ChemicalBook CAS DataBase List 3-(1-ADAMANTYL)-4-METHOXYBENZENEBORONIC ACID

3-(1-ADAMANTYL)-4-METHOXYBENZENEBORONIC ACID synthesis

4synthesis methods

Product Name:3-(1-ADAMANTYL)-4-METHOXYBENZENEBORONIC ACID
CAS Number:459423-32-6
Molecular formula:C17H23BO3
Molecular Weight:286.17

121-43-7

104224-63-7

3-(1-ADAMANTYL)-4-METHOXYBENZENEBORONIC ACID

459423-32-6

Step B. Synthesis of 3-(1-adamantyl)-4-methoxyphenylboronic acid Example 2: In a 1L three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel, a mixture of 8 g (0.33 mol) of magnesium shavings and 200 mL of anhydrous tetrahydrofuran was added. Subsequently 8 g (0.19 mol) of crushed anhydrous lithium chloride was added. The air in the flask was replaced with argon and subsequent operations were carried out under an inert atmosphere. Under vigorous stirring, 11 g (5 mL, 0.06 mol) of 1,2-dibromoethane was added all at once. After the vigorous reaction subsided, 50 g (0.16 mol) of 2-(1-adamantyl)-4-bromoanisole dissolved in 400 mL of tetrahydrofuran was slowly added dropwise, with the rate of titration controlled to maintain a slight reflux. After dropwise addition, stirring was continued and heated to slow reflux for 30 minutes. Stirring was stopped and the resulting Grignard reagent was decanted from the residual magnesium into a conical flask that had been pre-flushed with argon and cooled to 0°C and kept sealed for 2 hours. In another 1L three-necked flask, 33 g (36 mL, 0.35 mol) of trimethyl borate and 100 mL of anhydrous tetrahydrofuran were added and mixed with stirring. The resulting solution was cooled to 0-5 °C (ice-water bath) and the pre-prepared Grignard reagent was added dropwise over 10 min under vigorous stirring. The reaction mixture was allowed to stand overnight (16 hours) in a refrigerator at 0-5°C. Subsequently, cooling was withdrawn and 50 mL of hydrochloric acid (diluted in 50 mL of water) was added under vigorous stirring to quench the reaction. The mixture was transferred to a partitioning funnel for layering. The aqueous layer was diluted with 200 mL of water and extracted twice with 100 mL of diethyl ether. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent (water bath temperature about 50°C). The residue was treated with 200 mL of ethyl acetate and allowed to stand overnight in a refrigerator. The precipitate was collected by filtration and dried at 100 °C to give 30 g of 3-(1-adamantyl)-4-methoxyphenylboronic acid (68% yield) with a melting point of 300 °C. Example 10: The reaction was carried out according to the method described in Example 2, with the difference that the reaction of 3-(1-adamantyl)-4-methoxyphenylmagnesium bromide solution with trimethyl borate was carried out at -70°C, to ultimately obtain 30.6 g of 3-(1-adamantyl)-4-methoxyphenylboronic acid (69% yield).

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Yield: 94.8%

Reaction Conditions:

Stage #1:2-(1-adamantyl)-4-bromoanisole with n-butyllithium in tetrahydrofuran at -75 - -70; for 1 h;
Stage #2:Triisopropyl borate in tetrahydrofuran at -70 - 20;
Stage #3: with hydrogenchloride;water in tetrahydrofuran at 20;

Steps:

1.a
Example 1 : EPO a) - Preparation of 3-adamantyl-4-mβthoxyphβnylboronic acid (II) :100 g (0.311 mol) of 2- (1-adamantyl) -4-bromoanisole (IV) and 500 ml of THF are introduced, under nitrogen, into a 2 L three-necked reactor. The reaction medium is cooled to -75°C. 137 ml (0.342 mol) of a 2.5 M nBuLi solution are added. After stirring for 1 h at -70⁰C, 80 ml (0.342 mol) of triisopropyl borate are added. After returning to room temperature, the reaction mixture is hydrolysed with 1 litre of 1.2 N HCl. The aqueous phase is extracted with ethyl acetate and the combined organic phases are washed with 1 litre of saturated NaCl, and then with 1 litre of water. The organic phases are dried over sodium sulphate and the solvents are evaporated. 88.37 g of a white solid are obtained, which solid is reimpasted in 440 mL of heptane. After filtration, the precipitate obtained is rinsed with heptane, and then dried under reduced pressure at 35°C until a constant weight is obtained. 84.4 g of 3-adamantyl-4-methoxyphenylboronic acid are obtained in the form of a white solid - (yield = 94.8%; m.p. = 263°C) .¹H NMR (CDCl₃): δ: 1.77 (s; 6H); 2.10 (m; 3H); 2.20 (s; 6H); 3.91 (s; 3H); 7.00 (d; IH; J₁₌8.0 Hz); 8.05 (dxd; IH; J₂=I.5 Hz and Ji=8.0 Hz); 8.15 (d; IH, J₂=I.5 Hz)

References:

GALDERMA RESEARCH & DEVELOPMENT, S.N.C. WO2006/108717, 2006, A2 Location in patent:Page/Page column 8-9

104224-63-7 Synthesis

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459423-32-6
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References

121-43-7
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104224-63-7 Synthesis

104224-63-7
307 suppliers
$16.00/5g

459423-32-6
99 suppliers
$50.00/25mg