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CAS No. : | 210907-84-9 | MDL No. : | MFCD03453668 |
Formula : | C12H18BNO2 | Boiling Point : | - |
Linear Structure Formula : | NH2C6H4BOC(CH3)2C(CH3)2O | InChI Key : | YMXIIVIQLHYKOT-UHFFFAOYSA-N |
M.W : | 219.09 | Pubchem ID : | 2734655 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | at 80℃; for 12h; | Example 4 N-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-acetamide through halogen-metal exchange using n-butyllithium at benzhydryliden-(4-bromo-phenyl)-amine The synthetic of 3-aminophenylboronic acid pinacol ester is carried out as described in example 1. After completion of pinacolisation and phase separation the mixture is, however, not concentrated, rather the remaining organic phase is azeotropically dried. The residue, after adding 7.3 g (71.5 mmole) of acetic acid anhydride is stirred at 80 C. for 12 h. Thereafter the bulk of the solvent is removed by distillation and the mixture is cooled to -5 C. Thereby the product crystallizes in the form of colorless crystals and can be isolated by filtration. Thus, 9.37 g (35.9 mmole, 78%) of N-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-acetamide are obtained. Yield over all steps: 60%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Synthesis of l-(3-methanesulfonyl-phenyl)-3-[3-(4,4,5,5-tetramethyl- [l,3,2]dioxaborolan-2-yl)-pheny -urea (intermediate 24)[00431] 3-Methanesulfonyl-phenylamine (0.3 g, 1.44 mmol) was dissolved in 10 mL dichloromethane and diisopropylethylamine (0.376 mL, 2.15 mmol), then solid triphosgene (171 mg, 0.58 mmol) was added. By LCMS (MeOH quench), <10% starting material remained so 3-(4,4,5,5-tetramethyl-[l,3,2]dioxaborolan-2-yl)-phenylamine (315.5 mg, 1.44 mmol) and diisopropylethylamine (0.276 mL, 1.58 mmol) were added. The reaction was judged complete in lh by LCMS. MeOH (1 mL) was added and the reaction was stirred 18 h. The mixture was washed with DI water, saturated NaHC03, and 1 NHC1 and was dried over MgS04. After concentrtion in vacuo, an off-white solid was obtained. [M+H]+ m/z All. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | General procedure: An oven-dried Schlenk tube (A) equipped with a magnetic stir bar was charged with AgF (132.2 mg, 1.05 mmol, 3.5 equiv), sealed with a septum, and degassed by alternating vacuum evacuation and nitrogen backfill (three times) before freshly distilled EtCN (3 mL)was added. To the resulting suspension, which was precooled to -78 C (dry ice-acetone bath), was added TMSCF3 (149.3 mg, 1.05 mmol, 3.5 equiv) by microsyringe. The mixture was allowed towarm to r.t. and stirring was continued for an additional 15 min. In due course, AgF solid dissolved and a gray, dark solution of [Ag-CF3] formed. Another Schlenk tube (B) equipped with a magnetic stir bar was charged with the aniline (ArNH2; 0.30 mmol, 1.0 equiv) in freshly distilled EtCN (1.5 mL). To the resulting solution, which was precooled to 0 C (ice bath), aq HCl (12 M; 50.0 muL, 0.60mmol, 2.0 equiv) was added; precipitate formed immediately. After 5 min stirring, t-BuONO (37.7 mg, 0.33 mmol, 1.1 equiv) was added by microsyringe, and the mixture was allowed to stir at 0 C for 15 min. The resulting suspension in Schlenk tube (B) was degassed by alternating vacuum evacuation at -196 C (liquid nitrogen), then the solution was allowed to warm to r.t. under a nitrogen atmosphere (three times), and finally cooled to -78 C (dry ice-acetone bath). The gray, dark solution of [AgCF3] in Schlenk tube (A), which was precooled to -78 C (dry ice-acetone bath), was added to Schlenk tube (B) (ArN2+Cl-) by syringe at -78 C (dry ice-acetone bath) over a period of 1 h. After the addition was complete, the reaction mixture was stirred for 3 h at -78 C (dry ice-acetone bath), allowed to warm to r.t., and stirring was continued for an additional 1 h. An off-white precipitate was observed, and the reaction mixture was diluted with EtOAc (3 mL) and filtered through a short silica gel column. The solvent was removed under reduced pressure with a rotatory evaporator, and the crude residue was purified by silica gel column chromatography to give the desired trifluoromethylation product 3. The yields of products 3a, 3f, 3g, 3l, 3o, 3r, 3x, and 3zb are based on the 19F NMR spectra with 4-F3COC6H4OMe as internal standard. Analytical data for the representative product ethyl 4-(trifluoromethyl)benzoate (3i) are provided below. Data for other products can be found in the literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In tetrahydrofuran; methanol; water; at 70℃; for 24h;Inert atmosphere; | A vessel was charged with <strong>[1211596-82-5]4-bromo-1H-indole-7-carboxamide</strong> (2.08 g, 8.70 mmol, Preparation 2), 3- (4,4,5,5-tetramethyl- 1,3 ,2-dioxaborolan-2-yl)aniline (2.10 g, 9.57 mmol), sodium carbonate (2.77 g, 26.1 mmol), [1,1 ?-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (0.637 g, 0.870 mmol) and purged with nitrogen. A mixture of THF (71.4 mL), MeOH (10 mL), and water (10 mL) was added and the reaction was stirred at about 70 C for about 24 h. The mixture was filtered through Celite, the solvent was removed under reduced pressure and the residue was purified by column chromatograph on silica gel eluted with MeOH/DCM (0-10%) to provide a solid. The soid was triturated with ether to provide 4-(3-anzinophenyl)-]H-indole-7-carboxanzide (1.37 g, 63%): |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With triethylamine; HATU; In N,N-dimethyl-formamide; at 20℃; for 4h; | [0106] To a solution of 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)aniline, 3- aminophenylboronic acid pinacol ester, (600 mg, 2.74 mmol) and <strong>[89531-58-8]2-morpholinoacetic acid hydrochloride</strong>, morpholineacetic acid HC1 (522 mg, 0.2.88 mmol) in dry DMF (13.7 mL) was added TEA (831 mg, 2.74 mmol, 1.15 mL) followed by HATU (1.04 g, 2.74 mmol) at rt. The mixture was stirred and checked by LC-MS. After 4 h of stirring, the LC-MS showed the reaction was complete. The mixture was poured into water and extracted with EtOAc. The aqueous layer was separated and extracted 2x more with EtOAc. The combined organic layers were washed with water twice and dried over sodium sulfate. The solution was decanted from the drying agent and concentrated in vacuo to give 1.02 g of an off- white solid. The material was dissolved in a minimum amount of DCM and was loaded onto a 24 g column. Column chromatography (10percent EtOAc/Hexanes to 70percent EtOAc/Hexanes gradient) gave 630 mg, 65percent, of an off-white solid as the product. LC-MS shows the correct mass for the product. |
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