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USD 15-60
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USD 80+
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Structure of 111-83-1 * 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.
Stage #1: With sodium hydroxide In dimethyl sulfoxide at 90℃; for 2 h; Stage #2: at 20 - 65℃; for 19 h;
A mixture of imidazole (1 .36 g, 20.0 mmol) and sodium hydroxide (0.80 g, 20.0 mmol) in DMSO was heated to 90 °C for 2 h, and then cooled to room temperature. A solution of 1 -bromooctane (3.46 g, 19.0 mmol) in DMSO was added dropwise to the mixture. After stirring at room temperature for 3 h, the mixture was heated up slowly to 65 °C for 16 h with constant stirring. The solution obtained was mixed with water and the product was extracted 4 times with diethyl ether. The diethyl ether phases were combined and dried with sodium sulfate. Diethyl ether was removed under vacuum and the intermediate (9) was obtained as yellow liquid (2.89 g, 89 percent). 1 H NMR (DMSO-d6): δ 7.61 (s, 2H), 7.15 (s, 1 H), 6.87 (s, 1 H), 3.93 (t, 2H), 1 .68 (m, 2H), 1 .25 (m, 10H), 0.85 (t, 3H).
87.7%
With sodium hydroxide In dimethyl sulfoxide at 20 - 25℃; Inert atmosphere
To a flask equipped with a stirrer, Add the thermometer to the three necked flask 0 · 440 g (11.0 mmol) of NaOH, 0.714 g (10.5 mmol) of imidazole and 10 mL of dimethylsulfoxide (DMSO) were stirred under nitrogen at 20 ° C to 25 ° C to give a clear solution. To this was added dropwise 1.93 g (10.0 mmol)Bromo octane, reaction 4 ~ 6 h, the reaction into 10 mL of water extracted with chloroform 3 X 10 mL, and then washed with water chloroform layer 4 ~ 5 times, and then dried with anhydrous MgS04, filtered to get the filtrate, Removal of chloroform yielded a pale yellow liquid, 1.58 g of N-octylimidazole, in 87.7percent yield.
85%
With sodium hydroxide In tetrahydrofuran; waterReflux
General procedure: A solution of imidazole 3 (30 mmol) in THF (60 mL) was treated with NaOH (25 mL, 40percent aq) and the alkyl bromide (30 mmol), and the reaction was refluxed overnight. The solvent was evaporated and the crude reaction mixture was extracted with CH2Cl2 against water. The organic layer was washed with water, dried over MgSO4 and concentrated. The final product was distilled under vacuum (~5 mbar) to provide 4 as yellow oily liquid in 80-85percent yield.
82.3%
Stage #1: With potassium hydroxide In dimethyl sulfoxide at 20℃; for 2 h; Stage #2: for 4 h;
General procedure: A mixture of imidazole (30 mmol, 2.04 g), potassiumhydroxide (30 mmol, 1.68 g) and dimethyl sulfoxide(10 mL) was stirred for 2 h at room temperature. Afterthat, alkyl bromide (25.0 mmol of 1-bromohexane, 1-bromooctane,1-bromodecane, 1-bromododecane, 1-bromotetradecane,1-bromohexadecane, or 1-bromooctadecane)was dropped in slowly and the mixture was stirred for anadditional 4 h. Upon completion, water (30 mL) was addedto the resulting mixture followed by extraction with chloroform(5 x 30 mL). The combined organic layer wasdried over anhydrous magnesium sulfate and the filtratewas concentrated under reduced pressure. The residue wassubjected to flash chromatography with ethyl acetate aseluent to give N-alkyl imidazole. The respective yields ofN-hexyl imidazole, N-octyl imidazole, N-decyl imidazole,N-dodecyl imidazole, N-tetradecyl imidazole, N-hexadecylimidazole and N-octadecyl imidazole are 84.6, 82.3, 81.2,80.5, 80.4, 79.8 and 79.6 percent.
60%
Stage #1: With sodium hydride In tetrahydrofuran for 0.75 h; Inert atmosphere; Cooling with ice Stage #2: at 20℃; for 24 h; Inert atmosphere
Imidazole (3.41 g, 50 mmol) and NaH (1.34 g, 54 mmol) were dissolved in THF (10 mL) under N2 in an ice bath for 45 min, followed by addition of 1-bromooctane (9.65 g, 50 mmol). The solution was stirred for 24 h at room temperature and then concentrated under reduced pressure after filtration.The residue was purified by flash chromatography (SiO2; petroleum ether/ethyl acetate5 : 1 as eluent) to give 1 as alight yellow oil (5.97 g, 60 percent). δH (CDCl3, 400 MHz) 7.42 (1H, s), 7.01 (1H, s), 6.87 (1H, s), 3.89 (2H, t, J 8.0), 1.76–1.73 (2H, m), 1.31–1.25 (10H, m), 0.87 (3H, t, J 7.2). δC (CDCl3, 100 MHz) 136.2, 128.4, 118.1, 46.4, 31.2, 30.6, 28.6, 28.5,26.0, 22.1, 13.6. m/z (ESI) 181 ([M + H]+). m/z 181.1708. HRMS (ESI) Anal. Calc. for C11H21N2 ([M + H]+) 181.1705.
Reference：
[1] Synthetic Communications, 1993, vol. 23, # 13, p. 1783 - 1786
[2] Journal of Physical Chemistry B, 2013, vol. 117, # 48, p. 15014 - 15022
[3] ChemMedChem, 2017, vol. 12, # 11, p. 835 - 840
[4] Patent: WO2018/56902, 2018, A1, . Location in patent: Page/Page column 32
[5] Patent: CN103951702, 2016, B, . Location in patent: Paragraph 0039; 0040
[6] Journal of Materials Chemistry, 2011, vol. 21, # 33, p. 12280 - 12287
[7] Carbohydrate Research, 2015, vol. 412, p. 28 - 33
[8] New Journal of Chemistry, 2007, vol. 31, # 6, p. 879 - 892
[9] Journal of Surfactants and Detergents, 2016, vol. 19, # 4, p. 681 - 691
[10] Journal of Molecular Structure, 2004, vol. 697, # 1-3, p. 131 - 135
[11] Applied Organometallic Chemistry, 2017, vol. 31, # 5,
[12] Applied Organometallic Chemistry, 2018, vol. 32, # 2,
[13] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 17, p. 2863 - 2865
[14] Inorganic Chemistry, 2017, vol. 56, # 13, p. 7558 - 7565
[15] Australian Journal of Chemistry, 2015, vol. 68, # 5, p. 825 - 829
[16] Chemistry - A European Journal, 2018, vol. 24, # 50, p. 13322 - 13335
[17] Macromolecules, 2013, vol. 46, # 12, p. 4799 - 4804
[18] Journal of Organometallic Chemistry, 2000, vol. 598, # 2, p. 409 - 416
[19] Chemistry Letters, 2005, vol. 34, # 3, p. 442 - 443
[20] Journal of Chemical and Engineering Data, 2006, vol. 51, # 4, p. 1274 - 1279
[21] Dyes and Pigments, 2013, vol. 96, # 1, p. 16 - 24,9
[22] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 4, p. 423 - 427
[23] Journal of the Chinese Chemical Society, 2013, vol. 60, # 7, p. 745 - 754
[24] Chemical Biology and Drug Design, 2014, vol. 83, # 3, p. 278 - 288
[25] Bulletin of the Korean Chemical Society, 2014, vol. 35, # 6, p. 1675 - 1680
[26] RSC Advances, 2015, vol. 5, # 4, p. 2869 - 2881
[27] RSC Advances, 2015, vol. 5, # 71, p. 57968 - 57974
[28] Journal of Molecular Catalysis A: Chemical, 2016, vol. 411, p. 34 - 39
[29] RSC Advances, 2015, vol. 5, # 28, p. 21865 - 21876
[30] Patent: US2018/255777, 2018, A1, . Location in patent: Paragraph 0047; 0048; 0065
[31] Dalton Transactions, 2018, vol. 47, # 40, p. 14241 - 14253
Reference：
[1] Journal of Organic Chemistry, 2007, vol. 72, # 14, p. 5146 - 5151
[2] Journal of the American Chemical Society, 2000, vol. 122, # 17, p. 4032 - 4038
4
[ 111-83-1 ]
[ 17702-88-4 ]
Reference：
[1] Tetrahedron Letters, 1982, vol. 23, # 41, p. 4255 - 4258
[2] Liebigs Annalen der Chemie, 1990, # 12, p. 1175 - 1183
5
[ 111-83-1 ]
[ 6326-44-9 ]
[ 17702-88-4 ]
Reference：
[1] Nagasaki med.J., 1954, vol. 29, p. 385
6
[ 111-83-1 ]
[ 74-89-5 ]
[ 2439-54-5 ]
Reference：
[1] Journal of the American Chemical Society, 1952, vol. 74, p. 1704,1707
[2] J. Appl. Chem. USSR (Engl. Transl.), 1988, vol. 61, # 10, p. 2171 - 2174[3] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1988, vol. 61, # 10, p. 2365 - 2368
[4] Patent: US4572802, 1986, A,
7
[ 111-83-1 ]
[ 74-89-5 ]
[ 2439-54-5 ]
[ 4455-26-9 ]
Reference：
[1] Journal of the Chemical Society, 1947, p. 201
[2] Journal of the American Chemical Society, 1939, vol. 61, p. 722
[3] Journal of the American Chemical Society, 1939, vol. 61, p. 771
[4] Journal of the Chemical Society, 1947, p. 201
8
[ 111-83-1 ]
[ 28741-08-4 ]
Reference：
[1] Organic Letters, 2011, vol. 13, # 15, p. 3840 - 3843
[2] Angewandte Chemie - International Edition, 2011, vol. 50, # 45, p. 10612 - 10615
9
[ 121-43-7 ]
[ 111-83-1 ]
[ 28741-08-4 ]
Reference：
[1] Chemical Communications, 2016, vol. 52, # 28, p. 4995 - 4998
10
[ 111-83-1 ]
[ 111-42-2 ]
[ 15520-05-5 ]
Yield
Reaction Conditions
Operation in experiment
91%
With potassium carbonate In acetonitrile for 12 h; Inert atmosphere; Reflux
1 -bromooctane (3.0 g, 1.5 mmol), diethanolamine (2.4 g, 2.3 mmol), anhydrous potassium carbonate (4.28 g, 3.1 mmol) were taken in acetonitrile (40 mL) and the contents were refluxed for 12 h nitrogen atmosphere. After cooling reaction mixture was evaporated and extracted with dichloromethane and dried over anhy. Na2S04 removed under reduced pressure to get the crude productwhich was further purified by column chromatography using dichloromethane and methanol as eluentto obtain pure 2,2'-(octylazanediyl)bis(ethan-l-ol) as colorless oil (590 mg, 91 percent).1H NMR (CDC13): δ 4.22 (brs, 2H, OHCH2), 3.86 (t, 4H, JAB = 5 Hz, -CH2OH), 3.10 (t, 4H, JAB = 4.5 Hz, -CH2N), 2.94 (t, 2H, JAB = 8 Hz, -CH2N), 1.69-1.60 (m, 2H, -CH2), 1.30-1.25 (m, 10H, - CH2), 0.87 (t, 3H, JAB = 7 Hz, -CH3).
76.7%
With potassium carbonate; potassium iodide In acetonitrile for 12 h; Inert atmosphere; Reflux
(1) n-octyl bromide (6.0 g, 30 mmol), diethanolamine (4.73 g, 45 mmol),Anhydrous potassium carbonate (8.29 g, 60 mmol) and potassium iodide (1.0 g) were added to a 250 mL two-necked flask, 80 mL of acetonitrile was added and the nitrogen was bubbled through for 5 minutes to replace the air in the system and then refluxed for 12 h.(2) The reaction was stopped, acetonitrile was removed by steaming, 60 mL of dichloromethane and 60 mL of water were added, and the mixture was separated. The organic phase was washed twice with water to remove excess diethanolamine. The product has a certain solubility in water, washed, the water phase and then extracted twice with methylene chloride. The organic phase was separated and dried over anhydrous sodium sulfate.(3) steamed to remove methylene chloride to obtain a light yellow liquid 5.00g, yield 76.7percent JLC detection, ethyl acetate / petroleum ether = 1: 1 as the development agent, the target product than the value of Rf = 0.33 The(4) A 250 mL single-necked flask was charged with (3) the procedure to prepare 5.00 g (23 mmol) of octyldiethanolamine, bromopropyne3.56 g (30 mmo 1) and ethanol 1 OOmL, stirred and refluxed for 12 h under stirring.(5) The excess of bromopropyne and solvent ethanol were distilled off under reduced pressure to give 7.36 g of the crude product as brownish red viscous liquid,100percent. TLC detection, dichloromethane: methanol = 6: 1, the specific value of Rf = 0.50
Reference：
[1] Patent: WO2018/42367, 2018, A2, . Location in patent: Page/Page column 95; 96-97
[2] Molecular Crystals and Liquid Crystals (1969-1991), 1990, vol. 185, p. 131 - 140
[3] Patent: CN106187790, 2016, A, . Location in patent: Paragraph 0044-0050
[4] Patent: US2541088, 1946, ,
[5] European Journal of Medicinal Chemistry, 1976, vol. 11, p. 115 - 124
11
[ 64-17-5 ]
[ 111-83-1 ]
[ 929-61-3 ]
[ 123-29-5 ]
Reference：
[1] Journal of Organic Chemistry, 1991, vol. 56, # 13, p. 4320 - 4322
12
[ 64-17-5 ]
[ 111-83-1 ]
[ 201230-82-2 ]
[ 929-61-3 ]
[ 123-29-5 ]
Reference：
[1] Journal of Organic Chemistry, 1991, vol. 56, # 13, p. 4320 - 4322
13
[ 111-83-1 ]
[ 7795-95-1 ]
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 20, p. 5145 - 5149
[2] Synthesis (Germany), 2015, vol. 47, # 20, p. 3186 - 3190
14
[ 111-83-1 ]
[ 4724-48-5 ]
Yield
Reaction Conditions
Operation in experiment
95.1%
Stage #1: at 20 - 160℃; for 7 h; Stage #2: With hydrogen bromide In water for 5 h; Reflux
2.5 ml of 1-bromooctane was charged at room temperature into a 1000 ml flask, 12.9 g of aluminum trichloride was added, Stir evenly, And then heated to 85 deg C, 1.0 mol of triethyl phosphite was added dropwise, Temperature control between 85 ~ 105 deg C, 3.0h drop finished. After the dropwise addition, Heating up to 160 ° C, Insulation for 4h to continue the reaction. After the reaction, Cooling to 80 deg C, 506.0 g of a 40percent aqueous solution of hydrogen bromide was added dropwise to the reaction system, 60min drop finished. After the dropwise addition, Heated to reflux state, Maintain 4h to react. After the reaction, The aqueous bromine solution was distilled off at 105 ° C under normal pressure, Recovering these aqueous hydrogen bromide solutions; At a vacuum of 2.5 kPa, 90 under the conditions of 1 - bromooctane distillation; Then down to room temperature, A mixed solution of n-hexane and water in a volume ratio of 6: 1 was poured into a reactor, After mixing all into the separatory funnel, Extraction liquid separation; The lower aqueous liquid recovery, The upper oil phase is transferred to the flask, The n-hexane was distilled off at atmospheric pressure at 85 ° C, Recovering these n-hexane, To give 1-octylphosphonic acid; The yield of the reaction was 95.1percent; Sampling analysis, The chromatographic purity of the product was 98.2percent.
Reference：
[1] Patent: CN105153224, 2017, B, . Location in patent: Paragraph 0025; 0026; 0027; 0028; 0029; 0030; 0031-0036
[2] Journal of the American Chemical Society, 1945, vol. 67, p. 1182
[3] Patent: US2397422, 1945, ,
[4] Journal of Organic Chemistry, 1960, vol. 25, p. 1000 - 1006
[5] Patent: JP5664635, 2015, B2,
15
[ 111-83-1 ]
[ 123-08-0 ]
[ 24083-13-4 ]
Yield
Reaction Conditions
Operation in experiment
99%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 24 h;
Take a clean two bottle, add magnet,2.44 g of p-hydroxybenzaldehyde (about 20 mmol),19.31 g of bromooctane (about 100 mmol),13.82g Potassium Carbonate and 50mlThe waterless magnetic stirring,80 °C reaction 24h.After the reaction was completed, water/methylene chloride was extracted several times and the organic phases were combined. After separation by a chromatography column, 4.68 g (approximately 99percent yield) of a pale yellow liquid was obtained.
99%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 24 h;
Take a clean two-neck bottle and add magnets,3.05 g of p-hydroxybenzaldehyde (about 25 mmol),24.14g of bromooctane (about 125mmol),17.25 g of potassium carbonate 20 mL of anhydrous N,N-dimethylformamide solution. The reaction was carried out at 80 ° C for 24 hours under magnetic stirring.After the end of the reaction, the water/dichloromethane was extracted several times and the organic phases were combined. Separation by chromatography gave a pale yellow liquid (yield about 99percent).
95%
With potassium carbonate In acetonitrile at 80℃; for 10 h;
In a 500mL round-bottomed flask were successively added p-hydroxybenzaldehyde (12.5g, 0.1mol), potassium carbonate (16.5g,0.12mol), bromo-n-octane (23.2g, 0.12mol) and 150mL of acetonitrile, magnetic stirring, and the reaction temperature is controlled at80 deg. C for 10h. After completion of the reaction the solid residue was removed by filtration using frit funnel, the solvent was removed, dissolved in dichloromethane, washed with water several of times, the organic layer was dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation, and the residue was subjected to silica gel column chromatography, V (petroleum ether): V (ethyl acetate) = 10: 1 as eluent to give 22.2g of yellow liquid, yield 95percent.
95%
With potassium carbonate In acetonitrile at 80℃; for 10 h;
To a 500 mL round bottom flask was added p-hydroxybenzaldehyde (12.5 g, 0.1 mol) in that order,Potassium carbonate (16.5 g, 0.12 mol),Bromo-n-octane (23.2 g, 0.12 mol) and 150 mL of acetonitrile,Magnetic stirring,The reaction temperature was controlled at 80 ° C for 10 h.The reaction was stopped,The solid residue was removed by filtration through a suction funnel,Spin drying solvent,Diluted with methylene chloride,A lot of washing,And dried over anhydrous magnesium sulfate.The filtrate was collected by filtration,The solvent was removed under reduced pressure,The crude product was purified by column chromatography on silica gel (200-300 mesh) [eluent,V (petroleum ether): V (ethyl acetate) = 10: 1]To give pale yellow liquid intermediate 1 (22.2 g)Yield 95percent.
95%
With potassium carbonate In acetonitrile at 80℃; for 10 h;
Into a 250mL round bottom flask added the p-hydroxy benzaldehyde (12.5 g, 0.1mol), Potassium carbonate (16.5g, 0.12mol), bromooctane (23.2 g, 0.12 mol) and acetonitrile (150mL), with magnetic stirring, the reaction temperature is controlled at 80 ° C for 10 h; stop the reaction, the solid residue is removed by suction filtration funnel, the filtrate is extracted with dichloromethane, saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate is evaporated to remove the solvent by rotary evaporation, the crude product is purified by column chromatography on silica gel (200-300 mesh) [eluent, V (petroleum ether): V (ethyl acetate) = 20: 1] and then obtained light yellow liquid intermediate 1 (22.2 g),yield 95percent.
95%
With potassium carbonate In acetonitrile at 80℃; for 10 h;
P-hydroxybenzaldehyde (12.5 g, 0.1 mol), potassium carbonate (16.5 g, 0.12 mol), bromo-n-octane (23.2 g, 0.12 mol) and acetonitrile (150 ml) were added successively to a 250 ml round bottom flask. The reaction was carried out at 80 ° C for 10 h with magnetic stirring. The reaction was stopped and the solid residue was removed by suction filtration through a suction funnel. The filtrate was extracted with dichloromethane, washed with saturated brine and dried over anhydrous magnesium sulfate. The filtrate was evaporated to remove the solvent by rotary evaporation. The crude product was purified by silica gel (200-300 mesh) column chromatography [eluent, V (petroleum ether): V (ethyl acetate) = 20: 1] to give a pale yellow liquid intermediate 1 (22.2 g), 95percent
95%
With potassium carbonate In acetonitrile at 80℃; for 10 h;
In the 500 ml round-bottom flask was added p-hydroxybenzaldehyde (12.5g, 0.1mol), potassium carbonate (16.5g, 0.12mol), bromo-n-octane (23.2g, 0 . 12mol) and acetonitrile (150 ml), the reaction temperature is controlled at 80 °C magnetic stirring reaction 10h. After the reaction is ended funnel filtration to remove the solid residue of the sand core, the filtrate is extracted with ethyl acetate, saturated salt water washing, drying with anhydrous magnesium sulfate, get the crude product. The crude product using silica gel (200-300 mesh) column chromatography [eluant, V (petroleum ether): V (ethyl acetate) =10:1] yellow liquid intermediates purified to get 1,22.2g, yield 95percent.
91%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 9 h;
General procedure: 4-Hydroxybenzaldehyde (12.5 g, 0.1 mol), potassium carbonate (16.5 g, 0.12 mol) and dimethylformamide (300 mL) were placed in a three-necked 1 L round bottomed flask. The reaction mixture was heated to 80 °C and stirred. To the warm solution the appropriate alkylbromide (19.8 g for 1-bromohexane; 23.2 g for 1-bromooctane; 26.5 g for 1-bromodecane; 29.9 g for 1-bromododecane; 0.12 mol) was added dropwise over 1 h. The mixture was then heated at 80 °C for 8 h. After cooling down to room temperature the mixture was diluted with water (300 mL). The aqueous phase was extracted with dichloromethane (3.x.300 mL). The combined organic layer was washed twice with aq NaOH (10percentmol), water and dried with MgSO4. After evaporation of solvent on a rotary evaporator the corresponding products were obtained as pale yellow oils, which were subsequently used without purification.
86%
Stage #1: With potassium carbonate In N,N-dimethyl-formamide at 25℃; for 0.166667 h; Inert atmosphere Stage #2: at 25℃; Inert atmosphere
Procedure: Potassium carbonate (340 mg, 2.46 mmol, 1.5 eq.) and 4-hydroxybenzaldehyde(compound S5, 200 mg, 1.64 mmol, 1 eq.) were added to an oven-dried round-bottomed flask.This flask was evacuated using three nitrogen-vacuum purge cycles. Dry DMF (50 mL) was addedvia syringe and the reaction mixture stirred for 10 minutes at room temperature. 1-bromooctane(compound S6, 348 mg, 0.311 mL, 1.80 mmol, 1.1 eq.) was added via syringe and the reactionmixture stirred at room temperature for 14 hours under an inert nitrogen atmosphere. The reactionmixture was then diluted with water (100 mL) and extracted with diethyl ether three times (40 mLeach). The combined organic layer was dried over sodium sulfate, filtered, and concentrated ona rotary evaporator. The crude product was purified on a silica plug (eluent: 10percent ethyl acetate inn-hexanes) giving a yellow solid in 86percent yield (332 mg).
80%
Stage #1: With potassium carbonate In acetone at 20℃; for 0.0833333 h; Stage #2: With potassium iodide In acetone for 6 h; Reflux
4-Hydroxybenzaldehyde (0.61 g, 5 mmol) was dissolved in acetone. Potassium carbonate (0.759 g, 5.5 mmol) was added and the resulting mixture was stirred for 5 minutes at room temperature. To the mixture, 1-bromooctane (0.965 g, 5 mmol) and potassium iodide (0.83 g, 5 mmol) were added, followed by refluxing for 6 h. TLC showed the completion of the reaction. Solvent was removed in vacuo and the resulting residue was extracted with ethyl acetate (2 * 10 mL), treated with brine, and dried over sodium sulfate. Flash chromatography using 5percent ethyl acetate in hexane afforded a gummy colorless compound (0.94 g, 80percent). 1H NMR (600 MHz, CDCl3, δ): 9.88 (s, 1H), 7.83 (d, J = 8.7 Hz, 2H), 6.99 (d, J = 8.7 Hz, 2H), 4.04 (t, J = 6.5 Hz, 2H), 1.81 (quin., J1 = 6.6 Hz, J2 = 7.2 Hz, 2H), 1.46 (quin., J1 = 6.8 Hz, J2 = 7.6 Hz, 2H), 1.32 (m, 8H), 0.89 (t, J = 6.8 Hz, 3H).
77%
With potassium hydroxide In ethanol for 96 h; Reflux
General procedure: These compounds were prepared according to the Williamson synthesis of ethers by a known method [22-24]. 4-hydroxybenzaldehyde (8.72 g, 71.5 mmol) was added to a solution of potassium hydroxide (4 g) in ethanol (60 mL). The mixture was treated with n-alkyl halide(71.5 mmol) (methyl iodide was used in the preparation of A1, while n-alkylbromide used inthe preparation of A1-A13) and heated under reflux. The reaction was monitored by thin-layerchromatography (TLC) using chloroform as eluent, and the optimal time of each reaction was determined. The ethanol was evaporated and the residue was dissolved in diethyl ether. The ethereal was washed with an aqueous solution of potassium hydroxide (10percent) followed by water until a pH = 7 was obtained. The organic layer was dried over sodium sulfate anhydrous and evaporated to give the desired product. The details of the reaction conditions for the preparation of each compound are described in Table 1.
72%
Stage #1: With potassium hydroxide In acetonitrile at 20℃; for 1 h; Stage #2: for 4 h; Reflux
General procedure: To 80 mL CH3CN and 4-hydroxybenzaldehyde (42 mmol) wasadded potassium hydroxide (46 mmol). The solution was stirred at room temperature for 1h and then the bromoalkanes (46 mmol) corresponding were added. The reactionmixture was refluxed for 4 h and the precipitate was filtered off. The filtrate wasevaporated in vacuum and purified by distillation under a reduced pressure. All the aldehydes were obtained as pale yellow viscous liquids.
66%
Stage #1: With sodium ethanolate In ethanol at 70℃; for 0.333333 h; Stage #2: at 70℃; for 48 h;
General procedure: 4-Hydroxybenzaldehyde (244 mg, 2 mmol) was added to a solution of 46 mg (2 mmol) of sodium ethoxide in 12 mL of ethanol and stirred until completely consumed. Solution was kept under reflux (70 °C) with magnetic stirring for 20 min. The corresponding alkylation agent (n-alkyl bromide, 2 mmol) was added to the system and the temperature was maintained at 70 °C with stirring for 48 h. Compounds 2a-d were isolated by solvent extraction (ethyl acetate/water, 3:1) and then purified by distillation. Compound 2e was fussily purified by flash chromatography in silica gel (hexane/ethyl acetate; 95:05, Rf 0.4).Compound 2a (73percent yield); IR (NaCl, cm-1): ν 2985, 2935, 2738, 1692, 1260, 1163, 1040, 836; 1H NMR (250 MHz, CDCl3, TMS) δ (ppm): 9.87 (s, 1H), 7.82 (d, 2H, J = 8.9 Hz), 6.98 (d, 2H, J = 8.6 Hz), 4.12 (q, 2H, J = 7.0 Hz), 1.45 (t, 3H, J = 7.0 Hz); EI-MS, m/z 150 [M]+, 121 [HO-C6H4-CO]+, 93 [HO-C6H4]+. Compound 2b (75percent yield); IR (NaCl, cm-1): ν 2967, 2876, 2734, 1692, 1602, 1261, 1160, 834; 1H NMR (250 MHz, CDCl3, TMS) δ (ppm): 9.88 (s, 1H), 7.82 (d, 2H, J = 8.8 Hz), 6.99 (d, 2H, J = 8.8 Hz), 4.00 (t, 2H, J = 6.5 Hz), 1.85 (h, 2H, J = 7.3 Hz), 1.05 (t, 3H, J = 7.5 Hz);EI-MS, m/z 164 [M]+, 121 [HO-C6H4-CO]+, 93 [HO-C6H4]+. Compound 2c (73percent yield); IR (NaCl, cm-1): ν 2964, 2872, 2733, 1692, 1600, 1260, 1158, 828; 1H NMR (250 MHz, CDCl3, TMS) δ (ppm): 9.87 (s, 1H), 7.82 (d, 2H, J = 8.8 Hz), 6.99 (d, 2H, J = 8.7 Hz), 4.04 (t, 2H, J = 6.5 Hz), 1.80 (p, 2H, J = 6.9 Hz), 1.50 (h, 2H, J = 7.5 Hz), 0.99 (t, 3H, J = 7.3 Hz); EI-HRMS, calculated for C11H14O2m/z 178.0994, found: m/z 178.0898 [M]+, 121.0211 [HO-C6H4-CO]+ (calcd 121.0290), 93.0286 [HO-C6H4]+ (calcd 93.0340). Compound 2d (66percent yield); IR (NaCl, cm-1): ν 2931, 2856, 2741, 1697, 1600, 1254, 1156, 832; 1H NMR (250 MHz, CDCl3, TMS) δ (ppm): 9.87 (s, 1H), 7.83 (d, 2H, J = 8.8 Hz), 6.99 (d, 2H, J = 8.7 Hz), 4.03 (t, 2H, J = 6.5 Hz), 1.81 (p, 2H), 1.29-152 (m, 10H), 0.89 (t, 3H, J = 6.6 Hz); EI-MS, m/z 234 [M]+, 121 [HO-C6H4-CO]+, 93 [HO-C6H4]+. Compound 2e (isolated as a white solid, mp 44 °C, in 73percent yield); IR (KBr, cm-1): ν 2913, 2852, 2730, 1691, 1603, 1255, 1174, 837; 1H NMR (250 MHz, CDCl3, TMS) δ (ppm): 9.88 (s, 1H), 7.82 (d, 2H, J = 8.8 Hz), 6.99 (d, 2H, J = 8.8 Hz), 4.03 (t, 2H, J = 6.5 Hz), 1.81 (p, 2H, J = 6.7 Hz), 1.26-1.49 (m, 26H), 0.88 (t, 3H, J = 6.9 Hz); EI-HRMS, calculated for C23H38O2m/z 346.2872, found: m/z 346.2749 [M]+, 121.0077 [HO-C6H4-CO]+ (calcd 121.0290).
6.25 g
With sodium carbonate In ethanolReflux
4 g (33 mmoL) of p-hydroxybenzaldehyde was weighed out of a 250 mL round bottom flask,Dissolved in 50 mL of ethanol,And then added to it8 g of Na2CO3 was stirred. After 5 min, 7.6 g (39 mmol) of bromooctane was added and the mixture was refluxed overnight. The reaction solution was washed with saturated brine and dried over anhydrous sodium sulfate.After filtration, the solvent was removed by distillation under reduced pressure to give 6.25 g of a colorless oily liquid as an intermediate;
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16
[ 111-83-1 ]
[ 88-99-3 ]
[ 117-84-0 ]
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[ 88-99-3 ]
[ 117-84-0 ]
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[ 106-37-6 ]
[ 51554-93-9 ]
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19
[ 111-83-1 ]
[ 19812-93-2 ]
[ 52364-73-5 ]
Yield
Reaction Conditions
Operation in experiment
88%
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 48 h;
General procedure: 4'-Hydroxybiphenyl-4-carbonitrile (1) (20.0 g, 0.1 mol), potassium carbonate (28.0 g, 0.2 mol) and DMF (600 mL) were placed in a 1000 mL flask and stirred. The corresponding alkylbromide (20.0 g for 1-bromohexane, 23.0 g for 1-bromo-octane, 0.12 mol) was added and the reaction mixture was heated at 120 °C for 48 h. The mixture was then cooled to room temperature and poured onto ice water (1000 mL) and left to stand overnight. The precipitated product was isolated by filtration and crystallized from ethanol.
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[2] Chemistry - An Asian Journal, 2014, vol. 9, # 1, p. 104 - 109
23
[ 872-31-1 ]
[ 111-83-1 ]
[ 65016-62-8 ]
Yield
Reaction Conditions
Operation in experiment
68%
Stage #1: With magnesium In diethyl ether for 2 h; Inert atmosphere Stage #2: for 24 h; Cooling with ice
Compound 9 was synthesized from the reported process (Chochos CL, Economopoulos SP, Deimede V, Gregoriou VG, Lloyd MT, Malliaras GG, Kallitsis JK, et al. Synthesis of a soluble n-type cyano substituted polythiophene derivative: solar cells. J Phys Chem C 2007; 111: 10732-40).1-Bromooctane (28.7 mL)Was added dropwise to a solution of magnesium (4.63 g, 193 mmol) in anhydrous diethyl ether (130 mL). The mixture,And stirred in a nitrogen atmosphere for 2 h.The final Grignard reagent was added dropwise to a flask containing 3-bromothiophene (19 g, 116.6 mmol) and Ni (dppp) Cl2 (0.31 g, 0.571 mmol). After stirring and heating for 24 h,Contained in an ice bath,HCl (2N) was extracted with diethyl ether.The organic layer was dehydrated with sodium sulfate,Concentrated by evaporation under reduced pressure and purified by column chromatography with hexane to give a colorless oil (15.54 g, 68percent).
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[ 111-83-1 ]
[ 65016-62-8 ]
[ 161746-06-1 ]
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With n-butyllithium; diisopropylamine In tetrahydrofuran at 0 - 20℃; for 15 h; Inert atmosphere
Diisopropylamine (28.0 mL, 0.160 mol, 2.66 equiv.) was dissolved in dry THF (60 mL) under an argon atmosphere. n-butylithium (107.0 mL, 0.160 mol, 2.66 equiv.) was added dropwise at 0 °C and the solution was stirred for 1 h. Afterwards, a solution of 4,4′-dimethyl-2,2′-bipyridine (11.0 g, 0.060 mol, 1 eq.) in dry THF (300 mL) was slowly added and the orange solution was stirred for 3 h. The reaction mixture was kept at 0 °C and bromooctane (28.0 mL, 0.160 mol, 2.66 equiv.) in dry THF (20 mL) was added. The reaction mixture was then allowed to warm to room temperature. After stirring for 12 h the reaction was quenched first with water (20 mL), then poured into an ice/ water mixture and extracted with diethylether. The resulting yellow oil was recrystallized from hexane, redissolved in DCM, extracted with diluted NaOH, dried over MgSO4, filtered and the solvent removed in vacuo. Drying in high vacuum yielded the desired product (11.02 g, 0.027 mol, 45 percent). 1H NMR (500 MHz, DMSO) δ in ppm= 8.85 (s, 1H), 8.83 (s, 1H), 7.28 (s, 1H), 7.27 (s, 1H), 2.68 (t, J= 7.6 Hz, 4H), 1.62 (p, J= 8.2, 6.9 Hz, 4H), 1.32–1.11 (m, 24H), 0.83 (t, J= 6.5 Hz, 6H). HRMS (ESI) m/z: [M+H]+ calcd. for (C28H44) 409.358; found 409.3581.
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34
[ 111-83-1 ]
[ 128-59-6 ]
[ 85652-50-2 ]
Yield
Reaction Conditions
Operation in experiment
72%
With 18-crown-6 ether; potassium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 8 h;
Taking 1.21g (2.48mmol) 16, 17-dihydroxy Anthracyclinone purple puts in 100 ml flask, add 50mLN-methyl pyrrolidone, heating 10 min to 100 °C the 16, 17-dihydroxy Anthracyclinone purple disperse as much as possible. Then add 1.00g (7.2mmol) no water K2CO3, 0.98g (5.08mmol) 1-polybromide octane, and presence of 18-crown -6. Maintain reaction temperature 100 °C, reaction 8 hours the reaction is stopped.The reaction solution is poured into 100 ml water, fully mixing, filtering, drying to obtain the crude product. Dichloromethane is used for dissolving the crude product, filtering to remove undissolved components. turns on lathe does dichloromethane, to obtain the solid, dried to obtain 1.26g grams of product, yield is 72percent. The silica gel chromatographic column, to CH2Cl2: CH3OH=20 1 as eluant, further elution separation and purification.
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(a) Preparation of N-methyl-N-octyl amine N-methyl-N-octyl amine is prepared in the following way: STR6 405 g of a 37percent methyl amine solution in ethanol and 150 g of n-octyl bromide were introduced into a 1 liter autoclave. The autoclave is heated to 180° C. for 20 hours and then to 200° C. for 8 hours. The crude residue is evaporated to dryness after cooling. Thus, a grey crystalline residue is obtained, which is treated with 300 ml of a 20percent potassium solution. The aqueous phase is extracted with ether, the ethereal phase is dried on magnesium sulphate, followed by filtration and expulsion of the ether. The sought product is then recoered with a good yield by distillation (approximately 70percent). The boiling point is 75° to 78° C., under 13 mmHg.
A mixture of imidazole (1 .36 g, 20.0 mmol) and sodium hydroxide (0.80 g, 20.0 mmol) in DMSO was heated to 90 C for 2 h, and then cooled to room temperature. A solution of 1 -bromooctane (3.46 g, 19.0 mmol) in DMSO was added dropwise to the mixture. After stirring at room temperature for 3 h, the mixture was heated up slowly to 65 C for 16 h with constant stirring. The solution obtained was mixed with water and the product was extracted 4 times with diethyl ether. The diethyl ether phases were combined and dried with sodium sulfate. Diethyl ether was removed under vacuum and the intermediate (9) was obtained as yellow liquid (2.89 g, 89 %). 1 H NMR (DMSO-d6): delta 7.61 (s, 2H), 7.15 (s, 1 H), 6.87 (s, 1 H), 3.93 (t, 2H), 1 .68 (m, 2H), 1 .25 (m, 10H), 0.85 (t, 3H).
87.7%
With sodium hydroxide; In dimethyl sulfoxide; at 20 - 25℃;Inert atmosphere;
To a flask equipped with a stirrer, Add the thermometer to the three necked flask 0 · 440 g (11.0 mmol) of NaOH, 0.714 g (10.5 mmol) of imidazole and 10 mL of dimethylsulfoxide (DMSO) were stirred under nitrogen at 20 C to 25 C to give a clear solution. To this was added dropwise 1.93 g (10.0 mmol)Bromo octane, reaction 4 ~ 6 h, the reaction into 10 mL of water extracted with chloroform 3 X 10 mL, and then washed with water chloroform layer 4 ~ 5 times, and then dried with anhydrous MgS04, filtered to get the filtrate, Removal of chloroform yielded a pale yellow liquid, 1.58 g of N-octylimidazole, in 87.7% yield.
85%
With sodium hydroxide; In tetrahydrofuran; water;Reflux;
General procedure: A solution of imidazole 3 (30 mmol) in THF (60 mL) was treated with NaOH (25 mL, 40% aq) and the alkyl bromide (30 mmol), and the reaction was refluxed overnight. The solvent was evaporated and the crude reaction mixture was extracted with CH2Cl2 against water. The organic layer was washed with water, dried over MgSO4 and concentrated. The final product was distilled under vacuum (~5 mbar) to provide 4 as yellow oily liquid in 80-85% yield.
82.3%
General procedure: A mixture of imidazole (30 mmol, 2.04 g), potassiumhydroxide (30 mmol, 1.68 g) and dimethyl sulfoxide(10 mL) was stirred for 2 h at room temperature. Afterthat, alkyl bromide (25.0 mmol of 1-bromohexane, 1-bromooctane,1-bromodecane, 1-bromododecane, 1-bromotetradecane,1-bromohexadecane, or 1-bromooctadecane)was dropped in slowly and the mixture was stirred for anadditional 4 h. Upon completion, water (30 mL) was addedto the resulting mixture followed by extraction with chloroform(5 x 30 mL). The combined organic layer wasdried over anhydrous magnesium sulfate and the filtratewas concentrated under reduced pressure. The residue wassubjected to flash chromatography with ethyl acetate aseluent to give N-alkyl imidazole. The respective yields ofN-hexyl imidazole, N-octyl imidazole, N-decyl imidazole,N-dodecyl imidazole, N-tetradecyl imidazole, N-hexadecylimidazole and N-octadecyl imidazole are 84.6, 82.3, 81.2,80.5, 80.4, 79.8 and 79.6 %.
60%
Imidazole (3.41 g, 50 mmol) and NaH (1.34 g, 54 mmol) were dissolved in THF (10 mL) under N2 in an ice bath for 45 min, followed by addition of 1-bromooctane (9.65 g, 50 mmol). The solution was stirred for 24 h at room temperature and then concentrated under reduced pressure after filtration.The residue was purified by flash chromatography (SiO2; petroleum ether/ethyl acetate5 : 1 as eluent) to give 1 as alight yellow oil (5.97 g, 60 %). deltaH (CDCl3, 400 MHz) 7.42 (1H, s), 7.01 (1H, s), 6.87 (1H, s), 3.89 (2H, t, J 8.0), 1.76-1.73 (2H, m), 1.31-1.25 (10H, m), 0.87 (3H, t, J 7.2). deltaC (CDCl3, 100 MHz) 136.2, 128.4, 118.1, 46.4, 31.2, 30.6, 28.6, 28.5,26.0, 22.1, 13.6. m/z (ESI) 181 ([M + H]+). m/z 181.1708. HRMS (ESI) Anal. Calc. for C11H21N2 ([M + H]+) 181.1705.
General procedure: These compoundswere obtained fromthe reaction of the sodium salt of imidazole and 1-bromoalkanes, as follows: to a 3-necked round-bottom flask, provided with a reflux condenser, dropping funnel, and inlet for dry nitrogen was added a solution of imidazole (7.49 g; 0.11 mol) in dry ethanol (25 mL). Small pieces of sodium (2.53 g, 0.11 mol), were slowly introduced, the mixture was vigorously stirred until the metal has dissolved and then heated under reflux for 2 h. The mixture was cooled to room temperature; the appropriate 1-bromoalkane (0.10 mol; 16.50 g, 17.91 g, 19.31 g, 22.12 g for R ¼ C6; C7; C8 and C10, respectively)was added slowly (ca. 30 min); then the mixture was refluxed for 2 h. The mixture was cooled to room temperature, the precipitated NaBr was filtered off; the ethanol evaporated, the residual oilwas washed with water, and then dried with anhydrous MgSO4. The N-(1-alkyl)imidazoles were purified by fractional distillation (yields before distillation ca. 98%); their purity was confirmed with 1H NMR spectroscopy (results not shown).
General procedure: N-Hexadecylbromide (11.35 g, 37.2 mmol) was dissolved in dimethylformamide (DMF, 50 mL) and then added to a solution of the sodium salt of imidazole, which was formed by the reaction of imidazole (5.0 g, 74 mmol) with sodium hydride (2.66 g, 111 mmol) in DMF (50 mL). The mixture was heated at 60 C for 6 h, cooled, and diluted with water. After extraction with ethyl acetate (EtOAc), the extract was washed with brine and water, and then dried with sodium sulfate. The solvent was separated by reduced pressure distillation and N-alkylimidazole was obtained as a pale yellow oily product.
With potassium hydroxide; In acetonitrile; for 4h;Reflux;
General procedure: N-Butylimidazole and N-octylimidazole were synthesized fol-lowing the procedure of literature [44]: To a round-bottomedflask, imidazole (6.0 g, 88 mmol), 1-bromobutane/1-bromooctane(90 mmol), acetonitrile (50 mL) and potassium hydroxide (9.9 g,177 mmol), were added in sequence. The reaction mixture wasrefluxed for 4 h and then cooled down to room temperature. Afterevaporating the solvent, the residue was purified by a flash col-umn chromatography utilizing ethyl acetate/methanol (v/v = 25:1)as eluent. The pure product of 1-butylimidazole/1-octylimidazolewas isolated as a pale yellow oil (?83%). N-Octylimidazole:1H NMR: (CDCl3): (ppm) = 0.87 (t, J = 6.5 Hz,3H, CH3), 1.28 (br, 10H, CH2), 1.77 (br, 2H, CH2), 3.92 (t, J = 7.2 Hz,2H, CH2), 6.90 (s, 1H, ImH), 7.04 (s, 1H, ImH), 7.45 (s, 1H, ImH).13CNMR (CDCl3): (ppm) = 13.9, 22.5, 26.4, 28.9, 29.0, 31.0, 31.6, 46.9,118.7, 129.2, 136.9.
With sodium hydroxide; In acetone; at 20℃; for 12h;
N-alkylimidazoles were synthesized using a previously reported method with minor modification. Typically, to a solution of imidazole (1 mol equiv.) and sodium hydroxide (1 mol equiv.) in acetone (50 mE) was added 1 -bromoalkane (0.8 mol equiv.). After stirring at room temperature for 12 h, a Nal3r precipitate was filtered and acetone removed under reduced pressure. A residual oily mass was re-dissolved in dichloromethane and extracted three times with water. Finally, an organic phase was dried on anhydrous sodium sulfate and dicholoromethane was removed under reduced pressure to produce brown oil.
a) alpha-n-octyl-2,4-dichlorobenzyl cyanide Sodium hydride (0.13 moles as a 50% dispersion in mineral oil) is washed with 100 mil. of dry n-hexane to remove the mineral oil, then blanketed with dry nitrogen and suspended in 250 ml. of freshly distilled tetrahydrofuran. To this sodium hydride suspension is added dropwise at room temperature, a solution of 2,4-dichlorobenzyl cyanide (25g., 0.13 mole) dissolved in 100 ml. of tetrahydrofuran. When the addition is completed the temperature is maintained at 30 C. for an additional 0.5 hours. A solution of n-octylbromide (27g., 0.14 mole) is then added dropwise and the resultant reaction mixture is stirred at 40 C. overnight under nitrogen. The reaction mixture is poured into 1 liter of water and extracted with (3 * 200 ml.) of ether. The combined ether extracts are washed, with water, dilute hydrochloric acid, saturated sodium, bicarbonate solution saturated sodium chloride solution,d and dried over magnesium sulfate. The solvent is evaporated to give 39.8g. (100%) of product.
In tetrahydrofuran; hexane; water; mineral oil;
(a) alpha-n-octyl-2,4-dichlorobenzyl cyanide Sodium hydride (0.13 moles as a 50% dispersion in mineral oil) is washed with 100 ml. of dry n-hexane to remove the mineral oil, then blanketed with dry nitrogen and suspended in 250 ml. of freshly distilled tetrahydrofuran. To this sodium hydride suspension is added dropwise at room temperature, a solution of 2,4-dichlorobenzyl cyanide (25 g., 0.13 mole) dissolved in 100 ml. of tetrahydrofuran. When the addition is completed the temperature is maintained at 30 C. for an additional 0.5 hours. A solution of n-octylbromide (27 g., 0.14 mole) is then added dropwise and the resultant reaction mixture is stirred at 40 C. overnight under nitrogen. The reaction mixture is poured into 1 liter of water and extracted with (3*200 ml.) of ether. The combined ether extracts are washed, with water, dilute hydrochloric acid, saturated sodium, bicarbonate solution saturated sodium chloride solution, and dried over magnesium sulfate. The solvent is evaporated to give 39.8 g. (100%) of product.
General procedure: Synthesis was carried out using modified procedure [20]. Undernitrogen atmosphere a solution LDA (4.075 ml, 8.1 mmol), waschilled to a preset temperature of -75 C. This solution was stirredfor 15 min. A solution of 4,4'-dimethyl-2,2'-bipyridine (0.5 g,2.7 mmol in 10 ml THF) was added drop wise to LDA solution.The mixture was further magnetically stirred for another 90 minutes.A solution of 1-bromoalkane (5.9 mmol, 0.80 g for C5, 0.89 gfor C6, 0.97 for C7, 1.06 for C8, 1.11 g for C9) in 10 ml of THF wasadded drop wise to the reaction mixture. The resultant magneticallystirred reaction mixture was kept for 30 minutes at -75 Cand further slowly heated to temperature 26 C under nitrogenatmosphere. The yellow coloured solution after 12 h was pouredin 100 ml of millipore water and the organic layer was extractedin ethyl acetate and dried over anhydrous sodium sulphate. Theproduct was purified using column chromatography with ethylacetate in petroleum-ether. The yellow fraction was collected at10% ethyl acetate in petroleum ether and the solvent was reducedby rotary evaporator. The resulting off-white crystalline productwas recrystallized in petroleum ether subsequently and dried invacuum (Scheme 1).
45%
With n-butyllithium; diisopropylamine; In tetrahydrofuran; at 0 - 20℃; for 15h;Inert atmosphere;
Diisopropylamine (28.0 mL, 0.160 mol, 2.66 equiv.) was dissolved in dry THF (60 mL) under an argon atmosphere. n-butylithium (107.0 mL, 0.160 mol, 2.66 equiv.) was added dropwise at 0 C and the solution was stirred for 1 h. Afterwards, a solution of 4,4?-dimethyl-2,2?-bipyridine (11.0 g, 0.060 mol, 1 eq.) in dry THF (300 mL) was slowly added and the orange solution was stirred for 3 h. The reaction mixture was kept at 0 C and bromooctane (28.0 mL, 0.160 mol, 2.66 equiv.) in dry THF (20 mL) was added. The reaction mixture was then allowed to warm to room temperature. After stirring for 12 h the reaction was quenched first with water (20 mL), then poured into an ice/ water mixture and extracted with diethylether. The resulting yellow oil was recrystallized from hexane, redissolved in DCM, extracted with diluted NaOH, dried over MgSO4, filtered and the solvent removed in vacuo. Drying in high vacuum yielded the desired product (11.02 g, 0.027 mol, 45 %). 1H NMR (500 MHz, DMSO) delta in ppm= 8.85 (s, 1H), 8.83 (s, 1H), 7.28 (s, 1H), 7.27 (s, 1H), 2.68 (t, J= 7.6 Hz, 4H), 1.62 (p, J= 8.2, 6.9 Hz, 4H), 1.32-1.11 (m, 24H), 0.83 (t, J= 6.5 Hz, 6H). HRMS (ESI) m/z: [M+H]+ calcd. for (C28H44) 409.358; found 409.3581.
Four-necked flask, compound 1 (2.674g, 15.00mmol), bromo-octane (6.083g, 31.50mmol), potassium iodide (62.25mg, 2.5mol%), dimethyl sulfoxide (50mL) in addition, it was carried out for 30 minutes argon bubbling at room temperature (25C ). After cooling to 0C using an ice bath, potassium hydroxide (2.525g, 45.00mmol) was added, and the reaction was allowed to proceed for 6 days. The reaction solution was analyzed by liquid chromatography (HPLC), to confirm the disappearance of the raw materials. Thereafter, pure water was added to the reaction solution, was extracted the organic layer with hexane. Then, Exhibition It performs separation of the organic layer at column using hexane open solvent, drying of the component obtained by separating By causing to give Compound 2 4.11 g.
N-(1-octyl-4(1H)-pyridinylidene)octanamine monohydrobromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83%
In tetrahydrofuran; ether-tetrahydrofuran;
A. A mixture of <strong>[64690-19-3]4-octylaminopyridine</strong> (10 g., 0.048 mole) and octyl bromide (8 ml., 0.048 mole) was heated at 125 C. for 8 hr. on one day and for 4 more hr. on the next day. The resulting solid was slurried, first in ether, then in ether-tetrahydrofuran (2:1) and finally in tetrahydrofuran, collected by filtration, washed with ether on the filter, and dried (70 C., 0.1 mm.) affording N-(1-octyl-4(1H)-pyridinylidene)octanamine monohydrobromide (11.95 g., 83% yield, m.r. 108-112 C.), which is the monohydrobromide salt of the compound of Formula I wherein both R and R' are octyl.
1-[2,4-dichloro-beta-(2,4-dichlorobenzyloxy)phenethyl]3-n-octylimidazolium bromide; mp. 141.5°-143° C., from 1-[2,4dichloro-beta-(2,4-dichlorobenzyloxy)phenethyl]imidazole and n-octyl bromide after an overnight reflux.
With sodium hydroxide; In hexane; water; dimethyl sulfoxide;
1) 80 ml of dimethylsulfoxide, into which 22.0 g of <strong>[2713-28-2]o-fluoro-p-iodophenol</strong> had been dissolved, was added with sodium hydroxide solution in water (sodium hydroxide 7.4 g and water 30 ml) and stirred into a homogeneous state. The mixture was added with 21.2 g of n-octylbromide and stirred for 4 days at room temperature. The reactant was poured into ice water and then subjected to extraction using hexane. The resulted hexane layer was washed with water thrice and hexane was removed therefrom, then 25.0 g of oily p-n-octyloxy-m-fluoroiodobenzene was finally yielded.
2) To 700 g of <strong>[144292-32-0]2,3-<strong>[144292-32-0]difluoro-4-bromophenol</strong></strong> dissolved in 50 ml DMSO, were added 1.47 g of sodium hydroxide and 6.34 g of n-octylbromide, and stirred for 7 days at room temperature. The resulting reaction product was extracted with hexane and then washed with water, followed by distilling off hexane to obtain 9.45 g of oily 2,3-difluoro-4-bromooctyloxybenzene.
38.7 g (152 mmol) of indenofluorene are dissolved in 600 ml of dried DMSO in a flask which has been dried by heating. 87.8 g (914 mmol) of NaOtBu are added at room temperature. The suspension, which is now blue, is brought to an internal temperature of 80 C. At this temperature, 158 ml (914 mmol) of 1-octyl bromide are added dropwise to the solution, which is now violet, at such a rate that the internal temperature does not exceed 90 C. (duration: about 30 minutes). The batch is held at an internal temperature of 80 to 90 C. for a further 30 minutes, then poured into 1500 ml of ice-water and stirred for about 20 minutes. The precipitated solid is filtered off with suction and washed successively with about 200 ml of H2O and methanol. The yield is 104.9 g (98%) with an HPLC purity of 99.5%.
98%
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 1 being maintained and the results shown in the table being obtained.
84%
With n-butyllithium; In tetrahydrofuran; at -75 - 20℃;Product distribution / selectivity;
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 2 being maintained and the results shown in the table being obtained.
84%
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 1 being maintained and the results shown in the table being obtained.
84%
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 1 being maintained and the results shown in the table being obtained.
60%
With sodium hydride; In dimethyl sulfoxide; at 90℃; for 96h;Product distribution / selectivity;
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 2 being maintained and the results shown in the table being obtained.
25%
With sodium hydroxide; tetrabutylammomium bromide; In water; at 90℃; for 96h;Product distribution / selectivity;
The preparation is carried out analogously to Example 1, with the reaction conditions shown in Table 2 being maintained and the results shown in the table being obtained.
With N,N,N,N,-tetramethylethylenediamine; di-tert-butyl[dichloro({di-tert-butyl[4-(dimethylamino)phenyl]phosphaniumyl})palladio][4-(dimethylamino)phenyl]phosphanium; zinc; In water; at 20℃; for 48h;Inert atmosphere;
General procedure: In a 5 mL round-bottom flask under argon containing zinc powder (197 mg, 3 mmol) and PdCl2(Amphos)2 (7 mg, 0.01 mmol) was added 2% PTS solution in water (1.5 mL). N,N,N',N'-Tetramethylethylenediamine (TMEDA, 232 mg, 2 mmol) was added at rt followed by the addition of the alkyl halide (2 mmol) and the heteroaromatic halide (0.5 mmol). The flask was stirred vigorously at rt for the indicated time. The product was extracted with EtOAc.11 Silica gel (1 g) was added to the combined organic phase and solvents were removed under vacuum. The resulting dry, crude silica was introduced on top of a silica gel chromatography column to purify the product.
With N,N,N,N,-tetramethylethylenediamine; di-tert-butyl[dichloro({di-tert-butyl[4-(dimethylamino)phenyl]phosphaniumyl})palladio][4-(dimethylamino)phenyl]phosphanium; zinc; In water; at 20℃; for 48h;Inert atmosphere;
General procedure: In a 5 mL round-bottom flask under argon containing zinc powder (197 mg, 3 mmol) and PdCl2(Amphos)2 (7 mg, 0.01 mmol) was added 2% PTS solution in water (1.5 mL). N,N,N',N'-Tetramethylethylenediamine (TMEDA, 232 mg, 2 mmol) was added at rt followed by the addition of the alkyl halide (2 mmol) and the heteroaromatic halide (0.5 mmol). The flask was stirred vigorously at rt for the indicated time. The product was extracted with EtOAc.11 Silica gel (1 g) was added to the combined organic phase and solvents were removed under vacuum. The resulting dry, crude silica was introduced on top of a silica gel chromatography column to purify the product.
General procedure: NaH (60% oil, 0.8 g, 0.02 mol) was suspended to a solution of intermediate 13 (0.16 g, 0.01 mol) in DMF (10 mL), and the mixture was stirred at room temperature for 2 h. Then, 1-bromohexane (0.17 g, 0.01 mol) was added, the resulting mixture was heated to 80 C and stirred for 9 h. After filtration, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (hexane: EtOAc = 4:1, v/v) to give 14a as white solid (0.18 g, yield 75.0%).
1,1'-(2-(2,4-difluorophenyl)-2-hydroxypropane-1,3-diyl)bis(4-octyl-1H-1,2,4-triazol-4-ium) bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78.5%
In acetonitrile; at 80℃;
General procedure: To a solution of compound 6 (0.12 g, 0.4 mmol) in acetonitrile (10 mL) was added 1-butyl bromide (0.14 g, 1.0 mmol), 1-octyl bromide (0.19 g, 1.0 mmol), 1-dodecyl bromide (0.25 g, 1.0 mmol), or 1-hexadecyl bromide (0.30 g, 1.0 mmol) respectively. The mixture was stirred at 80 C. After the reaction came to the end (monitored by TLC, eluent, methanol/aqueous ammonia, 10/1, V/V), the solvent was evaporated under reduced pressure. The residue was washed three times with petroleum ether and dried in vacuum to give alkyl fluconazoliums 10a-d.
With 18-crown-6 ether; potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 100℃; for 8.0h;
Taking 1.21g (2.48mmol) 16, 17-dihydroxy Anthracyclinone purple puts in 100 ml flask, add 50mLN-methyl pyrrolidone, heating 10 min to 100 C the 16, 17-dihydroxy Anthracyclinone purple disperse as much as possible. Then add 1.00g (7.2mmol) no water K2CO3, 0.98g (5.08mmol) 1-polybromide octane, and presence of 18-crown -6. Maintain reaction temperature 100 C, reaction 8 hours the reaction is stopped.The reaction solution is poured into 100 ml water, fully mixing, filtering, drying to obtain the crude product. Dichloromethane is used for dissolving the crude product, filtering to remove undissolved components. turns on lathe does dichloromethane, to obtain the solid, dried to obtain 1.26g grams of product, yield is 72%. The silica gel chromatographic column, to CH2Cl2: CH3OH=20 1 as eluant, further elution separation and purification.
A mixture of <strong>[16292-17-4]bis(4-bromophenyl)amine</strong>) (4.90?g, 15.0?mmol), potassium tert-butoxide (2.02?g, 18.0?mmol) and 120?mL of anhydrous THF was stirred for 30?min at room temperature under a nitrogen atmosphere. 1-Bromooctane (63.47g, 18.0?mmol) was added and the mixture was stirred for 24?h at 60?C. After cooling to room temperature, the reaction mixture was poured into water and then extracted with dichloromethane. The combined organic layers were washed with water several times and dried over anhydrous MgSO4. The crude product was purified by column chromatography (hexane/DCM) 7:3, v/v) to give a colorless oil (5.25?g, 80%). 1H NMR (600?MHz, CDCl3): delta 7.37 (d, J?=?8.4?Hz, 4H), 6.87 (d, J?=?8.4?Hz, 4H), 3.64 (m, 2H), 1.65 (m, 2H), 1.32-1.27 (m, 10H), 0.87 (t, J?=?7.2?Hz, 3H). 13C NMR (150?MHz, CDCl3, delta): 146.77, 132.27, 122.57, 113.86, 52.45, 31.78, 29.35, 29.25, 27.26, 27.01, 22.62, 14.08. HR-MS (EI, [M]+): calculated for [C20H25Br2N]+: m/z 437.0354, found m/z 437.0352.
General procedure: Constant current electrolyses (I = 25 mA cm-2) were performed under a nitrogen atmosphere, at 20C, using an Amel Model 552 potentiostat equipped with an AmelModel 731 integrator. All the experiments were carried out in a divided glass cell separated through a porous glass plug filled up with a layer of gel (i.e., methylcellulose 0.5% vol dissolved in DMF-Et4NPF6 1.0 mol dm-3); Pt spirals (apparent areas 0.8 cm2) were used both as cathode and anode. MeCN-Et4NPF6 0.1 mol dm-3 was used as solvent-supporting electrolyte system (catholite: 20 cm3; anolite: 5 cm3).1 mmol of substrate was present in the catholyte (except for D-<strong>[68-41-7]cycloserine</strong>, which was added to the catholyte after the end of the electrolysis). After 145 C (if not otherwise stated) were passed, the current was switched off and 1 mmol of alkylating agent was added to the catholyte. The solution was kept under stirring at room temperature for 2 hours, than the solvent was evaporated under reduced pressure and the residue was extracted three times with diethyl ether. The products were purified by flash column chromatography, using a mixture of ethyl acetate/light petroleum ether 2/8 in volume. The reactions on D-<strong>[68-41-7]cycloserine</strong> were carried out following the general method, but the substrate was added to the catholyte after the end of the electrolysis. After 15 minutes at room temperature, the alkylating agent was added and the solution was kept under stirring at rt for 2 hours. The solvent was evaporated under reduced pressure and the residue was treated with 1 cm3 of saturated acqueous NaHCO3 and 1 mmol of ethyl chloroformate, at 0C, for 2 h. The solution was then acidified with diluted HCl (pH 4) and extracted with diethyl ether. The products were purified by flash column chromatography.
5,12-dihydroquino<2,3-b>acridine-7,14-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Ca. 85%
With tetrabutylammomium bromide; caesium carbonate; In dimethyl sulfoxide; at 25℃; for 4h;
To a 100 mL single-necked flask was added quinacridone (1.5616 g, 5 mmol), tetrabutylammonium bromide (TBAB) (0.323 mg, 1 mmol), cesium carbonate (0.326, 10 mol) and 30 mL of dimethylsulfoxide (DMSO) as solvent. At room temperature (25 ) Was added for 4 h, followed by addition of 1-bromooctane (3.863 g, 20 mmol) followed by TLC monitoring until quinacridone disappeared Should be complete. Stop the reaction, the reaction solution into the saturated salt water to precipitate solid, filter, filter cake washed in methylene chloride, The unreacted starting material was removed by filtration, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column to give a red solid of (III)The yield of the compound is about 85% by volume of the compound.
82%
5,12-Dihydroquino[2,3-b]acridine-7,14-dione (1.562 g, 5 mmol),tetrabutyl-ammonium bromide (TBAB) (0.323 mg, 1 mmol), andcesium carbonate (0.326, 10 mol) were dissolved in 30 mL DMSO,stirring for 4 h at room temperature, n-octyl bromide (3.863 g,20 mmol) were added slowly. After stirring for 24 h, the reactionwas quenched with water (50 mL) and filtered. The mixture wasdissolved in 20mL CH2Cl2 and filtered, then dried over Mg2SO4. Thesolventwas removed by rotary evaporation, and the resulting crudeproduct was purified by column chromatography eluting withCH2Cl2 yielding the product QA as red solid (2.2 g, 82%), m.p.187-188 C. 1H NMR (500 MHz, CDCl3)delta 8.69 (s, 2H), 8.52 (dd,J = 8.0, 1.6 Hz, 2H), 7.70 (m, J =8.6, 6.9, 1.6 Hz, 2H), 7.46 (d, J =8.8Hz, 2H), 7.22 (t, J =7.4 Hz, 2H), 4.61-4.27 (t, 4H), 2.07-1.88 (m, 4H),1.62 (m, J =15.4, 7.6 Hz, 4H), 1.47 (m, J =15.2, 6.9 Hz, 4H), 1.42-1.26(m, 12H), 0.91 (t, J =6.9 Hz, 6H).
With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 24h;
General procedure: To a solution of compound 1 (4.0 g, 14.6 mmol) and 1-Bromobutane (8 mL) in DMF (40 mL), anhydrous potassium carbonate (4.0 g, 28.9 mmol) was added. The mixture was allowed to stir at 100 C for 24 h and then poured into water. The organic phase was extracted by AcOEt, washed with brine and dried over MgSO4. After removal of the solvent under reduced pressure, the crude product was purified by silica chromatography, eluting with (AcOEt: Petroleum ether = 1:10) to give 2R1 as a yellow powder in 71.8% yield (3.46 g, 10.5 mmol).
7-(octyloxy)-4-(trifluoromethyl)-coumarin[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
98%
General procedure: To around bottomed flask equipped with a magnetic stir bar were added, the7-hydroxycoumarin substrate (1 equiv.), acetone (25 mL/mmol of substrate), and K2CO3 (3 equiv.). The solution wasstirred for 5 minutes at room temperature followed by addition of R3-X (1 equiv.; R3 = alkyl, X = Br or OTs.). The reaction mixture was placed under anArgon atmosphere (balloon) and stirred at reflux temperature for 16 hours atwhich point complete consumption of substrate was observed by TLC in all cases. The reaction was cooled to r.t., poured intowater, and extracted with EtOAc (x 3). The combined extracts were dried over MgSO4. The solvent was removed in vacuo and theremaining residue purified via flash chromatography over silica gel using gradient elution with EtOAc and Hexanes to yield Compounds 18-28.
7-(octyloxy)-3,4-dihydroisoquinolin-1(2H)-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With sodium hydroxide; In ethanol;Reflux;
General procedure: A solution of compound 6 (2.0 g, 12.3 mmol), alkyl bromide, or benzyl chloride derivatives(14.7 mmol), NaOH (0.5 g, 12.3 mol), and absolute ethanol (30 mL) were added to a round-bottomedflask, refluxed for 4-6 h. After the 2/3 solvent was removed, the residual solution was poured intoice-cold water. The residue was isolated and recrystallized in ethanol.
1-(4-(1-octyl-1H-tetrazol-5-yl)phenyl)ethan-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With potassium carbonate; In N,N-dimethyl-formamide; for 10.0h;Reflux;
Amixture of 1-(4-(1H-tetrazol-5-yl)phenyl)etan-1-on (1.00 g,5.32 mmol), anhydrous K2CO3 (0.88 g, 6.38 mmol) and 1-bromooctane(1.22 g, 6.38 mmol) and in 30 mL DMF was refluxed for 10 hand the reaction completion was checked by TLC. After refluxing,the reaction mixture was cooled to room temperature and evaporatedunder reduced pressure. The residue product was extractedwith ethyl acetate-water (30:10 mL). The organic layer was driedover Na2SO4 and the solvent evaporated. The product purified byCC (hexane/EtOAc, 6:1), yield 81%.
ethyl 2-(1-octyl-1H-tetrazol-5-yl)acetate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With potassium carbonate; In N,N-dimethyl-formamide; for 10h;Reflux;
A mixture of ethyl 2-(1H-tetrazol-5-yl)acetate (F1-2) (1.00 g,6.41 mmol), anhydrous K2CO3 (1.06 g, 7.69 mmol) and 1-bromooctane (1.48 g, 7.69 mmol) in 30 mL DMF was refluxed for 10 h and the reaction completion was checked by TLC. After refluxing, the reaction mixture was cooled to room temperature and evaporated under reduced pressure. The residue product was extracted with ethyl acetate-water (30:10 mL). The organic layer was dried over Na2SO4 and the solvent evaporated. The product purified by CC (hexane/EtOAc, 6:1). Yield 60%, yellow liquid.
With sodium hydride; In N,N-dimethyl-formamide; at 20℃;
General procedure: A mixture of <strong>[181950-57-2]4-chloroquinolin-7-ol</strong> 8 (0.72g, 4mmol) and anhydrous DMF (10mL) was stirred at room temperature until clear, and then, 60% NaH (0.4g, 10mmol) and halogenated alkane (20-30mmol) were added. The mixture was stirred at room temperature. After completion of the reaction as indicated by TLC, the solution was poured into H2O (100mL) and extracted with ethyl acetate. The organic phase was made acidic with concentrated hydrochloric acid. Upon removal of solvent, the residue was crystallized from acetone to afford a yellow solid. The solid was dissolved in water and made basic with sodium bicarbonate, and the aqueous mixture was extracted with ethyl acetate. The organic phase was washed with water and brine and then dried over anhydrous sodium sulfate, filtered and evaporated. The resulting oil was purified by column chromatography using a mixture of dichloromethane and methanol 100:1 as the eluent to successfully afford the target products 9a-k in good yield.
With potassium carbonate; In N,N-dimethyl-formamide; at 90℃;
Add 0.8 g of <strong>[5369-19-7]3-tert-butylaniline</strong> to a 100 mL reaction flask.2 mL bromo-n-octane,1.85 g potassium carbonate,8 mL of dimethylformamide,Stir,Heat to 90 ° C reaction,TLC tracking,The developing solvent was: petroleum ether: ethyl acetate = 90:10.After the reaction is completed, it is cooled to room temperature.Pour into 200 mL of clean water,Extracted with ethyl acetate twice,100 mL each time,The ethyl acetate layer was combined, washed with 50 mL of saturated brine, dried over anhydrous sodium sulfate for 30 min, filtered, and the filtrate was evaporated to dryness and purified by silica gel eluting with petroleum ether: ethyl acetate = 95:5. Dry to give product 1.3 g of intermediate I.
Add 2.2g to 50mL DMF solvent<strong>[1583-66-0]5-fluoroisophthalic acid</strong> (0.012 mol) and 4.8 g potassium bicarbonate(0.048 mol), stirred at room temperature to form a potassium salt.5.79 g of n-bromooctane (0.03 mol) was added to the mixed solution,The reaction was stirred at 90 C for 12 hours. Stop the reaction and allow the solution to cool to room temperature.It was poured into 300 mL of water and extracted with ethyl acetate.Dry over anhydrous sodium sulfate, filter and then dry the solvent.Petroleum ether/ethyl acetate (20/1) for crude productsColumn chromatography for the eluent.
To 50 mL of DMF solvent, 3 g of <strong>[23351-91-9]5-bromoisophthalic acid</strong> (0.012 mol) and 4.8 g of potassium hydrogencarbonate (0.048 mol) were added, and stirred at room temperature to form a potassium salt.5.79 g of n-bromooctane (0.03 mol) was added to the mixed solution,The reaction was stirred at 90 C for 12 hours. Stop the reaction and allow the solution to cool to room temperature.It was poured into 300 mL of water and extracted with ethyl acetate.Dry over anhydrous sodium sulfate, filter and spin dry solvent.The crude product was subjected to column chromatography using petroleum ether / ethyl acetate (15/1) as eluent to afford white solid.
(1) 0.5 g of <strong>[41037-28-9]6-bromo-4-methylquinoline</strong> was weighed into a 50 ml flask, and 20 ml of dry acetonitrile was added. After the dissolution, 0.5 g of bromooctane was added, and the mixture was reacted under reflux at 70 C for 6 hours. After completion of the reaction, most of the acetonitrile was removed under reduced pressure and the product was poured into anhydrous diethyl ether. After suction filtration, the filter cake was washed three times with anhydrous diethyl ether to give a pure product quinoline compound with a yield of 92%.
2.1 g of 2,7-dihydroxy-9H-indol-9-one (Compound 1) was mixed with 60 ml of DMF, and then 3 g of anhydrous potassium carbonate was added. The mixture was heated at 110 C for 1 hour.Then 5.8 g of 1-bromooctane was added dropwise.The mixture was heated at 110 C for 24 hours.The reaction product was cooled to room temperature and filtered.Extract with dichloromethane and wash several times with water.Drying over anhydrous magnesium sulfate then evaporating the solvent from a rotary evaporator afforded a red solid.The residue was purified by silica gel column chromatography.Using n-hexane as an eluent, 3.92 g of Compound 2 was obtained.
General procedure: To a solution of 3-amino 7-hydroxycoumarin (1.0 eq) in dimethylformamide (DMF) (20 mL) was added anhy. K2CO3 (2.5 eq) and stirredat room temperature for 10-15 min. To this mixture, alkyl bromide(1.0 mmol) was added and resulting solution was stirred at room temperature(rt) for 22-24 h. The completion of reaction was checked byTLC. After completion of reaction, the reaction mixture was pouredinto ice-cold water to give solid. The solid was filtered, washed withwater, dried and recrystallized from ethanol to give compound 13 asoffwhite solid. These compounds 14a-lwere directly used for next step.
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