Реакция #626151

Уравнение реакции

triisopropoxyborane

lithium 2,2,6,6-tetramethylpiperidide

n-butyllithium

benzonitrile

HCl

2,2,6,6-tetramethylpiperidine

→

2-cyanophenylboronic acid

Выход 34.0%

Растворители

ethyl acetate

hexane

THF

Условия реакции

Обработка

1. 1
   ТемператураThe temperature of the reaction solution was increased to room temperature
2. 2
   Другоеthe acid phase (pH<1) was separated
3. 3
   ЭкстракцияThe aqueous phase was extracted with 105 ml of ethyl acetate
4. 4
   workup.ADDITIONThen, the two organic phases were mixed
5. 5
   Промывкаwashed with 90 ml of saturated brine
6. 6
   СушкаThe resulting organic phase was then dried with anhydrous magnesium sulfate
7. 7
   Концентрированиеconcentrated
8. 8
   Другоеan evaporator
9. 9
   workup.ADDITIONThe concentrated solution was charged with 100 ml of dichloromethane
10. 10
    workup.ADDITIONthe solution was charged with 50 ml of hexane at 0° C
11. 11
    ФильтрацияThe precipitated crystals were filtered
12. 12
    Другоеdried

Методика

In a 300 ml nitrogen-substituted flask, 21.6 g (0.153 mol) of 2,2,6,6-tetramethylpiperidine was dissolved in 130 ml of THF. Then, to the resulting solution, 96 ml (0.153 mol) of a 15% solution of n-butyllithium in hexane was added dropwise at −10° C. to prepare lithium 2,2,6,6-tetramethylpiperidide. This solution was cooled to −78° C., and then 67 ml (0.291 mol) of triisopropoxyborane was added dropwise thereto. Next, 15 g (0.146 mol) of benzonitrile was added dropwise, and then the resulting solution was aged for 2 hours at the same temperature. The temperature of the reaction solution was increased to room temperature, and then the solution was hydrolyzed by 225 ml of 2N HCl. The solution was charged with 150 ml of ethyl acetate and stirred, and then the acid phase (pH<1) was separated. The aqueous phase was extracted with 105 ml of ethyl acetate. Then, the two organic phases were mixed and washed with 90 ml of saturated brine. The resulting organic phase was then dried with anhydrous magnesium sulfate and concentrated using an evaporator. The concentrated solution was charged with 100 ml of dichloromethane, and then the solution was charged with 50 ml of hexane at 0° C. The precipitated crystals were filtered and dried to obtain 7.3 g of 2-cyanophenylboronic acid crystals. The purity of the 2-cyanophenylboronic acid was 98.7%, in which 0.3 mol % of 1-phenyl-1-(2,2,6,6-tetramethylpiperidin-1-yl)methyl imine was included.

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