Structure of 115377-93-0
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CAS No. : | 115377-93-0 |
Formula : | C8H11BO4 |
M.W : | 181.98 |
SMILES Code : | COCOC1=CC=CC=C1B(O)O |
MDL No. : | MFCD10566597 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
(b) 2-Methoxymethoxyphenylboronic Acid. In a manner similar to that of Example 1(a), starting with 19.00 g (8.7 mmol) of 2-methoxymethoxybromobenzene, 11.00 g (70%) of the expected product are obtained in the form of a white solid with a melting point of 63-66 C. 1H NMR (CDCl3) δ 3.51 (s, 3H), 5.31 (s, 2H), 6.21 (s, 2H), 7.07 (d, 1H, J=7.3 Hz), 7.14 (d, 1H, J=8.8 Hz), 7.43 (dt, 1H, J=8.6/1.9 Hz), 7.87 (dd, 1H, J=7.3/1.8 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 108 3-[4-((3aR,9bR)-cis-9-Methoxy-1,2,3,3a,4,9b-hexahydro-[1]-benzopyrano[3,4-c]pyrrol-2-yl)butyl]-8-(4-hydroxyphenyl)-pyrazzino[2',3':4,5]thieno[3,2-d]pyrmidine-2,4(1H,3H)-dione The product of Example 16 (0.07 g,0.105 mmol) and 4 (methoxymethyloxy) phenyl boronic acid (0.02 g, 0.11 mmol) prepared by the procedure described in Tetr. Lett., 31, 27, (1990) were treated as described in Example 106 to yield 0.029 g (45%) of MOM-protected product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1,1'-bis-(diphenylphosphino)ferrocene; sodium carbonate; bis(dibenzylideneacetone)-palladium(0); In 1,2-dimethoxyethane; water; at 85℃; for 24h;Inert atmosphere; Sealed tube; | Under an argon atmosphere, a mixture of 7(50.0 mg, 89.9 lmol), 8a (24.6 mg, 0.135 mmol), Pd(dba)2 (5.2mg, 9.0 lmol), dppf (5.0 mg, 9.0 lmol), Na2CO3 (63.0 mg, 0.594mmol), DME (3.0 mL), and degassed water (0.2 mL) was heatedin a sealed tube at 85 C for 24 h. After cooling to room temperature,the mixture was evaporated and the products were extractedwith DCM. The extract was washed with water and brine, driedover Na2SO4, and evaporated. The residue was purified by flash chromatography over silica gel 60N (hexane-ethyl acetate = 4:1)to give 9a as a pale yellow solid (51.8 mg, 94%). Recrystallization from DCM-hexane gave a pale yellow needles. Mp 186-187 C. IR (KBr): 1688, 1473, 1379, 1256, 1226, 1190, 1114 cm1. 1H NMR(400 MHz, CDCl3): d 1.07 (d, J = 6.1 Hz, 1.5H), 1.20 (d, J = 6.1 Hz,1.5H), 1.21 (d, J = 6.1 Hz, 1.5H), 1.27 (d, J = 6.1 Hz, 1.5H), 1.42 (d,J = 6.1 Hz, 6H), 3.30 (s, 3H), 3.42 (br s, 3H), 3.59 (s, 3H), 3.81 (s,1.5H), 3.82 (s, 1.5H), 4.25 (sep, J = 6.1 Hz, 0.5H), 4.33 (sep, J = 6.1Hz, 0.5H), 4.66 (sep, J = 6.1 Hz, 1H), 4.86 (d, J = 6.9 Hz, 0.5H), 4.96(d, J = 6.9 Hz, 0.5H), 4.99 (d, J = 6.9 Hz, 0.5H), 5.04 (d, J = 6.9 Hz,0.5H), 6.75-6.89 (m, 4H), 6.93 (d, J = 7.6 Hz, 1H), 6.95-7.01 (m,1H), 7.04 (s, 1H), 7.08 (d, J = 8.3 Hz, 1H), 7.11-7.21 (m, 2H), 9.30(d, J = 7.6 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 21.7, 21.8, 21.9,21.9, 22.0, 22.2, 50.7, 55.3, 55.7, 56.0, 71.1, 71.1, 71.2, 95.1,105.6, 110.6, 111.4, 111.7, 112.0, 112.8, 114.6, 117.4, 118.1,118.2, 118.6, 119.0, 119.4, 119.8, 121.0, 121.2, 123.5, 123.9,124.1, 124.2, 124.4, 128.2, 128.3, 128.4, 130.4, 131.4, 131.8,132.3, 132.4, 146.9, 147.5, 148.5, 149.3, 149.9, 150.4, 155.6, 162.6. HRDARTMS m/z. Calcd for C36H40NO8 [(M+H)+]: 614.27539.Found: 614.27399. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Under an argon atmosphere, apentane solution of tert-butyllithium (1.52 M, 14.4 mL, 21.9 mmol) was added dropwise to a solution of S1 (2.38 g, 11.0 mmol) in THF (30 mL) at -78 C. After stirring for 1 h at -78 C, trimethyl borate (1.84 mL, 16.5 mmol) was added as a neat liquid and the mixture was stirred for 1 h at -78 C. The reaction mixture was allowed to warmto room temperature and stirred for an additional 1 h. The mixture was quenched with saturatedaqueous NH4Cl and concentrated. The products were adjusted to pH 3 with acetic acid and themixture was extract with dichloromethane. The extract was washed successively with water and brine, dried over Na2SO4, and evaporated. The residue was washed with hexane and dried underreduced pressure to give 8a as a colorless powder (1.41 g, 71%). This compound was used for thenext reaction without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 2h; | Into a 30-mL sealed tube, was placed benzyl 9-(3-amino-6-chloropyridazin-4-yl)-1-oxa-4, 9-diazaspiro[5.5]undecane-4-carboxylate (3.1 g, 7.4 mmol, 1.0 equiv), [2-(methoxymethoxy) phenyl]boronic acid (2.7 g, 0.1 mmol, 2.0 equiv), Pd(PPh3)4 (859.4 mg, 0.7 mmol, 0.1 equiv), and K2CO3 (3.1 g, 0.1 mmol, 3.0 equiv) in dioxane (5 mL) and H2O (1 mL). The resulting mixture was stirred for 12 hours at 100 C. in an oil bath, and then was extracted with ethyl acetate (20 mL*2). The combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was applied onto a silica gel column eluting with dichloromethane/methanol (10:1). This resulted in 3.2 g (83%) of benzyl 9-[3-amino-6-[2-(methoxymethoxy) phenyl]pyridazin-4-yl]-1-oxa-4, 9-diazaspiro[5.5]undecane-4-carboxylate as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water;Inert atmosphere; Heating; | Into a 50-mL round-bottom flask purged and maintained under an inert atmosphere of nitrogen, was placed 2-(3-[4-[3-(3-amino-6-chloropyridazin-4-yl)-3,8-diazabicyclo[3.2.1]octan-8-yl]pyridin-2-yl]propoxy)ethan-1-ol (650 mg, 1.55 mmol, 1.00 equiv), [2-(methoxymethoxy)phenyl]boronic acid (566 mg, 3.11 mmol, 2.00 equiv), dioxane (8 mL), water (2 mL), potassium carbonate (644 mg, 4.66 mmol, 3.00 equiv), Pd(PPh3)4 (180 mg, 0.16 mmol, 0.10 equiv). The resulting solution was stirred for 3 hours at 100 C. in an oil bath. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column with methanol/H2O (85:15). The collected fractions were combined and concentrated under vacuum. This resulted in 400 mg (50%) of 2-[3-[4-(3-[3-amino-6-[2-(methoxymethoxy)phenyl]pyridazin-4-yl]-3,8-diazabicyclo[3.2.1]octan-8-yl)pyridin-2-yl]propoxy]ethan-1-ol as yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water;Heating; | Into a 100-mL round-bottom flask, was placed benzyl 4-[2-([4-[3-(3-amino-6-chloropyridazin-4-yl)-3,8-diazabicyclo[3.2.1]octan-8-yl]pyridin-2-yl]oxy)ethyl]piperazine-1-carboxylate (390 mg, 0.7 mmol, 1.0 equiv), dioxane (8.0 mL), water (2.0 mL), potassium carbonate (279 mg, 2.0 mmol, 3.0 equiv), [2-(methoxymethoxy)phenyl]boronic acid (184.0 mg, 1.0 mmol, 1.50 equiv), Pd(PPh3)4 (78 mg, 0.07 mmol, 0.1 equiv). The resulting solution was stirred for 2 hours at 100 C. The resulting solution was extracted with ethyl acetate (20 mL*3), and the organic layers combined and concentrated under vacuum. The residue was applied onto a silica gel column eluting with dichloromethane/methanol (10:1). This resulted in 120 mg (26%) of benzyl 4-(2-[[4-(3-[3-amino-6-[2-(methoxymethoxy)phenyl]pyridazin-4-yl]-3,8-diazabicyclo[3.2.1]octan-8-yl)pyridin-2-yl]oxy]ethyl)piperazine-1-carboxylate as a brown solid. |
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