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[ CAS No. 681465-85-0 ]

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2D
Chemical Structure| 681465-85-0
Chemical Structure| 681465-85-0
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Product Details of [ 681465-85-0 ]

CAS No. :681465-85-0MDL No. :MFCD12168764
Formula : C11H15NO3 Boiling Point : 348.8°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :209.24Pubchem ID :43380211
Synonyms :

Computed Properties of [ 681465-85-0 ]

TPSA : 61.6 H-Bond Acceptor Count : 4
XLogP3 : 1.9 H-Bond Donor Count : 1
SP3 : 0.36 Rotatable Bond Count : 4

Safety of [ 681465-85-0 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P261-P305+P351+P338UN#:N/A
Hazard Statements:H302-H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 681465-85-0 ]

  • Upstream synthesis route of [ 681465-85-0 ]
  • Downstream synthetic route of [ 681465-85-0 ]

[ 681465-85-0 ] Synthesis Path-Upstream   1~5

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YieldReaction ConditionsOperation in experiment
100% With palladium 10% on activated carbon; hydrogen In methanol at 20℃; for 17 h; Inert atmosphere 3-Isopropoxy-4-aminomethylbenzoate
3-Isopropoxy-4-nitromethylbenzoate (2.60 g, 10.87 mmol) was dissolved in MeOH (91.0 mL) and degassed. Pd/C (10percent wt., 0.58 g, 0.54 mmol) was added and vacuum was applied under cooling to remove air.
The flask was flushed with H2 and the suspension was stirred for 17 hours at room temperature.
The catalyst was filtered over Celite®, washed with MeOH and the solvent was removed under reduced pressure.
The crude product was purified by flash chromatography (petroleum ether/EtOAc=7/3).
3-Isopropoxy-4-aminomethylbenzoate was obtained (2.27 g, 10.85 mmol, quantitative) as a light orange solid.
mp: 55-57° C.
1H NMR (400 MHz, CDCl3) δ 7.51 (dd, J=8.2, 1.7 Hz, 1H), 7.46 (d, J=1.7 Hz, 1H), 6.66 (dd, J=8.2, 5.1 Hz, 1H), 4.63 (sept, J=5.1 Hz, 1H), 3.85 (s, 3H), 1.36 (s, 3H), 1.35 (s, 3H) ppm.
13C NMR (100 MHz, CDCl3) δ 167.5, 144.24, 142.3, 124.0, 119.5, 114.1, 113.5, 70.9, 51.8, 22.3 ppm.
HRMS (ESI): Calculated for C11H16NO3 (M+H)+: 210.1130. found: 210.1126.
Reference: [1] Patent: US2016/145304, 2016, A1, . Location in patent: Paragraph 0387; 0388; 0389; 0390; 0391; 0392
[2] Organic and Biomolecular Chemistry, 2012, vol. 10, # 15, p. 2928 - 2933
[3] Organic and Biomolecular Chemistry, 2008, vol. 6, # 1, p. 138 - 146
[4] Journal of the American Chemical Society, 2015, vol. 137, # 24, p. 7608 - 7611
[5] Tetrahedron Letters, 2011, vol. 52, # 29, p. 3705 - 3709
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YieldReaction ConditionsOperation in experiment
90% With caesium carbonate In acetone for 10 h; Heating / reflux 4-Amino-3-isopropoxy-benzoic acid methyl ester (3-4). To a solution of 2.045 g (12.23 mmol) methyl 4-amino-3-hydroxybenzoate (3-3) in 40 ml acetone, 1.83 ml 2-iodopropane (18.34 mmol, 1.5 eq.) and 7.97g (24.45 mmol, 2.0 eq.) Cs2CO3 were added. The resulting mixture was refluxed for 10 h and 10 ml of concentrated ammonium hydroxide was added. The solution was refluxed for 30 min and then cooled to room temperature. The mixture was diluted with water and extracted with Et2O. The organic layers were combined and washed with brine then dried with MgSO4. The crude mixture was purified by column chromatography on silica gel (hexane/EtOAc=4/1) to yield 3-4 as a colorless oil (2.300g, 90percent). 1H-NMR (400 MHz, CDCl3): δ=1.31 (d, 6H, J=6.07 Hz, 2CH3), 3.82 (s, 3H, CH3), 4.32 (s, 2H, NH2), 4.57 (m, 1H, CH), 6.62 (d, 1H, J=8.17 Hz), 7.44 (d, 1H, J=1.71 Hz), 7.50 (dd, 1H, J1=8.21 Hz, J2=1.80 Hz). 13C-NMR (100 MHz, CDCl3): δ=21.87, 51.43, 70.47, 113.10, 113.68, 118.81, 123.70, 142.22, 143.81, 167.23. HRMS (ESI) m/z: calcd. for C11H16NO3 210.1101, found 210.2032 (M++H).
60% With caesium carbonate In acetone at 120℃; for 1 h; Microwave Methyl3-hydroxy-4-aminobenzoate (ABCR: 100 mg, 0.60 mmol) caesium carbonate (396 mg, 1.22 mmol) were taken up in acetone (4 mL) and 2-iodopropane (90 μl, 0.90 mmol) added and reaction heated in microwave (CEM discover; 150 W) to 120° C. and held for 30 mins A further aliquot of 2-iodopropane (90 μl, 0.90 mmol) was added and reaction heated again to 120° C. in microwave, holding for a further 30 minsThe reaction was repeated twice on a 0.89 mmol scaleReaction mixtures were combined and evaporated to dryness and the residue partitioned between, ethyl acetate (40 ml) and water (50 ml). The organic phase was separated and the aqueous re-extracted with ethyl acetate (40 ml). Combined organic extracts were washed with brine, dried over magnesium sulphate and evaporated to give a brown oil which was purified by column chromatography, on silica (40 g cartridge; ISCO companion) eluting with a rising gradient of 5-50percent ethyl acetate in iso-hexane. Product containing fractions were combined and evaporated to dryness to afford the product as a yellow oil (301 mg, 60percent)1H NMR (400.132 MHz, DMSO-D6) δ 1.28 (d, 6H), 3.75 (s, 3H), 4.53 (m, 1H), 5.51 (s, 2H), 6.66 (d, 1H), 7.31 (m, 1H), 7.37 (m, 1H); MS m/z 209.4 [M+H]+.
Reference: [1] Journal of the American Chemical Society, 2005, vol. 127, # 15, p. 5463 - 5468
[2] Patent: US2007/123592, 2007, A1, . Location in patent: Page/Page column 8; sheet 1
[3] Patent: US2008/9482, 2008, A1, . Location in patent: Page/Page column 115
[4] Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 6, p. 1375 - 1379
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YieldReaction ConditionsOperation in experiment
82.7%
Stage #1: With caesium carbonate In acetone for 6 h; Reflux
Stage #2: With ammonium hydroxide In acetone for 0.5 h; Reflux
This compound was prepared with minor modifications as described in PCT int. Appl. 2005079541 (01 Sept. 2005) as follows: To a solution of Methyl 4-amino-3 -hydro ybenzoate (l .Og, 6.0 mmol) in acetone (20 mL) at ambient temperature was added 2-bromopropane (l .lg, 9.0 mmol) followed by cesium carbonate (3.9g, 12 mmol) each in one portion. The resulting mixture was heated a reflux temperature for 6 hr. Concentrated ammonium hydroxide (5 mL) was added and the mixture was refluxed for an additional 30 min. After cooling to ambient temperature the mixture was diluted with water (100 mL) and extracted with 3X 75 mL of diethyl ether. The combined extracts were washed with 2X 50 mL of brine and dried over magnesium sulfate. The mixture was filtered and concentrated in vacuo. The residue was taken up in diethyl ether, silica gel was added and the mixture concentrated in vacuo. The residue was transferred to a pre- column and purified by chromatography using initially hexanes (1 min.) as eluent. The eluent was modified to 30percent ethyl acetate/hexanes over a 15 min. period and kept at 30percent ethyl acetate/hexanes for the remainder of the purification. Fractions containing the pure desired component were combined and concentrated in vacuo to give 1.03g (82.7percent yield) of a pale yellow oil that solidified on standing to a white solid. MS: m/z 210.1 (MKT). 1H NMR (500 MHz, DMSO-d6): δ 1.279 (d, 6H), 3.744 (s, 3H), 4.525 (m, 1H), 5.532 (s; 2H), 6.651 (d, 1H), 7.299 (d,lH), 7.363 (dd, 1H).
Reference: [1] Patent: WO2014/165816, 2014, A1, . Location in patent: Page/Page column 100-101
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Reference: [1] Tetrahedron Letters, 2011, vol. 52, # 29, p. 3705 - 3709
[2] Organic and Biomolecular Chemistry, 2012, vol. 10, # 15, p. 2928 - 2933
[3] Journal of the American Chemical Society, 2015, vol. 137, # 24, p. 7608 - 7611
[4] Patent: US2016/145304, 2016, A1,
  • 5
  • [ 619-14-7 ]
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Reference: [1] Organic and Biomolecular Chemistry, 2012, vol. 10, # 15, p. 2928 - 2933
[2] Journal of the American Chemical Society, 2015, vol. 137, # 24, p. 7608 - 7611
[3] Patent: US2016/145304, 2016, A1,
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