1-Chloro-2,4-dimethoxybenzene → 1-Methoxy-4-(2-methoxycyclopropyl)benzene

HRID 520987Notes

Reaction equation

HRID 520987 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1OC.COC1C=CC=[C:18]([O:39][CH3:40])[C:19]=1[C:20]1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:40][O:39][CH:18]1[CH2:19][CH:20]1[C:2]1[CH:3]=[CH:4][C:5]([O:8][CH3:9])=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 1389051-Chloro-2,4-dimethoxybenzeneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

Product 1

HCID 687461631-Methoxy-4-(2-methoxycyclopropyl)benzene

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
100 °C

Procedure

To form 2,4-dimethoxy-cyclopropylbenzene (4cc), the general procedure was followed using 1-chloro-2,4-dimethoxybenzene (3b) (173 mg, 1.00 mmol), cyclopropyl MIDA boronate (2h) (236 mg, 1.20 mmol), SPhos (41 mg, 0.10 mmol) and Pd(OAc)2 (11 mg, 0.048 mmol). The reaction temperature was modified so that the reaction mixture was heated to 100° C. for 6 h. Compound 4cc was isolated as a colorless liquid (175 mg, 97%). TLC (hexanes:EtOAc 9:1) Rf=0.65, visualized by UV (254 nm). 1H-NMR (500 MHz, CDCl3w/ TMS) δ 6.77 (d, J=8.5 Hz, 1H), 6.44 (d, J=2.5 Hz, 1H), 6.39 (dd, J=8.5, 2.5 Hz, 1H), 3.83 (s, 3H), 3.77 (s, 3H), 2.03 (m, 1H), 0.85 (m, 2H), 0.57 (m, 2H). 13C-NMR (125 MHz, CDCl3) δ 159.2, 158.6, 125.7, 124.2, 103.8, 98.4, 55.5, 55.3, 9.0, 6.9. HRMS (EI+) Calculated for C11H14O2 (M)+: 178.0994, Found: 178.0995. IR (thin film, cm−1) 3080, 3000, 2955, 2940, 2835, 1615, 1585, 1510, 1464, 1439, 1416, 1370, 1319, 1290, 1261, 1209, 1172, 1158, 1117, 1062, 1037, 938, 884, 834, 823, 799.

Sources & evidence

ORD record
ord-8c1ccdf4b8564d798ad65fd40d23c39e
Source dataset
uspto-grants-2016_05
Patent number
US09328102B2

Reaction notes

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