1H), 7.58 (s, 1H), 7.41 (d, J=7.9 Hz, 1H), 4.56 (s, 2H), 3.98 (s, 3H), 3.94 (s, 3H); FDMS 528 (M+).
82% With N-Bromosuccinimide; azobisisobutyronitrile In tetrachloromethane A.
Methyl 4-Bromomethyl-3-methoxybenzoate.
Methyl 3-methoxy-4-methylbenzoate (9.95 g; 55.2 mmol) and 10.81 g (60.7 mmol) of NBS were combined in 250 mL of CCl4 and heated to reflux. AIBN (0.75 g; 5.5 mmol) was added, and the resultant mixture was heated at reflux for 8 h.
The mixture was refrigerated, then filtered and concentrated under reduced pressure.
The residue was triturated with hexanes and filtered to give the title compound as white needles (11.7 g; 82percent yield).
1H NMR (CDCl3) δ 7.63 (d, J=7.6 Hz, 1H), 7.58 (s, 1H), 7.41 (d, J=7.9 Hz, 1H), 4.56 (s, 2H), 3.98 (s, 3H), 3.94 (s, 3H); FDMS 528 (M+).
80% With N-Bromosuccinimide; dibenzoyl peroxide In chloroform for 18.00 h; Heating / reflux (4-Bromomethyl)-3-methoxybenzoic acid methyl ester: N-bromosuccinimide (7.2 g, 40 mmol) and benzoyl peroxide (40 mg, 0.16 mmol) were added to a stirred solution of 3-methoxy-4-methylbenzoic acid methyl ester (7.2 g, 40 mmol) in chloroform (300 mL). The mixture was then heated at reflux for about 18 hours. The solvent was evaporated and the residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=30/1, 5/1, v/v, elution) to afford the title product (8.25 g, 80percent). 1H NMR (300 MHz, CDCl3) δ 7.61 (d, 2H, J=7.8 Hz), 7.54 (s, 1H), 7.38 (d, 1H, J=8.1 Hz), 4.55 (s, 2H), 3.95 (s, 3H), 3.88 (s, 3H); LC-MS: m/z=259 (MH)+.
76.9% With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 80℃; for 5.00 h; To a solution of methyl 3-methoxy-4-methylbenzoate (10 g, 55.6 mmol) and NBS (1 1.8 g, 66.7 mmol) in CCI4 (200 ml.) was added AIBN (900 mg, 5.56 mmol). The reaction was stirred for 5 hours at 80 0C. TLC showed the reaction was completed. The mixture was filtered and the solvent was removed under the reduced pressure to give the desired product of Step A (1 1 g, 76.9percent). 1H NMR (CDCI3, 300 MHz) δ 7.63 (dd, J=1.2 and 6.0 Hz, 1 H) ,7.55 (s, 1 H), 7.39 (d, J= 6 Hz, 1 H),4.56 (s ,2 H) ,3.96 (s, 3H) and 3.91 (s, 3H).
64% With bromine In tetrachloromethane; water l.
Methyl 4-bromomethyl-3-methoxybenzoate
A stirred solution of methyl 3-methoxy-4-methylbenzoate (121.2 g) in carbon tetrachloride (1.4 liter) was heated under gentle reflux with a 350 watt tungsten lamp and subjected to an air purge by means of a T-tube attached to a water aspirator.
A solution of bromine (107.2 g) in carbon tetrachloride (500 ml) was added dropwise over 4 h.
Evaporation of the solvent gave a light yellow solid which was triturated with 500 ml of 1:9 ether:hexane.
The solid was collected by filtration to give methyl 4-bromomethyl-3-methoxybenzoate (111.7 g, 64percent) as a pale yellow solid: mp 87°-90°; NMR (80 MHz, CDCl3): 3.9(2s, 6H, 2 x OCH3), 4.5(s, 2H, BrCH2), 7.4(m, 3H).
64% With bromine In tetrachloromethane; water j.
Methyl 4-bromomethyl-3-methoxybenzoate
A stirred solution of methyl 3-methoxy -4-methylbenzoate (121.2 g) in carbon tetrachloride (1.4 liter) was heated under gentle reflux with a 350 watt tungsten lamp and subjected to an air purge by means of a T-tube attached to a water aspirator.
A solution of bromine (107.2 g) in carbon tetrachloride (500 ml) was added dropwise over 4 hr.
Evaporation of the solvent gave a light yellow solid which was triturated with 500 ml of 1:9 ether:hexane.
The solid was collected by filtration to give methyl 4-bromomethyl -3-methoxybenzoate (111.7 g, 64percent) as a pale yellow solid: mp 87-90°; NMR (80 MHz, CDCl3): 3.9(2s, 6H, 2 x OCH3), 4.5(s, 2H, BrCH2), 7.4(m, 3H).

Reference: [1] European Journal of Medicinal Chemistry, 1997, vol. 32, # 7-8, p. 547 - 570
[2] Patent: WO2009/55077, 2009, A1. Location in patent: Page/Page column 391-392
[3] Synlett, 2014, vol. 25, # 17, p. 2485 - 2487
[4] Patent: WO2005/105802, 2005, A1. Location in patent: Page/Page column 120-121
[5] Patent: US6391901, 2002, B1
[6] Patent: US6284756, 2001, B1
[7] Patent: US2009/191183, 2009, A1. Location in patent: Page/Page column 51
[8] Patent: WO2009/32667, 2009, A1. Location in patent: Page/Page column 179-180
[9] Journal of Medicinal Chemistry, 2018, vol. 61, # 13, p. 5758 - 5764
[10] Journal of Medicinal Chemistry, 1990, vol. 33, # 6, p. 1771 - 1781
[11] Journal of Medicinal Chemistry, 1988, vol. 31, # 3, p. 692 - 696
[12] Patent: US5041460, 1991, A
[13] Patent: US5047402, 1991, A
[14] Patent: US2009/149662, 2009, A1. Location in patent: Page/Page column 8
[15] Patent: US2009/149662, 2009, A1. Location in patent: Page/Page column 8
[16] Patent: WO2015/168279, 2015, A1. Location in patent: Paragraph 48
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YieldReaction ConditionsOperation in experiment
82% With N-Bromosuccinimide; azobisisobutyronitrile In tetrachloromethane D.
Methyl 4-Bromomethyl-3-methoxybenzoate
Methyl 3-methoxy-4-methylbenzoate (9.95 g; 55.2 mmol) and N-bromosuccinimide (10.81 g; 60.7 mmol) were combined in 250 mL of CCl4 and heated to reflux. AIBN (0.75 g; 5.5 mmol) was added and the resultant mixture was heated at reflux for 8 h.
The mixture was refrigerated, then filtered and concentrated under reduced pressure.
The residue was triturated with hexanes and filtered to give the bromo ester as white needles (11.7 g; 82percent yield).
1H NMR (CDCl3) δ7.63 (d, J=7.6 Hz, 1H), 7.58 (s, 1H) 7.41 (d, J=7.9 Hz, 1H), 4.56 (s, 2H), 3.98 (s, 3H), 3.94 (s, 3H); FDMS 528 (M+).
Reference: [1] Patent: US6271227, 2001, B1
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Reference: [1] Patent: US5280039, 1994, A
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Reference: [1] Journal of Medicinal Chemistry, 1990, vol. 33, # 6, p. 1771 - 1781
[2] Journal of Medicinal Chemistry, 2018, vol. 61, # 13, p. 5758 - 5764
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Reference: [1] Organic Process Research and Development, 2009, vol. 13, # 1, p. 67 - 72
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