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Structure of 623-24-5 * 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.
2.3.2.1 Synthesis of 1,4-bis(bromomethyl)benzene 4 In a 250 ml round bottom flask p-xylene 1 (5 ml, 40.78 mmol), and 70 ml of carbon tetrachloride were taken and then the flask was kept on an oil bath. N-bromosuccinimide (29.86 g, 167.80 mmol) and benzoyl peroxide (5.83 g, 24.08 mmol) were added into the flask and the whole solution was refluxed for 12 h at 70 °C. After the completion of reaction, the solution was cooled to room temperature and thus formed solid imide which in turn was removed by filtration. From the filtrate, the solvent was eliminated by distillation to give the pale yellow solid, viz., 1,4-bis(bromomethyl)benzene 4. The yield was 90percent and the melting point was 142-144 °C. FT-IR (KBr, cm-1): 568 (C-Br), 1625 (C=C); 1H NMR (300 MHz, CDCl3): 4.28 (s, 4H, methylene), 7.182 (s, 4H, aromatic).
87.4%
for 5 h; Reflux; Irradiation
It was prepared as a method previously described [27]. Briefly, 29.6 mL (0.24 mol) dry p-xylene was introduced into the flask, stirring at 140 °C in an oil bath. When the xylene starts boiling, 24.6 mL (0.48 mol) of dry bromine were added dropwise over 2 h and using a 300-watt tungsten lamp lighted reaction. To continued at 140 °C for an additional 3 h. Then, the mixture is cooled over night and dissolved in resultant of warm chloroform. And the precipitate was dissolved in fresh chloroform solution and recrystallizing in it. Yield: 55.4 g (87.4percent). m.p.:143–146 °C. Anal. Calc. for C8H8Br2: C, 36.40; H, 3.05. Found: C, 36.29; H, 3.37percent. FT-IR (KBr, cm−1): 3050, 3036(=C–H); 2972(C–H); 1512, 1437(Cph–Cph; Cph=Cph); 611(C–Br). 1H NMR (500 MHz, DMSO-d6, δ/ppm): 7.43 (s, 4H, ph), 4.69 (s, 4H, –CH2).
85.8%
With N-Bromosuccinimide; Perbenzoic acid In tetrachloromethane at 80℃; for 6 h;
To the solution of 2.0 mL (21.82 mmol) 1,4-dimethylbenzene in CCl4 (60 mL), 5.8 g (26 mmol) of NBS and 0.10 g (1.03 mmol) of benzoyl mixture peroxide were added, then stirred at 80°C for 6 h. A crude product was obtained after heat filter and washed with absolute ethyl alcohol. Compound 1 was obtained as a white acicular crystalline solid (4.94 g, 85.8percent yield) from the crude product by recrystallization with absolute ethyl alcohol
84%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane at 80℃; for 8 h; Inert atmosphere
p-Xylene (6.2 mL, 50 mmol) and N-bromosuccinimide (NBS) (21.3 g, 110 mmol) were added to a solution of CCl4 (100 mL) in a 250 mL three-necked flask. After the temperature reached to 80 °C, BPO (0.1 mg) was added into the flask. The mixture was vigorously stirred for 8 h at 80 °C under N2. The residue was cooled and the filtrate was concentrated, subsequently recrystal by absolute ethyl alcohol. 1,4-bis-bromomethylbenzene was obtained as white powder in 84percent yield. FT-IR (KBr, cm-1): 1516, 1456 (γC=C); 750 (γC-Br). 1H NMR (500 MHz, CDCl3): δ 7.55-7.36 (m, 4H, Ph-H); 3.81-3.74 (m, 4H, -CH2Br).
80%
With sulfuric acid; hydrogen bromide; dihydrogen peroxide In 1,2-dichloro-ethane for 12 h; Cooling with ice; Irradiation
119 g of 50percent hydrogen peroxide (1.75 mol)Slowly add to 300 g in an ice bathOf 74 g (0.7 mol) 1,4-xylene in DCE,242 g (1.44 mol) of hydrobromic acid and 7 g of concentrated sulfuric acid,The resulting mixture was then irradiated with a visible light lamp (wavelength about 400 nm) for 12 hours,An organic layer (DCE) is formed,Precipitation crude product and aqueous layer,The crude product is also partially present in the organic layer.After removal of DCE from the crude product by evaporation under reduced pressure,Add 30 grams of methanol,After stirring at 60 ° C for one hour,Cool to room temperature,After filtration, 150 g of high-purity 1,4-bis (bromomethyl) benzene was obtained (yield 80percent, purity 98.2percent).
76%
at 52℃; for 18 h; Inert atmosphere; Irradiation
The photoreaction equipment of 100ml equipped with a stirrer and by a Liebig condenser (100 W high pressure mercury lamp), under a nitrogen atmosphere, 1H perfluorohexane (20 ml), p-xylene (5 g, 47 mmol) and bromine 8.9 g (56 mol, 1.2eq.) were charged, and were carried out under reflux (52 ) light irradiation for 18 hours. After the reaction, adding water, reducing the excess chlorine with sodium sulfite, separated, dried over sodium sulfate (Na2SO4), filtered, and the solvent removed at recrystallization of 1,4-bis (bromomethyl) benzene 9 .4g (76percent yield). In addition, deterioration of some in the reaction solvent in the F-NMR measurement 1H- perfluorohexane was observed.
47%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethaneInert atmosphere; Reflux
0.1 g (12.2 mL) of p-xylene and 0.1 mol (17.6 g) of N-bromosuccinimide as a starting material, 36 mL of a chloride as a solvent, 2.4 g of benzoyl peroxide as an initiator, an inert gas And the reaction was carried out for 4 to 5 hours. The unreacted N-bromosuccinimide was removed by suction filtration, and the solvent was evaporated under reduced pressure. The remaining pale yellow liquid was frozen to give a pale yellow solid which was washed with an alcoholic solvent Recrystallization gave compound 1 (12.4 g) as a white solid in 47percent yield
45.5%
With N-Bromosuccinimide; dibenzoyl peroxide In benzene at 80℃; for 4 h; Heating / reflux
A solution of 1.23 ml_ (10 mmol) of p-xylene, 3.54 g (20 mmol) of N-bromosuccinimide (NBS) and 45 mg (0.2 mmol) of benzoyl peroxide in 30 mL of benzene was heated under reflux (80 0C) and argon atmosphere for 4 hours. The mixture was cooled to 25 0C and diluted with aqueous NH4OH and NaHCO3, and solids (succinimide) were removed by filtration. The filtrate was extracted twice with diethyl ether, and the combined ether extract was washed with brine, dried (anhydrous Na2SO4), and concentrated to give white solids. The solids were crystallized in diethyl ether to provide 1.20 g (45.5percent yield) pure product, 1 ,4-di(bromomethyl)benzene, as white solids. The mother liquor was concentrated to give 1.40 g of a mixture of the product and by-products. 1H NMR 7.37 (s, 4 H, Ar), 4.48 (s, 4 H, CH2); 13C NMR 138.2 (s), 129.7 (d), 33.0 (t).
40%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane at 80℃; for 20 h; Inert atmosphere
Under argon, p-xylene (5.04 g, 47.53 mmol), NBS (30 g) and BPO (2 g) were added to a bottle with carbon tetrachloride as a solvent and heated. While heating to 70 ° C, The solid and liquid in the bottle began to melt. After stabilization, heating was continued until the temperature reached 80 ° C. and the reaction was refluxed for 20 hours. The mixture was cooled and cooled. The upper layer was white solid and the lower layer was yellowish, cooled to 40 ° C., filtered, and the filtrate was taken into the refrigerator ,After 24h, white crystals precipitated, about 5g, that is on the dibromobenzyl, yield 40percent.
40%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane at 70 - 80℃; for 20 h; Inert atmosphere
Under argon atmosphere, p-xylene (5.04g, 47.53mmol), NBS (30g) and BPO (2g dibenzoyl peroxide) (2g) were added to the flask with carbon tetrachloride as the solvent for heating. ,When heated to 70°C, the solids and liquids in the bottle begin to melt, after stabilization,Continue heating, return to 80 °C, reflux for 20 hours, cooling and cooling, white solid on the upper layer,The lower light yellow liquid is cooled to 40°C, filtered, and the filtrate is put into the refrigerator.After 24 h, white crystals precipitated, about 5 g, ie, dibromobenzyl, with a yield of 40percent.
5.4 g
With sodium bromate; sodium hydrogensulfite In water; ethyl acetate for 5 h;
Example 1 The compounds according to the first embodiment are preferably prepared by a scheme as illustrated in Figure 1 . Reference will be made to this scheme in describing this Example. This example describes the synthesis wherein R1 and R3 are 4-pyridinyl groups and R^ is hydrogen. 1 ,4-di(bromomethyl)benzene (33 in figure 1 ) was prepared according to the synthesis described by Kikuchi, D.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1998, 63, 6023-6026. To a solution of NaBrO3 (12.1 g, 80 mmol) in H2O (40 mL) was added a solution of p-xylene (2.47 mL, 20 mmol) in EtOAc (40 mL) and the mixture was vigorously stirred. A solution of NaHSO3 (8.3 g, 80 mmol) in H2O (80 mL) was added dropwise within 15 min and the reaction was stirred for 5 h. After the reaction mixture was poured out in Et2O (300 mL), the layers were separated and the aqueous layer extracted twice with Et2O. The combined organic layers were washed with 2 M Na2S2O3, dried (Na2SO4), filtered and concentrated. The resulting white solids were subjected to column chromatography (0→ 5percent EtOAc/light petroleum) and the product was obtained as a white solid (5.4 g), but not completely pure: H NMR (CDCI3, 400 MHz) δ 7.37 (s, 4H); 4.47 (s, 4H). 3C NMR (CDCI3, 100 MHz) δ 129.5; 32.8.
5.4 g
With sodium bromate; sodium hydrogensulfite In water; ethyl acetate for 5 h;
As described previously by Kikuchi et al.26 a solution of NaBrO3 (12.1 g, 80 mmol) in H2O (40 mL) was added to a solutionof p-xylene (2.47 mL, 20 mmol) in EtOAc (40 mL) and the mixture was vigorously stirred. A solution of NaHSO3 (8.3 g,80 mmol) in H2O (80 mL) was added dropwise within 15 min and the reaction was stirred for 5 h. After the reaction mixture was poured out in Et2O (300 mL), the layers were separated and the aqueous layer extracted twice with Et2O. The combined organic layers were washed with 2 M Na2S2O3, dried (Na2SO4),filtered and concentrated. The resulting white solids were subjected to column chromatography (0→5percent EtOAc/light petroleum) and the product was obtained as a white solid (5.4 g), but not completely pure. 1H NMR (CDCl3, 400 MHz) d 7.37 (s, 4H); 4.47 (s, 4H). 13C NMR (CDCl3, 100 MHz) d 129.5; 32.8.
Reference：
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2
[ 106-42-3 ]
[ 623-24-5 ]
[ 104-81-4 ]
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[2] Tetrahedron Letters, 2006, vol. 47, # 7, p. 1097 - 1099
[3] Tetrahedron Letters, 2006, vol. 47, # 40, p. 7245 - 7247
[4] Tetrahedron, 2009, vol. 65, # 22, p. 4429 - 4439
[5] Journal of Organic Chemistry, 1998, vol. 63, # 17, p. 6023 - 6026
[6] Tetrahedron Letters, 2005, vol. 46, # 41, p. 7047 - 7050
[7] European Journal of Organic Chemistry, 2006, # 2, p. 483 - 488
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Reference：
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9
[ 50-00-0 ]
[ 71-43-2 ]
[ 623-24-5 ]
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[2] Patent: DE937647, 1954, ,
[3] Asian Journal of Chemistry, 2013, vol. 25, # 17, p. 10004 - 10006
10
[ 4497-29-4 ]
[ 71-43-2 ]
[ 623-24-5 ]
Reference：
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11
[ 4497-29-4 ]
[ 71-43-2 ]
[ 623-24-5 ]
[ 100-39-0 ]
Reference：
[1] Journal of the Chemical Society, 1920, vol. 117, p. 525
12
[ 4497-29-4 ]
[ 5435-44-9 ]
[ 71-43-2 ]
[ 623-24-5 ]
[ 100-39-0 ]
Reference：
[1] Journal of the Chemical Society, 1920, vol. 117, p. 525
13
[ 623-24-5 ]
[ 622-75-3 ]
Yield
Reaction Conditions
Operation in experiment
91%
at 50 - 60℃; for 3 h;
A mixture of 1,4-bis(bromomethyl)benze d cyanopotassium (4.80 g, 73.6 mmol) in ethanol (80.0 mL) and water (40 mL) was stirred at 50-60 °C for 3 hours. Water (300 mL) was added into the mixture. The resulting mixture was extracted with DCM (3 x 200 mL). The combined organic layer was washed with water (200 mL) three times and brine (200 mL), then concentrated to afford 2,2'-(1,4-phenylene)diacetonitrile (4.3 g, 91percent yield) as a white solid.1H NMR (400 MHz, CDCl3) δ 7.39 (s, 4H), 3.79 (s, 4H).
With tetrabutylammomium bromide; sodium carbonate; In chloroform; water;Reflux;
1,4,8,11-Tetraazacyclotetradecane 1 (0.205 mol) was dissolved in a mixture of water(160 mL) and chloroform (160 mL); sodium carbonate (0.205 mol) and a, a0-dibromop-xylene 2 (0.1mol) were added, followed by addition of 10% of TBAB catalyst(0.0205 mol). The solution was refluxed for 1-2 h, cooled to room temperature, pouredinto ice cold water and extracted with toluene (3x200 mL). The organic phases werecombined, dried over anhydrous MgSO4 and concentrated in vacuo to give a white solid3. The obtained solid material was dissolved in a minimum amount of dry methanol(250 mL) and dry HCl gas was gently passed through the solution to form a white precipitatewhich was filtered and dried to give 3 octahydrochloride.
With potassium carbonate; In methanol; dichloromethane; acetonitrile;
a 1-[4-(bromomethyl)phenylmethyl]-4,8,11-tri-(t-butoxycarbonyl)-1,4,8,11-tetraazacyclotetradecane alpha,alpha'-Dibromo-p-xylene (36.0 g, 136 mmol) was stirred at 60 C. in acetonitrile (500 mL) until it dissolved. Potassium carbonate (3.5 g, 25.3 mmol) was added, followed by the dropwise addition of a solution of 1,4,8-tri-(t-butyloxycarbonyl)-1,4,8,11-tetraazacyclotetradecane (Boitrel, et. al., Tetrahedron Lett., 1995, 36, 4995) (6.0 g, 11.98 mmol) in acetonitrile (100 mL). The mixture was stirred for 6 hours, cooled and partially evaporated. The excess dibromoxylene was filtered off, the mother liquors evaporated under vacuum and chromatographed (silica gel, 50% dichloromethane/hexane to 2% methanol/dichloromethane) to afford the title compound as a foam (7.4 g, 90%). MS (ES+) m/e 683 and 685 [M+H]+
90%
With potassium carbonate; In methanol; dichloromethane; acetonitrile;
a 1-[4-(bromomethyl)phenylmethyl]-4,8,11-tri-(t-butoxycarbonyl)-1,4,8,11-tetraazacyclotetradecane alpha,alpha'-Dibromo-p-xylene (36.0 g, 136 mmol) was stirred at 60 C. in acetonitrile (500 mL) until it dissolved. Potassium carbonate (3.5 g, 25.3 mmol) was added, followed by the dropwise addition of a solution of 1,4,8-tri-(t-butyloxycarbonyl)-1,4,8,11-tetraazacyclotetradecane (Boitrel et. al., Tetrahedron Lett., 1995, 36, 4995) (6.0 g, 11.98 mmol) in acetonitrile (100 mL). The mixture was stirred for 6 hours, cooled and partially evaporated. The excess dibromoxylene was filtered off, the mother liquors evaporated under vacuum and chromatographed (silica gel, 50% dichloromethane/hexane to 2% methanol/dichloromethane) to afford the title compound as a foam (7.4 g, 90%). MS (ES+) m/e 683 and 685 [M+H]+.
88%
With potassium carbonate; potassium iodide; In acetonitrile; at 60℃; for 4h;
(6) Synthesis step of compound 6: Weigh 2.15 g (8.15 mmol) of alpha, alpha'-dibromo-p-xylene and dissolve it in 40 ml of acetonitrile, and then add 0.26 g (1.88 mmol) of potassium carbonate and 0.25 g to the solution. (1.51 mmol) of potassium iodide, and 10 ml of a solution of 0.42 g (0.84 mmol) of compound 5 in acetonitrile was added dropwise, and the reaction mixture was stirred at 60 C. for 4 h. The solution was concentrated by filtration and purified by silica gel chromatography to finally obtain compound 6 (0.51 g, 88%) as a white foam.
With potassium carbonate; In acetonitrile; at 60℃; for 12h;
K2CO3 (0.05 mol) was added to a solution of tri-Boc-protected cyclam (O.Olmole) and 1,4 dibromomethylbenzene (0.01 mol) in CH3CN at 60 0C. After stirring the reaction mixture for 12 h, tri-Boc-protected bromomethylbenzylcyclam was obtained (0.007 mol). It was then reacted with bis(2-pyridyliminoethyl)amine (0.01 mole) in CH3CN (100 mL) in the presence of K2CO3 (0.05 mol) at 60 C. After stirring for 12 h, the reaction mixture was filtered and concentrated. MeOH (50 mL) was added to this mixture, followed by the addition of NaBH4 (0.03 mol) at 25 0C. The mixture was stirred for another 2 h. The solution was partitioned between EtOAc and water. The organic layer was then separated, dried over MgSO4 (s), filtered, and concentrated to give a residue. The residue was treated with HCl/ether and purified by alumina column chromatography (EtOAc/MeOH = 1:2) to afford compound 49. LC/MS (M++l): 588.
[2]{1,4'-bis(3,5-di-tert-butylphenyloxymethyl)benzene}-{11'-tert-butyl-5',17',23',35',38',40',43',45'-octamethyldispiro[cyclohexane-1,2'-7',15',25',33'-tetraazaheptacyclo[32.2.2.23'.6'.216'.19'.221'.24'.19'.13'.127'.31']hexatetraconta-...]...[ No CAS ]
With sodium carbonate; In water; N,N-dimethyl-formamide;
EXAMPLE 1 N,N'-Dihydroxy-N,N'-di-tert-butyl-p-xylylenediamine A suspension of 3.0 g tert-butylhydroxylamine hydrochloride, 5.0 g of anhydrous sodium carbonate and 3.15 g of p-xylylene dibromide in 20 ml of N,N-dimethylformamide is heated at 80° C. under nitrogen for 3 hours. Dilution of the reaction mixture with water followed by crystallization from heptane affords 2.1 g of product as a white solid; m.p. 137°-138° C. Analysis: Calculated for C16 H28 N2 O2: C, 68.53; H, 10.06; N, 9.99. Found: C, 68.7; H, 9.8; N, 10.1.
General procedure: A solution of thehydroxyiminomethylpyridine (1.0 g, 8.2 mmol) and dibromoxylene(10.8 g, 40.9 mmol) in acetone (100 ml) wasstirred at reflux. The reaction mixture was cooled to the room temperature; the crystalline crude product was collectedby filtration, washed with acetone (320 ml) and recrystalizedfrom acetonitrile (MeCN).
73%
In acetone; at 20℃; for 4h;
In a typical experimental procedure a solution of 4-pyridinealdoxime (2.44 g, 20.00 mmol) in 50 mL dry acetone was added slowly to a stirred solution of alpha,alpha' dibromo-p-xylene (13.2 g, 50.00 mmol) in 100 mL dry acetone at room temperature. The mixture was stirred at r.t. for 4 h. The solids appeared were filtered off and washed repeatedly with hot dry acetone to give the intermediate 1-(4-bromomethyl benzyl)-4-(hydroxyimino methyl)-pyridinium bromide. The compound thus obtained was sufficiently pure for use in the next step. m.p. 194-96 C. Yield: 5.65 g (73%). All other intermediate pyridinium monooximes were prepared in a similar manner.
General procedure: 5,7-dibromoisatin 2 (1 g, 3.28 mmol) was taken up in anhydrous DMF (30 mL) and cooled on ice with stirring. Solid K2CO3 (544 mg, 3.94 mmol) was added in one portion, and the dark colored suspension was brought to room temperature and stirred for a further 1 h. 1-Bromo-3-chloropropane (620 mg, 3.94 mmol, 0.387 mL) was added slowly with constant stirring and the reaction mixture was stirred at 80 C for 4-8 h, until the 5,7-dibromoisatin starting material had been consumed (TLC). The reaction mixture was poured into HCl (0.5 M, 50 mL) and extracted with ethyl acetate (3 × 50 mL). The ethyl acetate layer was washed with brine and dried over MgSO4. The solvent was removed, and the crude product was purified by silica gel column chromatography (CH2Cl2 as eluent) to give pure 3 (0.93 g, 74%) as orange red crystals.
General procedure: Initially, mono (5 or 7) or di-substituted (5,7) or unsubstitutedisatins 1(ael) (10 mmol) were dissolved in anhydrous DMF (30 mL)and cooled on ice with stirring. Solid dry K2CO3 (11 mmol) wasadded in one portion, and the dark-colored suspensionwas broughtto room temperature and stirred for a further 1 h. 1,4-bis(bromomethyl)benzene (40 mmol) was added slowly withconstant stirring until the mono or di-substituted isatin startingmaterial had been consumed (TLC). The reaction mixture waspoured into cold water and extracted with ethyl acetate. The ethylacetate layer was washed with water, brine, and dried over MgSO4.The solvent was removed, and the crude product was purified bysilica gel column chromatography using (hexanes/EtOAc, 80:20) aseluent to yield the key intermediates (-N-(p-bromomethyl benzyl)isatins 2(ael) (yield 75-80%) as orange-red crystals.
5,7-dibromoisatin (10 mmol) was dissolved in anhydrous DMF (30 mL) and cooled on ice with stirring. Solid K2CO3 (11 mmol) was added and the dark-colored suspension was brought to room temperature and stirred for 1 hour. 1,4-bis(bromomethyl)benzene (40 mmol) was added slowly with constant stirring until the starting material had been consumed (monitored by TLC). The reaction mixture was poured into cold water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, brine and dried over MgSO4. The solvent was removed, and the crude product was purified by silica gel column chromatography using (hexanes/ethyl acetate, 80:20) as the eluent to yield the intermediate 5,7-dibromo-1-(4- bromomethylbenzyl)-1H-indole-2,3-dione as orange-red crystals.
General procedure: A butanone solution (40 mL) of the linker (2 equiv.) and the corresponding 4-substituted pyridine (1 equiv.) was stirred at room temperature for 3 h 21, 22, 23, 25 and 26 were isolated after filtration and thorough washing with butanone, ethyl acetate and diethyl ether. In the case of 24, 27 and 28, the reaction mixture was evaporated, and the crude products purified by flash column chromatography on silica gel using CH2Cl2/MeOH (10/0.5) as eluent.
Bisbromomethyl(bis-p-benzyl-<strong>[113682-56-7]4,4'-(1,4-phenylene)bispyridine</strong>)bis(hexyfluorophosphate) (DB·2PF6) alpha,alpha'-Dibromop-xylene (4.58 g, 17.2 mmol) was added to CH2Cl2 (30 mL) in a 250 mL round-bottomed three-neck flask, and the resulting mixture was refluxed while stirring until all of the solid material dissolved. Next, the temperature of the oil bath was raised to 90° C., allowing the reaction mixture to reflux, while a suspension of ExBIPY (400 mg, 1.72 mmol) in MeCN (60 mL) was added in five aliquots slowly over 1 h. After only 30 min, however, a yellow precipitate, indicative of DB·2Br formation, began to appear. After heating under reflux for 48 h, the reaction mixture was cooled to room temperature, and the yellow precipitate was collected by filtration and washed with CH2Cl2. The yellow solid was dissolved in cold (?25° C.) MeOH (?500-750 mL) followed by the addition of NH4PF6 (?100-200 mg) and cold (?25° C.) H2O (?2 L), resulting in the precipitation of pure DB·2PF6 (1.41 g, 92percent) that was collected by filtration as a white solid. HRMS-ESI for DB·2PF6: calcd for C32H28Br2F12N2P2, m/z=743.0256 [M-PF6]+, 597.0536 [M-2PF6]2+. found, 743.0262 [M-PF6]+, 597.0538 [M-2PF6]2+. 1H NMR (500 MHz, CD3CN, ppm): deltaH 8.66 (AA' of AA'XX', J=6.9 Hz, 4H), 8.19 (XX' of AA'XX', J=6.9 Hz, 4H), 7.97 (s, 4H), 7.40 (AA' of AA'BB', J=8.2 Hz, 4H), 7.31 (BB' of AA'BB', J=8.2 Hz, 4H), 5.58 (s, 4H), 4.46 (s, 4H). 13C NMR (125 MHz, CD3CN, ppm): deltaC 155.0, 144.3, 139.9, 136.7, 132.9, 129.8, 129.1, 129.1, 125.6, 63.1, 32.3.
General procedure: Ligands (L1-L6) were prepared according to the similar or modified references [26,28,29]. A mixed solution of pyrazole (1.02 g, 15 mmol) (L1) or its derivates (3,5-dimethyl-1H-pyrazole (1.47 g, 15 mmol) (L2), 4-iodo-1H-pyrazol (2.19 g, 15 mmol) (L3), <strong>[2033-45-6]4-iodo-3,5-dimethyl-1H-pyrazole</strong> (3.33 g, 15 mmol) (L4), 4-nitro-1H-pyrazole (1.70 g, 15 mmol) (L5), 4-nitro-3,5-dimethyl-1H-pyrazol (2.12 g, 15 mmol) (L6)) and 82% potassium hydroxide (1.02 g, 15 mmol) in DMSO (10 mL) were vigorously stirred at 80 C for 1 h. Then, 1,4-bis(bromomethyl)benzene (1.98 g, 7.5 mmol) in DMSO (15 mL) was added dropwise to the solution above over 30 min, keeping the reaction at 80 C to continue stirring for 5-10 h. The mixture was poured into 200 mL of H2O and an amount of precipitates occurred. Finally, the precipitate was filtered and dried in the air. The precipitate was dissolved in the fresh chloroform solution and re-crystallized from it. The characterization data of the ligands L1-L6 were listed in Table 1 and the detailed appointments of the IR spectra data are given in Table S1.
88.4%
A mixture of 1.47g (15mmol) of 3,5-dimethylpyrazole, 1.02g (15mmol) of potassium hydroxide, and 10ml of DMSO was stirred at 80C for 1h. A solution of 1.98g (7.5mmol) of 1,4-bis(dibromomethyl)benzene in 10ml of DMSO was added dropwise, the mixture was stirred for 8h at 80C, diluted with 200ml of water, and the precipitate was filtered off ,washed with the mixture of ethanol and water, dried under reduced pressure.
1,4-bis(2-methylmercaptobenzimidazol-1-ylmethyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
66%
General procedure: A mixture of KOH and 2-methylmercaptobenzimidazole was stirred in DMF at room temperature for 1 h. The dibromo compound was added to the above reaction mixture was allowed to stir continuously at room temperature for 24 h. The reaction was quenched by adding water. The resulting powder was collected by filtration and was dried.
1,4-bis{2,2-bis[(3aR,8aS)-8,8a-dihydro-3aH-indeno[1,2-d]oxazol-2-yl]ethyl}benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
98%
Stage #1: bis[(3aR,8aS)-8,8a-dihydro-3aH-indeno[1,2-d]oxazol-2-yl]methane With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
Stage #2: 1,4-bis(bromomethyl)benzene In tetrahydrofuran for 10h; Inert atmosphere; Heating;
With potassium carbonate; In acetone; for 4h;Reflux; Inert atmosphere;
General procedure: K2CO3 (5.8 mmol, 7 eq.) and p-xylylene dibromide (0.42 mmol, 0.5 eq.) or m-xylylene dibromide(0.42 mmol, 0.5 eq.) were added to the solution of silybin (1 or 1a or 1b, 400 mg, 0.83 mmol, 1 eq.) in dry acetone (20 mL). The mixture was stirred and refluxed for 4 h under nitrogen. The reaction was quenched by the addition of conc. HCl (1 mL), diluted with water (50 mL) and extracted with ethyl acetate (2 × 30 mL). The organic layer was dried over Na2SO4 and evaporated. The residue was purified by flash chromatography (linear gradient from chloroform/acetone 85:15 to acetone 100%) and the title compound was isolated as a white amorphous solid.
N9-[4-(bromomethyl)benzyl]-N6,N6-bis(tert-butoxycarbonyl)adenine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; for 2h;Inert atmosphere;
General procedure: A solution of compound 1 (0.838 g, 2.5 mmol), 2 (0.567g, 2.5mmol), or 3 (0.540 g, 2.5 mmol), Cs2CO3 (0.888 g, 2.725 mmol), and 1,4-bis(bromomethyl)benzene (1.96 g, 7.5 mmol) in anhyd DMF (14 mL) was stirred for 2 h at r.t. under argon. The solvent was evaporated; the residue was dissolved in CH2Cl2 and washed with H2O (2 × 50 mL). The organic layer was dried (Na2SO4), filtered,and concentrated under vacuum. The residue was purified by column chromatography [silica gel, EtOAc (for 4) and CH2Cl2-EtOAc, 4:1 (for 7 and 8)].
1,4-phenylenebis(methylene) bis(3-fluoro-4-hydroxybenzoate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
With sodium hydrogencarbonate; In N,N-dimethyl-formamide; at 105℃;Inert atmosphere;
General procedure: A mixture of the corresponding dibromide derivate (1.0 mmol),<strong>[350-29-8]3-fluoro-4-hydroxybenzoic acid</strong> (343 mg, 2.2 mmol), and NaHCO3 (210 mg,2.5 mmol) in anhydrous DMF (15 ml) under an argon atmospherewas heated at 105°C overnight. The mixture was cooled and thensaturated aqueous NaHCO3 (7 ml), saturated aqueous NaCl (10 ml),and AcOEt (50ml) were added. Themixture was filtered through a pad ofCelite and after decantation the aqueous layer was extracted with AcOEt(2 20 ml). The combined organic layers were dried over anhydrousMgSO4 and concentrated in vacuo. Finally, the crude product was purifiedby silica gel column chromatography (eluent: AcOEt/hexane, 1:3).
General procedure: A mixture of the ditertiary amine (Compound 2) (11.52 g, 0.05 mol) and water (15 g) was charged into a reaction flask fitted with thermometer, stirrer and reflux condenser and heated to 65°C. Epichlorohydrin (4.63 g, 0.05 mol) was then added into the reactor. The temperature was gradually raised to 76°C and the reaction was carried out for 3 h. After the reaction, the resulted product was purified via vacuum distillation to remove unreacted reactants. The product was a clear and yellowish liquid (15.10 g, yield: 93.49percent).
2,4,6-tris(benzylpyridinium-4-yl)-1,3,5-triazine tris(hexafluorophosphate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
10072] TPT133 PF5. A solution of 1,4-bis(bromomethyl) benzene (7.98 g, 30.2 mmol) in 1:1 (v/v) MeCN-CH2C12 (120 mE) was heated to 90 C. in an atmosphere of argon and treated with solid TPT (703 mg, 2.25 mmol) in small portions. The mixture was stirred for 72 h, producing a yellow suspension over time. Afier cooling to room temperature, the suspension was diluted with CH2C12 (500 mE) and the solid was isolated by filtration. The filter cake was washed with copious amounts of CH2C12 and then triturated with MeOH (45 mE). The combined fractions were added to saturated aqueous NH4PF6 (500 mE), resulting in the precipitation of TPTI3 3 PF5 as a white solid (1.70 g, 1.31 mmol, 58%). ?H-NMR (500 MHz, CD3CN) oe 9.25 (d, J=6.5 Hz, 6H), 9.08 (d, J=7 Hz, 6H), 7.57 (d, J=8 Hz, 6H), 7.53 (d, J=8.5 Hz, 6H), 5.88 (s, 6H), 4.62 (s, 6H). ?3C-NMR (125 MHz, CD3CN) oe 170.2, 150.5, 147.2, 141.4, 133.5, 131.5, 130.8, 128.6, 65.5, 33.5. HRMS (ESI) Calcd. for C42H358r3F12N5P2: mlz=1 152.9809 [M-PF5]. found: 1152.9816.
bis-[α,α'-[para-(Boc-aminoethyl)phenoxy]]-p-xylene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
97%
General procedure: A mixture of N-Boc-tyramine A and K2CO3 in dry MeCN was refluxed under Ar during 30 min. The bromomethylbenzenederivative was added and reflux was continued during 24 h (TLCmonitoring; SiO2, CH2Cl2/MeOH 99.8:0.2 to 98:2). After cooling,the solvent was evaporated to dryness, and the solid residue wasdissolved in CH2Cl2. The insoluble materials were filtered off, andthe concentrated filtrate was chromatographed (SiO2;CH2Cl2/MeOH X:Y%) to give the desired n-[para-(Bocaminoethyl)-phenoxymethyl] benzene.
N,N'-(1,4-phenylenebis(methylene))bis(1-(2-chlorophenyl)-N-methylmethanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(1-(3-chlorophenyl)-N-methylmethanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(1-(2-fluorophenyl)-N-methylmethanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(1-(3-fluorophenyl)-N-methylmethanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(1-(3-methoxyphenyl)-N-methylmethanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(N-methyl-1-(pyridin-3-yl)methanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
N,N'-(1,4-phenylenebis(methylene))bis(N-methyl-1-(pyridin-4-yl)methanamine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With potassium carbonate; In acetonitrile; for 3h;Reflux;
General procedure: To a solution of 1,4-bis(bromomethyl)benzene (1 mmol) in anhydrous acetonitrile (10 mL) was added potassium carbonate (3 mmol) and the corresponding secondary amine (2.2 mmol). The reaction mixture was heated at reflux for 3 h. The resulting mixture was diluted with water (20 mL) and extracted with ethyl acetate (15 mL) three times. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude was purified by column chromatography with methanol/dichloromethane (150:1, v/v) to give the title compound as a colorless liquid or a white solid.
5-(benzyloxy)-2-(4-(benzyloxy)phenyl)-1-(4-(bromomethyl)benzyl)-3-methyl-1H-indole[ No CAS ]
1,4-bis((5-(benzyloxy)-2-(4-(benzyloxy)phenyl)-3-methyl-1H-indol-1-yl)methyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
22%; 63%
A solution of the indole 5, (1.0 g, 2.4 mmol) in THF (10 mL) wasadded dropwise to a stirring mixture of NaH (10 equiv, 571 mg,23.8 mmol) in THF (10 mL) at 0 C under N2 atmosphere. The mixturewas stirred for 10 min, at which point the a,a-dibromop-xylene (61) (0.5 equiv, 310 mg, 1.19 mmol) was added and themixture was stirred for 30 min at 0 C. The reaction was refluxedfor a further 30 min under N2 atmosphere, the mixture wasallowed to cool at which point water was added dropwise untilthe solution became clear. The solvent was evaporated underreduced pressure to obtain a brown oil. The resin was dissolvedin DCM (50 mL) and the extract was washed with water(3 50 mL), brine (50 mL) and dried over Na2SO4. The solventwas evaporated under reduced pressure to obtain a brown oil.The material was purified via flash chromatography on silica gel(DCM/EtOAc, gradient 4:1 to 3:1) to afford the product as a yellowsolid. (1.4 g, 63%); Mp 130-133 C. IR: mmax (KBr) cm1: 3438.9 (br),3032.0, 2925.9, 2862.0, 1605.5, 1505.3, 1453.1, 1277.5, 1245.5,1189.5, 1003.8, 839.9, 695.8. 1H NMR (CDCl3, 400 MHz) d 8.01-8.16 (m, 4H, Ar-H), 7.30-7.52 (m, 22H, Ar-H), 7.02-7.13 (m, 4H,Ar-H), 6.85-6.94 (m, 2H, Ar-H), 6.74-6.84 (m, 2H, Ar-H), 5.99-6.10 (m, 4H, Ar-H), 5.15 (s, 4H, 2 CH2), 5.12 (s, 2H, CH2), 5.09(s, 2H, CH2), 3.05-3.22 (m, 4H, 2 CH2), 1.61 (s, 6H, 2 CH3). 13CNMR (CDCl3, 100 MHz) d 160.1 (C-OBn), 151.8 (C-OBn), 145.8(Cq), 136.5 (Cq), 136.0 (Cq), 133.3 (Cq), 129.4, 128.2, 128.1, 127.9,127.7, 127.6, 127.2, 127.1, 127.1, 120.1, 114.4, 113.6, 108.9,108.7, 70.0 (CH2), 69.7 (CH2), 23.9 (CH3). HRMS (EI): Found941.4326 (M+H)+, C66H57N2O4 requires 941.4318.
1,1’-[1,4-phenylenebis(methylene)]bis(4-phenyl-4H-1,2,4-triazol-1-ium) dibromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
In dichloromethane;Schlenk technique; Reflux;
General procedure: 1,4-bis(Bromomethyl)benzene (0.20 g, 0.76 mmol) and the appropriateimidazole or triazole (1.60 mmol) in DCM (3 mL) were refluxed for 12.16 h in a 10 mL Ace pressure tube. The reaction mixture was cooledto room temperature and extracted with water (3 ~ 5 mL). The aqueousphase was dried in vacuo and the crude product crystallised frommethanol/acetone (1:4) to give pure product as a white solid.
N-bis(1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazol-5ylamino)benzyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89.3%
With potassium hydroxide; In toluene; at 20℃; for 3h;Sonication; Microwave irradiation; Heating;
(Fixed power 150 W) was charged with 50 mL of toluene, 10.0 g of 3-cyano-4-trifluoromethylsulfinyl-5-amino-1- (2,6-dichloro-4-trifluoromethylbenzene And the mixture was stirred at room temperature for 60min. After the shock, the spray switch was turned on. The mist was sent to the top of the microwave reactor through the trachea, and the microwave reactor was turned on. The power The reaction was started at 300W. When the solvent in the ultrasonic atomizer was about to be atomized, the atomization was stopped and the inlet of the microwave reactor was turned off and the reaction was continued for 120 min.After the completion of the reaction, the product was washed with water and dried by filtration to obtain 14.24 g of compound 8.Yield: 89.3%.
4,4'-(1,4-phenylenebis(methylene))bis(1-methyl-1,2,4-triazol-4-ium) dibromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
In dichloromethane; at 120℃; for 12 - 16h;Schlenk technique; Glovebox; Inert atmosphere;
General procedure: In a typical run, a 10-mL thick wall pressure tube was charged with 1,4-bis(bromomethyl)benzene (0.20 g,0.76 mmol), the corresponding 1-alkyl-1H-1,2,4-triazoles(1.60 mmol) and DCM (3 mL). The reaction mixture was heated at 120 C for 12?16 h. The reaction mixture was cooled to room temperature and extracted with water(3 9 5 mL). The collected aqueous phase was dried by rotovap, and the crude product was recrystallized from methanol/acetone (1:4) to give the product as a white solid.
4,4'-(1,4-phenylenebis(methylene))bis(1-ethyl-1,2,4-triazol-4-ium) dibromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
In dichloromethane; at 120℃; for 12 - 16h;Schlenk technique; Glovebox; Inert atmosphere;
General procedure: In a typical run, a 10-mL thick wall pressure tube was charged with 1,4-bis(bromomethyl)benzene (0.20 g,0.76 mmol), the corresponding 1-alkyl-1H-1,2,4-triazoles(1.60 mmol) and DCM (3 mL). The reaction mixture was heated at 120 C for 12-16 h. The reaction mixture was cooled to room temperature and extracted with water(3 9 5 mL). The collected aqueous phase was dried by rotovap, and the crude product was recrystallized from methanol/acetone (1:4) to give the product as a white solid.
With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl acetamide; at 140℃; for 0.5h;Microwave irradiation;
Reference example 16 (0563) (0564) 1,4-bis(bromomethyl)benzene (2.57g, 9.73mmol) and DIPEA (0.850mL, 4.86mmol) were added into DMA (15mL) solution of Compound iii-35 (1.00g, 3.24mmol), and the mixture was stirred and heated at 140C for 30 minutes by microwave device. After water added into the reaction mixture, the mixture was extracted with ethyl acetate. After the organic layer was washed with brine, and the mixture was dried with magnesium sulfate anhydrous, the solvent was removed in vacuo. The obtained residue was purified by silica gel column chromatography (hexane-chloroform) to give Compound iii-36 (1.12g, 70%). LC/MS (ESI): 491 (M+1)
With sodium hydroxide; In water; N,N-dimethyl-formamide; for 4h;
A. Add 5 g of <strong>[18113-03-6]2-chloro-4-methoxyphenol</strong> to a mixture of 17 g of alpha,alpha-dibromo-p-xylene to a stirred mixture of 2.5 g of 50:50 (w/w) NaOH:H2 O and 50 mL of DMF. Stir the so-formed mixture for 4 hours. Partition the reaction mixture with methylene chloride and water. Separate the organic layer and remove the solvent by rotary evaporation to obtain a solid residue. Purify the residue on a silica gel chromalography column using pure hexane to pure methylene chloride as the eluants to provide 8 g of 1-[4-alpha-bromomethylbenzyl]-<strong>[18113-03-6]2-chloro-4-methoxyphenol</strong>.
After dissolving 5.28 g of 1,4-dibenzyl bromide in 100 ml of ethanol,14.18 g of N, N-diethylbenzylamine,50 C for 12 hours,Stop the reaction filtration,The filter cake was washed with 20 ml of ethyl acetate,15 ml of ether three times,11.5 grams Gemini quaternary salt 4 was obtained.
A mixture of 1,4-bis(bromomethyl)benze d cyanopotassium (4.80 g, 73.6 mmol) in ethanol (80.0 mL) and water (40 mL) was stirred at 50-60 C for 3 hours. Water (300 mL) was added into the mixture. The resulting mixture was extracted with DCM (3 x 200 mL). The combined organic layer was washed with water (200 mL) three times and brine (200 mL), then concentrated to afford 2,2'-(1,4-phenylene)diacetonitrile (4.3 g, 91% yield) as a white solid.1H NMR (400 MHz, CDCl3) delta 7.39 (s, 4H), 3.79 (s, 4H).
2,2'-((1,4-phenylenebis(methylene))bis(sulfanediyl))dinicotinic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
2.2 Synthesis of 2,2'-((1,4-phenylenebis(methylene))bis(sulfanediyl))dinicotinic acid (H2pbsd) Ligand H2pbsd was synthesized following the reported process [28] . <strong>[38521-46-9]2-Mercaptonicotinic acid</strong> (2.35 g, 17 mmol) was added in ethanol solution (100 mL) of sodium (1.0 g, 43 mmol) under nitrogen with stirring, and the stirring was continued for 10 min 1,4-bis(bromomethyl)benzene (1.65 g, 5 mmol) was added in the resulting suspension and the reaction mixture was stirred under refluxing for 6 h. The solid was hot filtered and dissolved in water. After removing any undissolved substance by filtration, the filtrate was acidified with dilute hydrochloric acid to give a light-yellow precipitate, which was collected and rinsed with water and hot ethanol. Yield: 63%. 1H NMR (400 MHz, DMSO-d6, ppm): delta = 4.34 (s, 2H), 7.25 (m, 2H), 7.35 (s, 2H), 8.22 (m, 1H), 8.66 (m, 1H), 13.45 (s, 1H).
Add about 2.6 mL (6 mmol) of <strong>[1116-76-3]trioctylamine</strong> to 15 mL of chloroform in a 100 mL three-necked flask.Further, 0.5 g (about 1.9 mmol) of p-benzyl bromide (trade name alpha,alpha -dibromo-p-xylene) was dissolved in 5 mL of chloroform and transferred to a constant pressure dropping funnel.Slowly drip the liquid in the constant pressure dropping funnel into the three-neck bottle.After refluxing for 6 h, a colorless clear liquid was obtained, and the solvent was removed under reduced pressure;A colorless viscous liquid is obtained, which is then purified using a silica gel column.Using CH2Cl2/C2H5OH (v/v=50:1?10:1) as the eluent,A colorless viscous liquid was obtained, and the structural characterization results showed the desired product.The product characterization data is as follows:Yield 80.5%.
1.0g (4mmol) was added to a 100mL three-necked bottle p-dibenzyl bromide (trade name alpha,alpha -dibromo-p-xylene) was dissolved in 30 ml of chloroform. At the same time, 435 ul (1 mmol) of tri-n-octylamine was dissolved in 5 ml of chloroform, transferred to a constant pressure funnel, and slowly added dropwise to a three-necked flask. After 6 h of reaction, a colorless clear liquid was obtained, and the solvent was evaporated under reduced pressure to give a colorless viscous liquid. The colorless viscous liquid was dissolved in an appropriate amount of CH2Cl2 , and the product was purified using a silica gel column, using CH2 Cl2 and ethanol as an eluent (v/v=50:1?10:1), and eluting with a gradient to obtain a colorless 438.5 mg of the viscous liquid, Compound 1, the characterization data is as follows:
bis(4-bromomethyl) (bis-p-benzyl-4,4’-(1,4-phenylene)bispyridine)bis(hexafluorophosphate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
The synthetic protocol was adopted from the literature procedure.[Gong, X. et al., J. Am. Chem. Soc. 2017, 139, 4107-4116] alpha,alpha'--Dibromo-p-xylene (3.69 g, 13.86 mmol) was introduced into a round-bottomed flask and dry CH2C12 (30 mL) was added to the flask. The mixture was heated under reflux at 50 C to obtain a clear solution. Once all the chemicals had dissolved the temperature was raised to 90 C. ExBIPY? (322 mg, 1.38 mmol) was dissolved in dry MeCN (60mL) and added to the reaction mixture over 1 h (4-5 portions). The yellow precipitate started forming after 30 mm. The reaction mixture was stirred for 2 days at 90 C. Then it was brought to the room temperature and the yellow precipitate was filtered off and washed with CH2C12 to remove the unreacted starting materials. Finally, the solid was dissolved in H20 and excess of NH4PF6 was added to precipitate the crude product. Excess of NH4PF6 was washed several timeswith H20 to obtain the pure whitish yellow product in 80% yield. 1H NMR (500 MHz, CD3CN,25 C): = 8.80 (AA? of AA?XX?, J= 7 Hz, 4H), 8.33 (XX? of AA?XX?, J= 6.5 Hz, 4H), 8.12 (s,4H), 7.55 (AA? of AA?BB?, J= 8Hz, 4H), 7.47 (BB? of AA?BB?, J= 8.5 Hz, 4H), 5.73 (s, 4H),4.61 (s, 4H). ?3C NMR (125 MHz, CD3CN, 25 C): = 155.0, 144.3, 139.9, 136.7, 132.9, 129.8,129.1, 129.1, 125.6, 63.1, 32.3.
With sodium azide; copper(I) oxide; In water; at 100℃; for 1h;
General procedure: In round-bottomed flask α,α'-dibromo-p-xylene (0.5 mmol,1 equiv.), NaN3, (1.2 mmol, 1.2 equiv.), terminal alkyne(1.2 mmol, 1.2 equiv.) and 5 mg Cu2ONPs were taken inwater (10 mL). The mixture was magnetically stirred underreflux (100 C) for 60 min. The progress of the reaction wasmonitored by the formation of solid on the wall of thereaction container. After completion of the reaction, themixture was cooled to room temperature and the solutionwas decanted. The leftover residue was washed with dil.NH4Cl : NH3 solution (2 x 9 10 mL) whereupon copper gotremoved as blue colour copperamine species followed bywashing with ethyl acetate (2 x 9 10 mL) and the remainingsolid product was dried under vacuum.
1.1
(1) Dissolve 4,6-dimethylpyrimidine (100 μL to 110 μL) and 1,4-dibromomethylbenzene (178 μL to 180 μL) in 5 mL of acetonitrile in a 25 mL round bottom flask. The stirred mixture was heated under reflux at 80-85°C for 24 hours. After cooling to room temperature, excess acetonitrile in the mixture was removed. Separation and purification by column chromatography on silica gel (petroleum ether:dichloromethane=1:3, v/v) gave a white solid, which is an intermediate product (82 mg, yield: 31.3%).
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