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Structure of 16518-62-0 * Storage: {[proInfo.prStorage]}
* 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.
Reference：
[1] Journal of the American Chemical Society, 1993, vol. 115, # 22, p. 9939 - 9941
[2] Organic and Biomolecular Chemistry, 2007, vol. 5, # 23, p. 3778 - 3786
[3] Journal of the American Chemical Society, 1940, vol. 62, p. 344
[4] Journal of the Chemical Society, 1927, p. 1145
[5] Chemische Berichte, 1919, vol. 52, p. 285
[6] Chemical Communications, 2008, # 15, p. 1780 - 1782
2
[ 50-00-0 ]
[ 591-19-5 ]
[ 16518-62-0 ]
Reference：
[1] Journal of Organic Chemistry, 2014, vol. 79, # 8, p. 3374 - 3382
[2] Angewandte Chemie - International Edition, 2018, vol. 57, # 9, p. 2436 - 2440[3] Angew. Chem., 2018, vol. 130, # 9, p. 2461 - 2465,5
[4] Journal of Organometallic Chemistry, 2005, vol. 690, # 24-25, p. 5581 - 5590
[5] Journal of the American Chemical Society, 2014, vol. 136, # 25, p. 8887 - 8890
Reference：
[1] Organic and Biomolecular Chemistry, 2007, vol. 5, # 23, p. 3778 - 3786
[2] Organic Letters, 2012, vol. 14, # 19, p. 5034 - 5037
[3] Chemical Communications, 2014, vol. 50, # 5, p. 620 - 622
9
[ 109-72-8 ]
[ 16518-62-0 ]
[ 99-64-9 ]
Reference：
[1] Journal of the American Chemical Society, 1940, vol. 62, p. 344
10
[ 16518-62-0 ]
[ 2107-43-9 ]
Reference：
[1] Journal of the American Chemical Society, 2014, vol. 136, # 10, p. 3792 - 3795
11
[ 16518-62-0 ]
[ 178752-79-9 ]
Yield
Reaction Conditions
Operation in experiment
61%
Stage #1: With n-butyllithium; Trimethyl borate In tetrahydrofuran; hexanes at -78 - -20℃; for 1.41667 h; Stage #2: With hydrogenchloride In tetrahydrofuran; hexanes; water for 0.0833333 h;
3-Bromo-N,N-dimethylaniline (500 mg, 2.50 mmol) was dissolved in THF (8 mL) and the solution was cooled to -78° C. n-Butyllithium (1.6M in hexanes, 1.56 mL, 3.75 mmol) was added drop-wise at -78° C. and the reaction mixture was stirred at this temperature for another 5 min. Trimethylborate (1.11 mL, 10.0 mmol) was added and the mixture was stirred for 1 h at -78° C. and was then left to warm to -20° C. over a period of 20 min. 2M HCl (3 mL) was added and the mixture was stirred for 5 min and was then neutralized by the addition of sat. NaHCO3 solution. The mixture was extracted with AcOEt (3.x.10 mL) and the combined organics were concentrated under reduced pressure to provide the crude boronic acid. Flash chromatography on silica gel eluting with acetone/CH2Cl2 1:1 provided 3-dimethylaminophenylboronic acid (251 mg, 61percent).
61%
Stage #1: With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 0.0833333 h; Stage #2: With Trimethyl borate In tetrahydrofuran; hexanes at -78 - -20℃; for 1.33 h; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexanes for 0.0833333 h;
[0230] (a) 3-Dimethylaminophenylboronic acid. 3-Bromo-N,N- dimethylaniline (500 mg, 2.50 mmol) was dissolved in THF (8 mL) and the solution was cooled to -78°C. n-Butyllithium (1.6M in hexanes, 1.56 mL, 3.75 mmol) was added drop- wise at -780C and the reaction mixture was stirred at this temperature for another 5 min. Trimethylborate (1.11 mL, 10.0 mmol) was added and the mixture was stirred for 1 h at -78°C and was then left to warm to -20°C over a period of 20 min. 2M HCl (3 mL) was added and the mixture was stirred for 5 min and was then neutralized by the addition of sat. NaHCO3 solution. The mixture was extracted with AcOEt (3x10 mL) and the combined organics were concentrated under reduced pressure to provide the crude boronic acid. Flash chromatography on silica gel eluting with acetone/CH2Cl2 1:1 provided 3-dimethylaminophenylboronic acid (251 mg, 61percent).
Reference：
[1] Patent: US2006/270686, 2006, A1, . Location in patent: Page/Page column 26
[2] Patent: WO2008/8059, 2008, A1, . Location in patent: Page/Page column 68
[3] Journal of the American Chemical Society, 2012, vol. 134, # 28, p. 11667 - 11673
[4] Organic Letters, 2012, vol. 14, # 18, p. 4814 - 4817,4
12
[ 121-43-7 ]
[ 16518-62-0 ]
[ 178752-79-9 ]
Reference：
[1] Patent: US5914327, 1999, A,
13
[ 4248-19-5 ]
[ 16518-62-0 ]
[ 1160436-95-2 ]
Reference：
[1] Journal of Organic Chemistry, 2009, vol. 74, # 12, p. 4634 - 4637
Stage #1: 3-bromo-N,N-dimethylaniline With magnesium In diethyl ether for 5h; Reflux;
Stage #2: With sulfur In diethyl ether at 20℃; for 14h;
1-1 Synthesis of 3-dimethyl-amino-benzenethiol
Magnesium (1.38g, 56.7mmol) in diethyl ether (170mL) and 3-bromo -N, N- dimethylaniline (11.0g, 55mmol) and the mixture brown Grignard solution of magnesium is exhausted to reflux for 5 hours It was obtained. Sulfur (1.85g, 57.8mmol) in diethyl ether (40mL) was added and the stirring for the Grignard solution in the solution after 14 hours at room temperature, 10% sodium hydroxideAnd extracted three times with 25mL. After putting a 6M hydrochloric acid solution to the aqueous layer extracted three times with 25mL of diethyl ether to give the title compound after drying over magnesium sulfate, filtered, concentrated under reduced pressure (3.79g, 45%).
Stage #1: 3-bromo-N,N-dimethylaniline With magnesium In tetrahydrofuran for 2h; Heating;
Stage #2: With sulfur In tetrahydrofuran for 2h; Heating;
Stage #1: 3-bromo-N,N-dimethylaniline With magnesium In tetrahydrofuran for 2h; Heating / reflux;
Stage #2: With sulfur In tetrahydrofuran at 20℃; for 2h; Heating / reflux;
Stage #3: With hydrogenchloride In tetrahydrofuran; water
1
EXAMPLE 1 Preparation of Di-3-(N,N-dimethylamino)phenyl Disulfide (4): 3 -Bromo-N,N-dimethylaniline (1.0 g, 5.0 mmol) was added to a stirred mixture of Mg turnings (0.243 g, 10.0 mmol) in 10 mL of anhydrous THF. The resulting mixture was heated reflux for 2 h and then cooled to ambient temperature. Sulfur powder (0.39 g, 5.0 mmol) was added and the resulting mixture was heated at reflux for 2 h. The reaction mixture was cooled to ambient temperature and then poured over 6 g of ice. Ten mL of 5% HCl was added and the resulting mixture was filtered through a pad of Celite.
EXAMPLE 9 Boronic acid, [3-(dimethylamino)phenyl]- To a -78 C. solution of n-butyllithium (4.8 ml of a 2.5 molar solution in hexanes; 12 mmol) in ether (5 ml) was added 3-bromo-N,N-dimethylaniline (1.72 g, 10.0 mmol, Giumanini, A. G., Chiavari, G., Musiani, M. M., Rossi, P., Synthesis, 1980, 743.) dropwise. Five minutes later, a solution of trimethylborate (1.35 ml 13 mmol) in 5 ml. of ether was added dropwise over 10 minutes. The reaction was stirred for 1 hour then warmed to room temperature and stirred overnight. The reaction mixture was diluted with water (20 ml), and concentrated in vacuo. To the residue was added glacial acetic acid (HOAc) (1.5 ml) and EtOH (20 ml). The resulting mixture was then heated at reflux for 30 minutes, and concentrated in vacuo. The residue (3.16 g) was a clear yellow oil which solidified to a thick white gum.
1-(3-dimethylaminophenyl)-1-(4-methyl-5-thiazolyl)-methanol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Example 47 1-(3-Dimethylaminophenyl)-1-(4-methyl-5-thiazolyl)methanol The title compound was prepared from <strong>[82294-70-0]4-methyl-5-thiazolecarbaldehyde</strong> and 3-bromo-N,N-dimethylaniline using the method of Example 32. M.p. 135-138 C. 1 H Nmr (CDCl3) 2.44 (3H, s), 2.75 (1H, s), 2.96 (6H, s), 6.04 (1H, s), 6.65-6.8 (3H, m), 7.23 (1H, t) and 8.60 (1H, s) ppm.
3-Bromo-N,N-dimethylaniline (500 mg, 2.50 mmol) was dissolved in THF (8 mL) and the solution was cooled to -78 C. n-Butyllithium (1.6M in hexanes, 1.56 mL, 3.75 mmol) was added drop-wise at -78 C. and the reaction mixture was stirred at this temperature for another 5 min. Trimethylborate (1.11 mL, 10.0 mmol) was added and the mixture was stirred for 1 h at -78 C. and was then left to warm to -20 C. over a period of 20 min. 2M HCl (3 mL) was added and the mixture was stirred for 5 min and was then neutralized by the addition of sat. NaHCO3 solution. The mixture was extracted with AcOEt (3×10 mL) and the combined organics were concentrated under reduced pressure to provide the crude boronic acid. Flash chromatography on silica gel eluting with acetone/CH2Cl2 1:1 provided 3-dimethylaminophenylboronic acid (251 mg, 61%).
61%
[0230] (a) 3-Dimethylaminophenylboronic acid. 3-Bromo-N,N- dimethylaniline (500 mg, 2.50 mmol) was dissolved in THF (8 mL) and the solution was cooled to -78C. n-Butyllithium (1.6M in hexanes, 1.56 mL, 3.75 mmol) was added drop- wise at -780C and the reaction mixture was stirred at this temperature for another 5 min. Trimethylborate (1.11 mL, 10.0 mmol) was added and the mixture was stirred for 1 h at -78C and was then left to warm to -20C over a period of 20 min. 2M HCl (3 mL) was added and the mixture was stirred for 5 min and was then neutralized by the addition of sat. NaHCO3 solution. The mixture was extracted with AcOEt (3x10 mL) and the combined organics were concentrated under reduced pressure to provide the crude boronic acid. Flash chromatography on silica gel eluting with acetone/CH2Cl2 1:1 provided 3-dimethylaminophenylboronic acid (251 mg, 61%).
With caesium carbonate;tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 160℃; for 0.416667h;Microwave irradiation;
[0124] 2-Chloro-5-methyl-pyrimidin-4-ylamine (0.343 g, 2.38 mmol, 1 equiv), (3-bromo- phenyl)-dimethyl-amine (0.524g, 2.62 mmol, 1.1 equiv), cesium carbonate (2.3 g, 7.15 mmol, 3 equiv), 4,5-bis(diphenylphosphino)-9,9-dimethyl xanthene (0.276 g, 0.476 mmol, 0.2 equiv) and tris(dibenzylideneacetone) dipalladium (0.218 g, 0.238 mmol, 0.1 equiv) were combined in 30ml microwave vessel. Reactants were then diluted with 12ml dioxane and microwaved for 25 minutes at 160 C. Reaction vessel was then spun down, decanted and evaporated to dryness. Resulting solids were diluted with DCM and adsorbed onto silica gel. Chromatography (gradient of 0% methanol in DCM up to 25% methanol in DCM) afforded the title intermediate 18 as orange solid (0.184 g, 29% yield). MS (ESI+): 263.02 (M+H), r.t. = 1.72 min.
Stage #1: 3-bromo-N,N-dimethylaniline With n-butyllithium In tetrahydrofuran at -78 - -35℃; for 1h;
Stage #2: N-methoxy-N-methylbutanamide In tetrahydrofuran at -78℃; for 0.75h;
26
To a stirred solution of (3-bromophenyl)dimethylamine (7.5 g, 37.5 mmol) in THF (50 mL) at -78°C, was added n-butyllithium (2.88 g, 45.0 mmol). The resulting solution was stirred at -35°C for 1 h and was then cooled to -78°C and treated dropwise with a solution of N- methyl-/V-(methyloxy)butanamide (4.92 g, 37.5 mmol) (Description 25) in dry THF (15 mL). The resulting mixture was stirred for 45 min at -78°C and then worked up using water (100 mL) and ethyl acetate (200 mL). The crude material was purified by chromatography on silica gel, eluting with a gradient of 0-20% ethyl acetate in hexane, to afford the title compound (3.48 g). LCMS (B) m/z: 192 [M+1 ]+, Rt 2.29 min.
It was prepared as outlined in Scheme 1 In an oven-dried 50 mL round bottom flask under an atmosphere of anhydrous argon, THF (10 mL) was added followed by 3-bromo-N,N-dimethylaniline (5.00 mmol, 1.00 g). This clear, colourless solution was cooled to -90 C using a Juablo cooler with a cold finger and an isopropanol bath in an appropriate sized Dewar. The aniline reagent solution was stirred at this temperature for 15 min to ensure the solution was sufficiently cold. Butyl lithium (3.44 mL, 1.60 M in hexanes) was added dropwise at -90 C over 20 min. The resulting clear light yellow solution was stirred for 15 min at -90 C. To this 3-lithium N,N-dimethylaniline intermediate was added <strong>[104863-67-4]N-methoxy-N-methyl-2,2,2-trifluoroacetamide</strong> (5.50 mmol, 0.857 g) dissolved in anhydrous THF (4 mL), dropwise over 15 min. The resulting solution was stirred at -90 C for 30 min then warmed to room temperature by removing the reaction flask from the cooling bath. The resulting reaction mixture was stirred for 16 h at room temperature then extracted with 1 M HCl (3 * 10 mL). The combined aqueous layers were added to a separatory funnel and solid NaHCO3 was added until the solution stopped bubbling. During this addition a yellow liquid formed on the top of the aqueous layer. The aqueous layer was extracted with diethyl ether (3 * 15 mL). The combined organic layers were dried over Na2SO4, gravity filtered and concentrated in vacuo. The crude viscous yellow liquid was purified by flash chromatography on silica gel (5% ethyl acetate/94% hexanes/1% triethylamine, Rf: 0.38) to afford the desired product as a clear yellow liquid (0.854 g, 79%): 1HNMR (CDCl3): d 3.02 (s, 6H), 7.02-7.05 (m, 1H), 7.36-7.38 (m,3H) (Supplementary Fig. S1). 13C NMR (CDCl3): d 40.0, 112.3,116.8 (q, JC,F = 298.2 Hz), 117.9, 119.1, 129.5, 130.4, 150.5, 181.0(q, JC,F = 34.3 Hz) (Supplementary Fig. S2). IR (Neat): 2898 (m),2814 (w), 1709 (s), 1600 (s), 1573 (s), 1503 (s), 1437 (m), 1363(m), 1105 (s), 1007 (s) cm1 (Supplementary Fig. S3). LRMS m/z: 218 (M+1, 11), 217 (M+, 100), 216 (74), 148 (24), 120 (24), 119(13), 118 (10), 104 (10), 77 (11), 74 (13) (Supplementary Fig. S4). HRMS (ESI): MH+ found 218.0786, calculated for C10H11F3-NO+ = 218.0787(Supplementary Fig. S5). HPLC: retention time 2.59 min; purity 96.1% (Supplementary Fig. S6).
With copper(l) iodide; sodium iodide; N,N`-dimethylethylenediamine In 1,4-dioxane; N,N-dimethyl-formamide at 110℃; for 22h; Inert atmosphere;
97%
With copper(l) iodide; sodium iodide; N,N`-dimethylethylenediamine In 1,4-dioxane at 110℃; for 22h; Inert atmosphere;
3-Iodo-N,N-dimethylaniline
Prepared according to a modified literature procedure.9a To a suspension of NaI (39.0 g, 260 mmol), CuI (1.24 g, 6.50 mmol), and N,N′-dimethylethylenediamine (1.40 mL, 13.0 mmol) in 1,4-dioxane (130 mL) at RT was added 3-bromo-N,N-dimethylaniline (prepared from 6 following the reaction step a; 18.6 mL, 130 mmol). The reaction mixture was stirred for 22 h at 110 °C16 and then cooled to RT, treated with aq NH4OH (28%, 650 mL) and H2O (300 mL), and extracted with CH2Cl2 (3 * 1.5 L). The combined organic layers were dried (Na2SO4) and concentrated in vacuo to give 3-iodo-N,N-dimethylaniline as a brownish oil; yield: 31.3 g (97%). 1H NMR (500 MHz, CDCl3): δ = 7.01-7.03 (m, 2 H, C4H, C6H), 6.91-6.94 (m, 1 H, C5H), 6.65-6.67 (m, 1 H, C2H), 2.92 [s, 6 H, N(CH3)2]. 13C NMR (125 MHz, CDCl3): δ = 151.6 (C1), 130.4 (C5), 125.2 (C4), 121.1 (C6), 111.6 (C2), 95.5 (C3), 40.3 (N(CH3)2). The spectral data were in agreement with literature data.3a,9c
With hydrogenchloride; cobalt(II,III) oxide; titanium(IV) oxide; In water; for 6h;UV-irradiation;
General procedure: A method for alkylation of aniline with Cu2O/TiO2 as a catalyst (loading amount is 0.01) and methanol as a carbon source, including the following processes:A 50 mL photoreaction flask with a stirrer was charged with 40 mL of methanol/water (water occupies 18% of the total volume of the reaction solvent (methanol+water)) solution, 250 mg of photocatalyst Cu2O/TiO, 5 mg of HCl and 0.2 mmol of substrate aniline.Then, the photoreaction flask was irradiated in a 365nm ultraviolet light source and stirred for 6 hours.Centrifuge the mixed solution system, add excess hydrochloric acid to adjust the pH to 1-2, and then rotate to evaporate all the methanol.The remaining aqueous reaction mixture was adjusted to pH 8 with sodium carbonate solution, and then extracted with water and ethyl acetate (5 times, 3 mL each time). The organic layer was washed with brine,Dry with Na2SO4 and evaporate to obtain a crude product.Distill and crystallize to obtain the product.The invention adopts a type II heterojunction photocatalyst, so that all the sub-steps of alkylation can be completed on the surface of the recombined catalyst under light conditions.After measurement, the final N-alkylation product yield was 99%, among which, the first-stage N-alkylation yield was 0.9%, and the second-stage N-alkylation yield was 99.1%. The results are shown in Table 1.
Stage #1: 3-bromo-N,N-dimethylaniline With iodine; magnesium In tetrahydrofuran for 2h; Reflux;
Stage #2: chloro-diphenylphosphine In tetrahydrofuran at 0℃; Reflux;
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