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Chemical Structure| 76579-64-1

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Product Details of [ 76579-64-1 ]

CAS No. :76579-64-1
Formula : C11H16BrNO
M.W : 258.16
SMILES Code : CN(C)CCCOC1=CC=C(Br)C=C1
MDL No. :MFCD03718813

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Application In Synthesis of [ 76579-64-1 ]

* 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 [ 76579-64-1 ]

[ 76579-64-1 ] Synthesis Path-Upstream   1~2

  • 1
  • [ 76579-64-1 ]
  • [ 61676-62-8 ]
  • [ 627899-90-5 ]
YieldReaction ConditionsOperation in experiment
45%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.16667 h; Inert atmosphere
Stage #2: at -78 - 20℃; for 24 h; Inert atmosphere
To a 100-mL flame-dried two necked flask was added M1 (3.0g, 11.6mmol) and freshly distilled THF (80mL). The resulting solution was cooled at−78°C and 8.7mL n-butyllithium (13.9mmol, 1.6M in hexane) was added over 10min under a nitrogen atmosphere. The mixture was stirred at−78°C for 1h. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.6g, 13.9mmol) was added rapidly to the solution, and the resulting mixture was slowly warmed to room temperature for 24h. The mixture was poured into 50mL water and extracted with CHCl3 (300mL). The combined organic layers were washed with brine and dried over anhydrous MgSO4. The solvent was removed by rotary evaporation, and the residue purified by column chromatography on silica gel (ethylacetate:dichloromethane as eluent) to obtain the product as a light-yellow oil (1.6g, yield: 45.0percent). 1H NMR (400MHz; CDCl3; Me4Si): δ=7.77 (d, 2H, J=8.8Hz), 6.90 (d, 2H, J=8.8Hz), 3.94 (t, 2H, J=6.4Hz), 2.46 (t, 2H, J=6.8Hz), 2.26 (s, 6H), 1.88 (m, 2H, J=6.8Hz) 1.25 (s, 12H). 13C NMR (100MHz; CDCl3; Me4Si): 161.57; 136.73; 113.41; 83.13; 74.40; 66.02; 54.09; 45.42; 27.43; 25.00. Anal. Calcd for: C17H28BNO3: C, 66.90; H, 9.25; N, 4.59. Found: C, 66.73; H, 9.23; N, 4.63. IR (KBr, cm−1): 2981, 2936, 2816, 2716, 1566, 1463, 1281, 1245.
45%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 2 h; Inert atmosphere
Stage #2: at -78 - 20℃; for 26 h; Inert atmosphere
Dissolved in dry 30 Compound A 3g in a nitrogen atmosphere, THF, -78° C after the temperature was reduced to 2.2equivalent of n-butyllithium(nBuLi,Aldrich Co.) was slowly added. The reaction mixture was stirred at -78° C for 2 hours andthen, 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,Aldrich) was added, and the mixture was stirred while the temperature gradually to room temperature after stirring at -78° Cfor 2 hours, the height for 24 hours. After the reaction was completed to extract the organic material with chloroform, to giveafter washing the column with water to obtain the compound B, 1.6 g (yield 45.0percent).
References: [1] Dyes and Pigments, 2015, vol. 113, p. 210 - 218.
[2] Patent: KR2015/122308, 2015, A, . Location in patent: Paragraph 0094; 0095; 0098; 0099.
  • 2
  • [ 76579-64-1 ]
  • [ 73183-34-3 ]
  • [ 627899-90-5 ]
YieldReaction ConditionsOperation in experiment
42.4% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 90℃; for 16 h; Inert atmosphere NrV-Dimethyl-3-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenoxy]propan-l- amine N,N-Dimethyl-3-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenoxy]propan-l -amine is available commercially from several suppliers including Apollo Scientific Ltd., Whitefield Rd, Bredbury, Stockport, Cheshire, SK6 2QR, UK. CAS number [627899-90- 5], catalogue number OR12268. Alternatively, it can be prepared as follows: A 1 : 1 complex of [l, -bis(diphenylphosphino)ferrocene]dichloropalladium(II) with dichloromethane (8.64 mg, 10.58 μιηο) was added to 3-(4-bromophenoxy)-N,N- dimethylpropan-1 -amine (546 mg, 2.12 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2- dioxaborolane) (644 mg, 2.54 mmol) and potassium acetate (830 mg, 8.46 mmol) in 1,4- dioxane (6 mL) warmed to 90°C under nitrogen. The resulting suspension was stirred at 90 °C for 16 h. The reaction mixture was evaporated to dryness and re-dissolved in DCM (25 mL), and washed with water (20 mL). The organic layer was dried with a phase separating cartridge, filtered and evaporated to afford crude product. The crude product was purified by FCC, elution gradient 0 to 10percent MeOH in DCM. Pure fractions were evaporated to dryness to afford the desired material as a brown waxy solid (274 mg, 42.4 percent). NMR Spectrum: NMR (500MHz, CDCls) δ 1.33 (12H, s), 1.89 - 2.08 (2H, m), 2.32 (6H, s), 2.53 (2H, dt), 4.05 (2H, t), 6.86 - 6.91 (2H, m), 7.71 - 7.76 (2H, m). Mass Spectrum: m/z (ES+)[M+H]+ = 258.
42.3% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 90℃; for 16 h; Inert atmosphere Dichloro [1,1 ‘-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct(0.063 g, 0.08 mmol) was added to 3-(4-bromophenoxy)-N,N-dimethylpropan-1-amine(2g, 7.75 mmol), 4,4,4’,4’,5 ,5 ,5’,5 ‘-octamethyl-2,2’-bi(1 ,3 ,2-dioxaborolane) (2.36 g, 9.30 mmol) and potassium acetate (3.04 g, 30.99 mmol) in 1,4-dioxane (35 mL) and the mixture degassed for 15 minutes. The resulting suspension was stirred at 90 °C for 16 hours under an inert atmosphere. The reaction mixture was evaporated to dryness, redissolved in DCM(25 mL), washed with water (20 mL) and the organic layer was dried with a phase separating cartridge, filtered and evaporated. The crude product was purified by flash silica chromatography, elution gradient 0 to 10percent MeOH in DCM, to afford the desired material as a brown oil (1.000 g, 42.3 percent) which solidified on standing. NMR Spectrum: ‘H NMR (400MHz, CDC13) ö 1.33 (12H, s), 1.96 - 2.07 (2H, m), 2.34(6H, s), 2.52 - 2.65 (2H, m), 4.04 (2H, t), 6.83 - 6.94 (2H, m), 7.68 - 7.78 (2H, m).Mass Spectrum: mlz (ES+) [M+H]+ = 306
References: [1] Patent: WO2017/76895, 2017, A1, . Location in patent: Page/Page column 46; 47.
[2] Patent: WO2019/57757, 2019, A1, . Location in patent: Page/Page column 56; 57; 58.
 

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