* 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.
With N-Bromosuccinimide; water In chloroform for 3 h; Reflux
General procedure: In around-bottom flask, diarylmethanes (1.0 mmol), NBS (889.9 mg, 5.0 mmol) andwater (0 or 5.0 mmol) were dissolved in CHCl3 (4.0 mL). After refluxing for 3 h in the air, the reaction mixture was quenched withNa2S2O3·5H2O, cooled to roomtemperature, washed with 5mL CH2Cl2, dried with MgSO4,and filtered to get clear organic solution. The solvent was removed reduced pressure by a rotary evaporator, and the resulting residue was subjected to column chromatography on silica gel using co-solvent(ethyl acetate / petroleum ether, v/v) as eluent to give the corresponding diaryllketones.
Reference:
[1] Organic Letters, 2014, vol. 16, # 7, p. 2000 - 2002
[2] Journal of Organic Chemistry, 1948, vol. 13, p. 786,788
[3] Journal of Organic Chemistry, 1937, vol. 2, p. 139,143
[4] Journal of the American Chemical Society, 1930, vol. 52, p. 2881,2887
[5] Journal of Organic Chemistry, 1939, vol. 4, p. 1,9
[6] Justus Liebigs Annalen der Chemie, 1939, vol. 540, p. 83,96
[7] Journal of Medicinal Chemistry, 1979, vol. 22, p. 1347 - 1354
[8] Journal of the Chemical Society, 1961, p. 1405 - 1407
[9] Advanced Synthesis and Catalysis, 2018, vol. 360, # 13, p. 2522 - 2536
3
[ 18982-54-2 ]
[ 23450-18-2 ]
Yield
Reaction Conditions
Operation in experiment
55%
With iron(III) chloride In benzene for 12 h; Reflux
Benzene (20 mL) was added slowly to 2-bromobenzyl alcohol (8.0 g,42 mmol) and FeCl3 (3.2 g, 20 mmol), then the mixture was heated atreflux for 12 h. Once cooled to r.t., the solvent was removed under reducedpressure and the residual solid purified by column chromatography(eluent: pentane) affording 3a as a white solid; yield: 4.67 g(55percent).1H NMR (400 MHz, CDCl3): δ = 7.59 (dd, J = 8.0, 1.2 Hz, 2 H, ArH), 7.32(t, J = 7.6 Hz, 2 H, ArH), 7.26–7.21 (m, 4 H, ArH), 7.16 (dd, J = 7.6, 1.7Hz, 1 H, ArH), 7.10 (td, J = 8.0, 1.7 Hz, 1 H, ArH), 4.14 (s, 2 H, ArCH2).13C NMR (100 MHz, CDCl3): δ = 41.6, 124.9, 126.2, 127.4, 127.8, 128.5,129.0, 131.0, 132.8, 139.9, 140.4.
Reference:
[1] Chemistry - A European Journal, 2018, vol. 24, # 63, p. 16895 - 16901
[2] Journal of the American Chemical Society, 2017, vol. 139, # 1, p. 245 - 254
[3] New Journal of Chemistry, 2016, vol. 40, # 11, p. 9030 - 9033
[4] RSC Advances, 2015, vol. 5, # 104, p. 85291 - 85295
[5] European Journal of Medicinal Chemistry, 2000, vol. 35, # 1, p. 41 - 52
[6] Tetrahedron Letters, 2015, vol. 56, # 50, p. 7005 - 7007
5
[ 71-43-2 ]
[ 3433-80-5 ]
[ 23450-18-2 ]
Reference:
[1] Journal of Materials Chemistry, 2004, vol. 14, # 8, p. 1342 - 1346
[2] Journal of Organic Chemistry, 2015, vol. 80, # 9, p. 4532 - 4544
[3] Organic Letters, 2011, vol. 13, # 20, p. 5628 - 5631
[4] Chemische Berichte, 1992, vol. 125, # 4, p. 941 - 950
[5] Chemical Communications, 2016, vol. 52, # 44, p. 7138 - 7141
[6] Journal of the American Chemical Society, 2017, vol. 139, # 45, p. 16210 - 16221
6
[ 18982-54-2 ]
[ 71-43-2 ]
[ 23450-18-2 ]
Reference:
[1] Journal of Organic Chemistry, 2007, vol. 72, # 9, p. 3289 - 3292
[2] Angewandte Chemie - International Edition, 2012, vol. 51, # 12, p. 2939 - 2942
[3] Journal of Organic Chemistry, 1997, vol. 62, # 20, p. 6997 - 7005
[4] Organic Letters, 2013, vol. 15, # 21, p. 5542 - 5545
[5] Tetrahedron Letters, 2014, vol. 55, # 32, p. 4458 - 4462
7
[ 5467-74-3 ]
[ 100-44-7 ]
[ 2116-36-1 ]
[ 23450-18-2 ]
Yield
Reaction Conditions
Operation in experiment
63%
at 100℃; for 24 h; Sealed tube
To a 10 mL reaction tube containing a magnet was added (4-bromophenyl) boronic acid (201 mg, 1.0 mmol)Lithium tert-butoxide (80 mg, 1.0 mmol).Trifluorotoluene (2 mL) and benzyl chloride (63 mg, 0.5 mmol) were added.Stuffed rubber stopper,The reaction was performed on a 100 ° C electromagnetic heating stirrer for about 24 hours.After the reaction,Cool to room temperature,The organic solvent is removed using a rotary evaporator,And purified by column chromatography to give 1-benzyl-4-bromobenzeneAnd 1-benzyl-2-bromobenzene (82 mg, 63percent).The compound is a colorless oily liquid,
88.889 % de
Stage #1: Schlenk technique; Inert atmosphere Stage #2: at 100℃; for 24 h; Schlenk technique; Inert atmosphere
General procedure: Arylboronic acid (1.0 mmol), LiOtBu (1.0 mmol) was added to a Schlenk tube. The tube was charged with nitrogen and then PhCF3 (2 mL) and benzyl chloride (0.5 mmol) were added. The reaction mixture was stirred at 100 °C for 24 h. After the mixture was cooled down to room temperature, solvent was removed under reduced pressure to leave a crude product. The crude product was purified by column chromatography on silica gel, eluting with petroleum ether to afford the coupling product.
Reference:
[1] Patent: CN106478326, 2017, A, . Location in patent: Paragraph 0098; 0099; 0100; 0101; 0102
[2] Tetrahedron, 2016, vol. 72, # 49, p. 8022 - 8030
8
[ 108-86-1 ]
[ 100-44-7 ]
[ 2116-36-1 ]
[ 23450-18-2 ]
Reference:
[1] Transition Metal Chemistry, 2016, vol. 41, # 2, p. 225 - 233
9
[ 98-80-6 ]
[ 3433-80-5 ]
[ 23450-18-2 ]
Reference:
[1] Patent: US2018/305381, 2018, A1,
10
[ 6630-33-7 ]
[ 23450-18-2 ]
Reference:
[1] Tetrahedron, 1976, vol. 32, p. 1921 - 1930
[2] Organic Letters, 2013, vol. 15, # 21, p. 5542 - 5545
[3] Tetrahedron Letters, 2014, vol. 55, # 32, p. 4458 - 4462
[4] Tetrahedron Letters, 2015, vol. 56, # 50, p. 7005 - 7007
[5] New Journal of Chemistry, 2016, vol. 40, # 11, p. 9030 - 9033
[6] Journal of the American Chemical Society, 2017, vol. 139, # 1, p. 245 - 254
[7] Chemistry - A European Journal, 2018, vol. 24, # 63, p. 16895 - 16901
11
[ 911707-65-8 ]
[ 71-43-2 ]
[ 23450-18-2 ]
Reference:
[1] Synlett, 2006, # 11, p. 1729 - 1733
Reference:
[1] Angewandte Chemie - International Edition, 2016, vol. 55, # 4, p. 1417 - 1421[2] Angew. Chem., 2016, vol. 55, # 4, p. 1439 - 1443,5
15
[ 108-86-1 ]
[ 23450-18-2 ]
Reference:
[1] Tetrahedron Letters, 2015, vol. 56, # 50, p. 7005 - 7007
[2] New Journal of Chemistry, 2016, vol. 40, # 11, p. 9030 - 9033
[3] Journal of the American Chemical Society, 2017, vol. 139, # 1, p. 245 - 254
[4] Chemistry - A European Journal, 2018, vol. 24, # 63, p. 16895 - 16901
Reference:
[1] Journal of Organic Chemistry, 1960, vol. 25, p. 2091 - 2094
30
[ 23450-18-2 ]
[ 40276-63-9 ]
Reference:
[1] Journal of Organic Chemistry, 2015, vol. 80, # 9, p. 4532 - 4544
[2] Journal of the American Chemical Society, 2017, vol. 139, # 45, p. 16210 - 16221
31
[ 121-43-7 ]
[ 23450-18-2 ]
[ 40276-63-9 ]
Reference:
[1] Chemical Communications, 2016, vol. 52, # 44, p. 7138 - 7141
With iron(III) chloride at 100℃; for 12h; Inert atmosphere;
65%
With iron(III) chloride for 12h; Heating;
1 Preparation of Intermediates 3 and 4.
Substrate 1: 4.68 g (25 mmol), anhydrous FeCl3: 405 mg (2.5 mmol), anhydrous benzene: 50 mL. To an oven-dried 200 mL high-pressure round-bottomed flask with screw-cap and stir bar was added 1 and FeCl3 followed by benzene. The cap was tightly fitted and the flask was stirred in 100° oil bath for 12 hours. A TLC check in 100% hexanes under short wave UV indicated complete conversion of the starting alcohol. The reaction was filtered through a silica plug in a glass fritted funnel, washing through with 50 mL of Et2O. The combined solution was concentrated under vacuum to a brown oil. This was purified by silica column chromatography, eluting with 100% hexanes. Concentration of the pure fractions under vacuum gave the known compound 3 as 4.02 g of colorless oil, 65%.
75 % Chromat.
With scandium tris(trifluoromethanesulfonate) at 115 - 125℃; for 8h; Heating;
With iron(III) chloride at 100℃; for 10h;
With boron trifluoride diethyl etherate at 80℃; for 2h;
General procedure for preparation of diarylmethanes
General procedure: In a round-bottom flask, phenylmethanol (0.54 g, 5.0 mmol) and BF3-OEt2(755 μL, 6.0 mmol) were dissolved in benzene (5.0 mL). After stirring for 2 hat 80 oC, the mixture was cooled to room temperature and then directly purified by column chromatography on silica gel using petroleum ether as eluent to give diphenylmethane(colorless oil, 0.67 g, 80% yield). The same procedure was utilizedfor all the synthesis of benzylic alcohols and diarylmethanes (2a-d, 2j-w).
1-[2-(phenylmethyl)phenyl]-4-dimethylaminocyclohexanol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30.6%
With n-butyllithium; In tetrahydrofuran; hexane; water; toluene;
EXAMPLE 1 1-[2-(Phenylmethyl)phenyl]-4-dimethylaminocyclohexanol To 24.7 g of 2-bromodiphenylmethane and 100 ml of dry tetrahydrofuran (THF, hereinafter) is added 55 ml of 2.4 molar solution of n-butyllithium in hexane dropwise with stirring at -40 to 50 C. under a dry nitrogen atmosphere. The resultant solution is stirred one hour after addition of the n-butyllithium is completed. A solution of 15.5 g <strong>[40594-34-1]4-dimethylaminocyclohexanone</strong> in 50 ml of dry THF is added dropwise with stirring while maintaining the temperature below -40 C. The resultant solution is stirred at -400 to -50 C. for two hours after addition of the ketone is completed and further stirred under N2 atmosphere overnight (16 hours) at room temperature. The solution is cooled to 0 C. and 350 ml of water and 400 ml of hexane are added thereto. The aqueous phase of the resultant mixture is removed and the product crystallized out of the organic phase. After filtration (washing the filter cake with hexane) the organic phase is washed three times with 100ml portions of water and cooled overnight. A second crop is obtained, combined with the first crop and recrystallized from 50 ml of toluene to yield 9.46 g (30.6% yield) of 1-[2-(phenylmethyl)phenyl]-4-dimethylaminocyclohexanol, m.p. 140-141 C. Analysis: Calculated for C21 H27 NO: 81.51% C, 8.79% H, 4.53% N; Found: 81.38% C, 8.74% H, 4.45% N.
500 ml of three-necked flask was placed in 12.4 g of 1-Benzyl-2-bromo-benzene, placed in a nitrogen system, 150 ml of tetrahydrofuran (THF) was added, cooled and cooled to -85 C with stirring, and 24 ml of n-butyllithium , Stir for 30 minutes. 14.3 g of 4-Bromo-fluoren-9-one was dissolved in 150 ml of tetrahydrofuran (THF), and the mixture was dropped into a three-necked flask and stirred for 1 hour.After the reaction was quenched with water, extraction was carried out using ethyl acetate, and the organic layer was collected and concentrated.Concentrated by adding 75 ml of acetic acid and 7.5 ml of hydrochloric acid, heated to reflux for 2 h. After cooling, methanol was added, the precipitated solid was collected, recrystallized from THF, and filtered to give a white solid. The product was dried 15 g, yield 54%.
10H-spiro[anthracene-2-bromo-9,9'-fluorene][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
Stage #1: 2-benzyl-1-bromobenzene With n-butyllithium In tetrahydrofuran; hexane for 0.5h; Cooling;
Stage #2: 2-bromofluoren-9-one In tetrahydrofuran; hexane at 20℃; for 1h;
1.1-1 Synthesis of Step 1-1 and Step 2- 1
After dissolving SM1 (1eq) in tetrahydrofuran (THF) (excess), lower the temperature to -7 ° C 2.5M n-BuLi (1.5eq)Was added dropwise, and after 30 minutes, SM2 (1.05 eq) shown in Table 1 was added and raised to room temperature (RT), followed by stirring for 1 hour.After adding 1N HCl (excess), stirring for 30 minutes, separating the layers, removing the solvent, purifying with ethyl acetate, and then adding the obtained solid to acetic acid (excess), 1 ml of sulfuric acid was added dropwise and stirred to reflux.After lowering the temperature to room temperature and neutralizing with water, the filtered solid was recrystallized with tetrahydrofuran and ethyl acetate toA1-1 to A1-12 of Table 1 were prepared.In the above preparation examples, R101 to R104 each represent a substituent, and a, b, c and d each represent a number of substituents.
Stage #1: 1-chlorocarbazole; 2-benzyl-1-bromobenzene With tert.-butyl lithium at 60℃; for 2h; Inert atmosphere;
Stage #2: boron tribromide With N-ethyl-N,N-diisopropylamine at 20℃; for 1h;
7 Synthesis of Compound 75:
In a 250ml three-necked flask, under the protection of nitrogen,Add 0.005mol of raw material 12 and 0.005mol of raw material 13,0.015mol tert-butyl lithium,Stir and mix 150ml tert-butylbenzene,Heat to 60°C, stir and react for 2 hours;Then cool to room temperature naturally,Drop 0.015mol BBr3 and 0.1mol diisopropylethylamine,Stir the reaction at room temperature for 1 hour,The sampling point board shows that there is no raw material 12 remaining and the reaction is complete;Add water and dichloromethane for extraction and liquid separation;Take the organic phase, add anhydrous magnesium sulfate to remove water, filter, the filtrate undergoes vacuum rotary evaporation (-0.09MPa, 25°C), and passes through a neutral silica gel column.Intermediate 5 was obtained with an HPLC purity of 98.0% and a yield of 59.3%;