2'-HYDROXY-6'-METHOXYACETOPHENONE

2'-HYDROXY-6'-METHOXYACETOPHENONE Property

Melting point:

58-60 °C(lit.)

Boiling point:

141 °C16 mm Hg(lit.)

Density 

1.158

refractive index 

1.5500 (estimate)

Flash point:

141°C/16mm

storage temp. 

Sealed in dry,Room Temperature

pka

9.79±0.10(Predicted)

form 

solid

color 

Light yellow to yellow

BRN 

1869049

LogP

2.390 (est)

CAS DataBase Reference

703-23-1(CAS DataBase Reference)

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-37/39

WGK Germany 

3

Hazard Note 

Irritant

TSCA 

N

HS Code 

29145090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

2'-HYDROXY-6'-METHOXYACETOPHENONE Chemical Properties,Usage,Production

Chemical Properties

Yellow crystalline powder

Uses

2''-Hydroxy-6''-methoxyacetophenone is useful in the synthesis of an aminopyrazole compound which is used to treat cancer and inhibits Chk1. 2''-Hydroxy-6''-methoxyacetophenone is also used to prepare 5,?4''-?disubstituted flavones, predicted androgen receptor antagonists and naphthopyrazolyl carbothioamides which are anticancer agents.

Uses

2′-Hydroxy-6′-methoxyacetophenone was used as starting material in the synthesis of 5-methoxyflavaone. It was also used in synthesis of 5,6-dihydroxyflavone.

Preparation

Preparation by reaction of methyl iodide on 2,6-dihydroxyacetophenone with potassium carbonate in boiling acetone (56%).

Definition

ChEBI: 2'-Hydroxy-6'-methoxyacetophenone is an aromatic ketone.

General Description

An organometallic synthetic route to 2′-hydroxy-6′-methoxyacetophenone was reported.

Synthesis

Under argon protection, TBAF (157 mg, 0.60 mmol) was dissolved in DMA (1.2 mL), followed by addition of a solution of 3-methoxy-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (53 μL, 0.20 mmol) in DMA (0.8 mL). The reaction mixture was stirred at room temperature for 3 hours. Upon completion of the reaction, the reaction was quenched by the addition of water (0.1 mL). The reaction mixture was concentrated under reduced pressure and the residue was purified by fast silica gel column chromatography (eluent: ethyl acetate/hexane = 1/20 to 1/8 containing 2% dichloromethane) to afford 2-hydroxy-6-methoxyacetophenone (10, 11.3 mg, 34%), 2-(N,N-dimethyl)amino-6-methoxyacetophenone (11, 3.8 mg, 10%) and 3-methoxy- N,N-dimethylaniline (12, 1.3 mg, 5%). 2-Hydroxy-6-methoxyacetophenone (10): colorless crystals, melting point 57-57.5 °C (ethyl acetate/hexane). IR (KBr) νmax 3110, 3009, 2947, 1623, 1594, 1459 cm?1.1 1H NMR (CDCl3) δ 13.23 (1H, s), 7.33 (1H, t, J = 8.0 Hz ), 6.56 (1H, dd, J = 8.0, 1.0 Hz), 6.39 (1H, dd, J = 8.0, 1.0 Hz), 3.90 (3H, s), 2.67 (3H, s).13C NMR (CDCl3) δ 205.1, 164.6, 161.5, 136.0, 111.3, 110.7, 101.1, 55.6, 33.7.MS (EI+) m/z 83 (100), 166 (M+, 3).HRMS (EI+) calculated value of C9H10O3 (M+) 166.0624, measured value 166.0646. 2-(N,N-dimethyl)amino-6-methoxyacetophenone (11): colorless oil. ir (CHCl3) νmax 2942, 1702, 1577, 1468 cm?1. 1H NMR (CDCl3) δ 7.23 (1H, br t, J = 8.0 Hz), 6.67 (1H, br d, J = 8.0 Hz), 6.56 ( 1H, br d, J = 8.0 Hz), 3.78 (3H, s), 2.72 (6H, s), 2.50 (3H, s).13C NMR (CDCl3) δ 205.2, 156.2, 151.8, 130.2, 125.3, 111.0, 104.7, 55.8, 44.8, 31.8.MS (EI+) m/z 83 (100), 193 (M+, 0.4). HRMS (EI+) calculated value C11H15NO2 (M+) 193.1097, measured value 193.1121. 3-Methoxy-N,N-dimethylaniline (12): colorless oily substance. ir (KBr) νmax 2955, 1610, 1493, 1465 cm?1. 1H NMR (CDCl3) δ 7.15 (1H, t, J = 8.0 Hz), 6.36 (1H, dd, J = 8.0, 2.5 Hz), 6.31-6.27 (2H, m), 3.80 (3H, s), 2.94 (6H, s).13C NMR (CDCl3) δ 160.6, 151.9, 129.7, 105.7, 101.3, 99.1, 55.1, 40.6.MS (EI+) m/z 83 (100), 151 (M+, 0.4).HRMS (EI+) calculated values C9H14NO (M++H+) 152.1070, measured value 152.1055.

References

[1] Tetrahedron, 2012, vol. 68, # 1, p. 179 - 189
[2] Tetrahedron, 2012, vol. 68, # 1, p. 179 - 189