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

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

Melting point:

239-242

Boiling point:

475.0±55.0 °C(Predicted)

Density 

1.20±0.1 g/cm3(Predicted)

storage temp. 

Inert atmosphere,2-8°C

pka

8.94±0.10(Predicted)

Appearance

White to off-white Solid

InChI

InChI=1S/C17H23BO3/c1-21-16-3-2-14(18(19)20)7-15(16)17-8-11-4-12(9-17)6-13(5-11)10-17/h2-3,7,11-13,19-20H,4-6,8-10H2,1H3

InChIKey

FPZOBRFHRPQGAA-UHFFFAOYSA-N

SMILES

B(C1=CC=C(OC)C(C23CC4CC(CC(C4)C2)C3)=C1)(O)O

Safety

Hazard Codes 

Xi

Hazard Note 

Irritant/Keep Cold

HS Code 

2931900090

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

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P304+P340IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.

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

P405Store locked up.

3-(1-ADAMANTYL)-4-METHOXYBENZENEBORONIC ACID Chemical Properties,Usage,Production

Uses

Promotes the ortho hydroxalkylation of phenols by aldehyde. Used as reagent in the proection of thiols as cyclic boronates. This has been utilized to trap cis thiols in oder to prevent over oxidation during dihydroxylation reaction by osmium (4)oxide.

Synthesis

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).

References

[1] Russian Journal of General Chemistry, 2010, vol. 80, # 4, p. 868 - 869
[2] Russian Journal of General Chemistry, 2010, vol. 80, # 4, p. 868 - 869
[3] Patent: US2010/160677, 2010, A1. Location in patent: Page/Page column 3-4