反応 #1772044

反応方程式

Thionyl chloride

6-(3-bromophenyl)hexanoic acid

aluminum trichloride

→

2-bromo-7,8,9,10-tetrahydrobenzo[8]annulen-5(6H)-one

収率 67.4%

溶媒

carbon disulfide

反応条件

後処理

1. 1
   その他excess reagent was removed in vacuo
2. 2
   workup.DISSOLUTIONThe acid chloride was dissolved in carbon disulfide (550 mL)
3. 3
   温度heated
4. 4
   温度at reflux
5. 5
   温度cooled
6. 6
   その他decanted
7. 7
   濃縮concentrated
8. 8
   workup.STIRRINGthe resultant solids were stirred in diethyl ether/THF (1:1, 1 L)
9. 9
   workup.WAIT1N HCl (500 mL) for 1.5 hours
10. 10
    ろ過The organic layer was filtered
11. 11
    洗浄washed with water, and brine

実験手順

Thionyl chloride (13.2 mL, 181 mmol) was added (neat) to Example 2a, 6-(3-bromophenyl)hexanoic acid (16 g, 59.2 mmol) in a 1 L round-bottomed flask under a nitrogen atmosphere. The mixture was warmed to 60° C. for 2 h, excess reagent was removed in vacuo, and the residue was subjected to azeotropic conditions (benzene 3×). The acid chloride was dissolved in carbon disulfide (550 mL) and cannulated into a solution of aluminum trichloride (26.3 g, 198 mmol) in carbon disulfide (1315 mL) heated at reflux. The reaction was stirred 20 h, cooled, decanted, concentrated, and the resultant solids were stirred in diethyl ether/THF (1:1, 1 L), and 1N HCl (500 mL) for 1.5 hours. The organic layer was filtered, washed with water, and brine to give Example 3c, 2-bromo-7,8,9,10-tetrahydrobenzo[8]annulen-5(6H)-one 10.1 g (66%) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.55 (d, J=8.4 Hz, 1H), 7.38 (dd, J=8.4 Hz, 1.8 Hz, 1H), 7.33 (d, J=1.8 Hz, 1H), 2.99 (t, J=6.6 Hz, 2H), 2.89 (t, J=6.6 Hz, 2H), 1.85-1.73 (m, 4H), 1.52-1.44 (m, 2H). RT=2.8 minutes (condition 2); LRMS: Anal. Calcd. for C12H13BrO: 253.02. found: 253.15 (M+H).

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