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Chemical Structure| 375853-82-0 Chemical Structure| 375853-82-0

Structure of 375853-82-0

Chemical Structure| 375853-82-0

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Product Details of [ 375853-82-0 ]

CAS No. :375853-82-0
Formula : C11H20BNO2
M.W : 209.09
SMILES Code : CC1(C)OB(OC1(C)C)C1=CCNCC1
MDL No. :MFCD11506075
InChI Key :AIPUNCFCQBDNDJ-UHFFFAOYSA-N
Pubchem ID :21105461

Safety of [ 375853-82-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 375853-82-0 ]

* 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.

  • Upstream synthesis route of [ 375853-82-0 ]
  • Downstream synthetic route of [ 375853-82-0 ]

[ 375853-82-0 ] Synthesis Path-Upstream   1~2

  • 1
  • [ 375853-82-0 ]
  • [ 1121057-75-7 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogenchloride In tert-butyl methyl ether at 20℃; Method 3: General conditions for the deprotection of a 7V-Boc carbamate in the presence of a boronate ester: The boronate ester is dissolved in te/t-butylmethylether (0.4 M final ester concentration) after which point HCl (g) is bubbled in over the course of 15 min. The reaction is allowed to stir at room temperature for an additional hour after which point the solvent is removed under a stream of nitrogen to provide the desired HCl amine salt as a white solid in quantitative yield.; Example 2: Tetrahydropyridine 2 was prepared in 3 steps starting with the deprotection of 1 using Method 3. The resulting HCl amine salt was dissolved in dichloromethane (0.2 M). Benzyl chloroformate (1.2 equiv) was added followed by triethylamine (3.0 equiv). The reaction was allowed to stir at room temperature for 2h after which point it was diluted with IN HCl and extracted with excess dichloromethane. The organic layer was dried over MgSψ4 and concentrated to provide the desired carbamate in quantitative yield, which was converted directly to boronic acid 2 using Method 2. [M-H]- = 260.1 m/z. Activity: B
100% With hydrogenchloride In 1,4-dioxane at 20℃; for 4 h; To a solution of tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)-5,6-dihydropyridine-1(2H)-carboxylate (5g, 16 mmol) in dioxane (10 mL) was added 4N HCl dioxane solution (24.2 mL, 97 mmol) at RT, and the reaction was stirred at RT for 4 h. The mixture was concentrated under reduced pressure to afford the title compound (4 g, yield 100percent) as a white solid.MS (ES+) C11H21BCINO2 requires: 209, found 210 [M+H]+.
100% With hydrogenchloride In ethyl acetate at 0 - 26℃; for 3 h; Tert-butyl 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1 (2H)- carboxylate (ARK PHARMA, 25 g, 80.851 mmol) was dissolved in 250 mL of EtOAc and HCI 4N in EtOAc (SYMAX FINE CHEMICALS, 250 mL) was added at 0 °C. The mixture was allowed to 26 °C and stirred for 3 h. The reaction mixture was evaporated under reduced pressure. The crude was washed with diethyl ether and filtered to give title compound (20 g, quantitative). NMR (400 MHz, DMSO-d6) δ ppm: 9.30 (br s, 2H), 6.40-6.30 (m, 1 H), 3.64- 3.52 (m, 2H), 3.15-3.00 (m, 2H), 2.34-2.22 (m, 2H), 1.21 (s, 12H).
96% With hydrogenchloride In 1,4-dioxane; dichloromethane at 20℃; To tert-butyl 4-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine- 1 -carboxylate 51 (3 g, 9.7 mmol) in dichloromethane (5 mL) was added hydrochloric acid in 1,4-dioxane (4 N, 5 mL). The reaction was stirred at room temperature overnight, then concentrated twice from toluene. The residue was washed with ethyl acetate and dried under vacuum to produce compound 52 as an HC1 salt (2.3 g, 96percent). The data from the lH NMR spectrum were consistent with the structure of the compound.
90% With hydrogenchloride In diethyl ether; tert-butyl methyl ether at 20℃; tert-butyl 4-(4,4,5 ,5-tetramethyl- 1,3 ,2-dioxaborolan-2-yl)-5 ,6-dihydropyridine- 1(2H)-carboxylate (2 g, 6.47 mmol) was suspended in MTBE (8.1 mL) and 2M HC1 in Et20 (24 mL). The reaction was stirred rt overnight, the white precipitate formed collected by filtration and washed with Et20 to give the title compound (1.434 g, 90 percent).UPLC-MS: 0.51 mm, 210.3 [M+H]+, method 9.
90% With hydrogenchloride In diethyl ether; tert-butyl methyl ether at 20℃; tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (2 g, 6.47 mmol) was suspended in MTBE (8.1 mL) and 2M HCl in Et2O (24 mL). The reaction was stirred rt overnight, the white precipitate formed collected by filtration and washed with Et2O to give the title compound (1.434 g, 90percent).UPLC-MS: 0.51 min, 210.3 [M+H]+, method 9.
8 g With hydrogenchloride In dichloromethane; isopropyl alcohol for 12 h; Step 1:
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridinium chloride
Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (10 g) is dissolved in dichloromethane (100 mL) and 5 M HCl in isopropanol (120 mL) and stirred for 12 hours.
The solvents are evaporated, the residue is redissolved in toluene and the solvent is again evaporated to give the title compound. Yield: 8 g; LC (method 11): tR=0.68 min; Mass spectrum (ESI+): m/z=210 [M+H]+.
8 g With hydrogenchloride In dichloromethane; isopropyl alcohol for 12 h; Tert-butyl 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1 (2H)- carboxylate (1 0 g) is d issolved in d ichloromethane (1 00 m L) and 5 M HCI in isopropanol (120 mL) and stirred for 12 hours. The solvents are evaporated, the residue is redissolved in toluene and the sollvent is again evaporated to give the title compound. Yield: 8 g; LC (method 1 1 ): tR = 0.68 min; Mass spectrum (EST): m/z = 210 [M+H]+.
8 g With hydrogenchloride In dichloromethane; isopropyl alcohol for 12 h; Tert-butyl 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1 (2H)- carboxylate (10 g) is dissolved in dichloromethane (100 mL) and 5 M HCI in isopropanol (120 mL) and stirred for 1 2 hours. The solvents are evaporated, the residue is redissolved in toluene and the sollvent is again evaporated to give the title compound. Yield: 8 g; LC (method 1 1 ): tR = 0.68 min; Mass spectrum (EST): m/z = 210 [M+H]+.

References: [1] Patent: WO2010/118159, 2010, A1, . Location in patent: Page/Page column 64; 65-66.
[2] Patent: WO2018/218197, 2018, A2, . Location in patent: Paragraph 0364; 0365.
[3] Patent: WO2019/34701, 2019, A1, . Location in patent: Page/Page column 37; 38.
[4] Patent: WO2014/100620, 2014, A2, . Location in patent: Paragraph 0318.
[5] Patent: WO2015/91685, 2015, A1, . Location in patent: Page/Page column 138; 139.
[6] Patent: US2015/166549, 2015, A1, . Location in patent: Paragraph 0858; 0859; 0860.
[7] Patent: WO2011/143495, 2011, A1, . Location in patent: Page/Page column 85.
[8] Patent: US2013/252937, 2013, A1, . Location in patent: Paragraph 0512.
[9] Patent: WO2013/144097, 2013, A1, . Location in patent: Page/Page column 96.
[10] Patent: WO2013/144098, 2013, A1, . Location in patent: Page/Page column 149.
  • 2
  • [ 375853-82-0 ]
  • [ 1616388-38-5 ]
References: [1] Patent: WO2014/100620, 2014, A2, .
 

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