* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With tetrabutylammomium bromide In cyclohexane; water; ethyl acetate; toluene
Step A is conducted by adding tetrabutylammonium bromide (950 mg-3 mmol-0.05 eq.) and powder potash (23.1 g-411 mmol-7 eq.) under agitation to a solution of 2-pyrrolidinone (5.00 g-58.8 mmol) and bromododecane (18.5 mL, 76.4 mmol, 1.3 eq.) in toluene (60 mL). The mixture is heated to 50° C. overnight. After disappearance of the 2-pyrrolidinone (verified by TLC using a 4:1 v/v mixture of ethyl acetate and cyclohexane, and phosphomolybdic acid for detection) and cooling, 60 mL of water is added and the mixture left under agitation for a further 15 minutes. The aqueous and organic phases are separated and the aqueous phase is extracted once with diethylether (60 mL). The organic phases are combined, dried over Na2SO4, filtered and concentrated. After vacuum distillation (146° C.-0.5 mbars), N-dodecylpyrrolidin-2-one is obtained (Yield: 80percent) for which the 1H and 13C NMR characterisations are as follows: 1H NMR (400 MHz, CDCl3) δ (ppm): 0.88 (t, 3H, J=7.0 Hz, CH3); 1.25-1.31 (m, 18H, CH2); 1.47-1.54 (m, 2H, Alk-CH2-CH2-N); 1.97-2.05 (m, 2H, CO-CH2-CH2-CH2-N); 2.38 (t, 2H, J=8.0 Hz, CO-CH2-CH2-CH2-N); 3.26 (t, 2H, J=7.5 Hz, Alk-CH2-CH2-N); 3.37 (t, 2H, J=7.0 Hz, CO-CH2-CH2-CH2-N). 13C NMR (100 MHz, CDCl3) δ (ppm): 14.3 (CH3); 18.1 (CO-CH2-CH2-CH2-N); 22.9; 27.0 (CH2alk); 27.5 (Alk-CH2-CH2-N); 29.5; 29.7; 29.8; 29.9 (CH2alk); 31.3 (CO-CH2-CH2-CH2-N); 32.1 (CH2alk); 42.7 (Alk-CH2-CH2-N); 47.2 (CO-CH2-CH2-CH2-N); 174.9 (CO).
Reference：
[1] Journal of Pharmaceutical Sciences, 1983, vol. 72, # 11, p. 1354 - 1356
3
[ 105-60-2 ]
[ 143-15-7 ]
[ 59227-89-3 ]
Yield
Reaction Conditions
Operation in experiment
99.6%
With sodium hydroxide In water; toluene
EXAMPLE 1 A 1l reactor is charged with 34 g (0.3 mole) of azacycloheptane-2-one, 112 g (0.45 mole) of dodecyl bromide, 300 g of toluene, 3.4 g (3.3 mole percent based on the azacycloheptane-2-one) of crystalline tetrabutylammonium hydrogensulfate (TBAHS) and 90 g (2.25 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. After the mixture was cooled to 40° C., 135 g of water was added to the mixture, followed by stirring at 40° C. for 30 minutes. The oil layer was separated and the oil layer thus obtained was subjected to distillation, giving 84.0 g of 1-dodecylazacycloheptane-2-one having a boiling point of 195° to 200° C./3 mmHg (yield of 99.6percent based on the azacycloheptane-2-one), and also 0.8 g of dodecyl ether (yield of 1.0percent based on the dodecyl bromide).
95%
With sodium hydroxide In toluene
EXAMPLE 3 A 1l reactor was charged with 57 g (0.5 mole) of azacycloheptane-2-one, 125 g (0.5 mole) of dodecyl bromide, 182 g of toluene, 3.2 g (2 mole percent) of crystalline tetrabutylammonium bromide (TBAB) and 60 g (1.5 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. The same aftertreatment as in Example 1 was repeated, giving 133.5 g of 1-dodecylazacycloheptane-2-one (yield of 95.0percent) and 0.7 g of dodecyl ether (yield of 0.8percent)
92.8%
With sodium hydroxide; tetrabutylammomium bromide; potassium carbonate In cyclohexane
EXAMPLE 1 Preparation of 1-n-dodecylazacycloheptan-2-one at a bath temperature of 55° C. 117 g of caprolactam (1.033 mole), 10 g of tetrabutylammonium bromide (0.03 mole), 100 g of anhydrous potassium carbonate (0.7 mole, dried for 2 hrs at 120 C.), 100 g of pulverized sodium hydroxide (2.5 mole), and 1 L of cyclohexane were placed in a flask equipped with a funnel, reflux condenser and a mechanical stirrer. To this mixture were added dropwise a solution of 250 ml of 1-bromododecane (1.033 mole) and 250 ml of cyclohexane with vigorous stirring over one-half hour at a bath temperature of 55° C. The stirring was continued; in the meanwhile thin-layer chromatography was used to monitor the course of the reaction, and it was found that the reaction was completed after 7 hours. The reaction mixture was then cooled to room temperature and filtered. The filtrate was washed with water (3*500 ml) to remove remaining caprolactam. The organic phase was dried over anhydrous magnesium sulfate. The filtrate was evaporated using a rotary film evaporator to remove cyclohexane (which can be used again), and the residue was distilled at reduced pressure to yield 270 g of colorless, odorless, transparent liquid product (yield: 92.8percent), b,p.200-201 C/0.7 mmHg.
Reference：
[1] Patent: US4812566, 1989, A,
[2] Patent: US4812566, 1989, A,
[3] Patent: US4973688, 1990, A,
[4] JAOCS, Journal of the American Oil Chemists' Society, 1996, vol. 73, # 7, p. 847 - 850
[5] Journal of Pharmaceutical Sciences, 1993, vol. 82, # 2, p. 214 - 219
[6] Journal of Pharmaceutical Sciences, 1989, vol. 78, # 9, p. 738 - 741
4
[ 143-15-7 ]
[ 59227-89-3 ]
Reference：
[1] Patent: US4422970, 1983, A,
5
[ 143-15-7 ]
[ 3553-94-4 ]
[ 59227-89-3 ]
Reference：
[1] Patent: US4692523, 1987, A,
6
[ 105-60-2 ]
[ 143-15-7 ]
[ 59227-89-3 ]
Reference：
[1] Patent: US4310525, 1982, A,
7
[ 105-60-2 ]
[ 1634-04-4 ]
[ 143-15-7 ]
[ 59227-89-3 ]
Reference：
[1] Patent: US5986092, 1999, A,
8
[ 105-60-2 ]
[ 143-15-7 ]
[ 59227-89-3 ]
Reference：
[1] Patent: US4525199, 1985, A,
9
[ 288-32-4 ]
[ 143-15-7 ]
[ 4303-67-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With potassium carbonate In acetone for 7 h; Reflux
Imidazole 1 (0.68 g, 10 mmol), bromododecane (2.5 g, 10 mmol)Anhydrous potassium carbonate (2.76 g, 20 mmol) was placed in a 50 mL round-bottomed flask and dissolved in 20 mL of acetone.The combined solution was heated at reflux for 7 h. The acetone solvent was removed by rotary evaporation and subjected to column chromatography(Ethyl acetate as eluent), the ethyl acetate solvent was removed by rotary distillation under reduced pressure, and dried in vacuo,The yield of purified N-dodecylimidazole was 90percent.
88.1%
With sodium hydroxide In dimethyl sulfoxide at 20 - 25℃; Inert atmosphere
Equipped with a stirrer, a thermometer, a three-necked flask was added 0.440 g (11.0 mmol) NaOH, 0.714 g (10.5 mmol) of imidazole and 10 mL of dimethyl sulfoxide (DMSO), at 20 ° C ~ 25 ° C under nitrogen atmosphere stir until a clear solution, to which was added dropwise 2.49 g (10.0 mmol) of bromo dodecane, reacted for about 4 ~ 6 h, the reaction was poured into 10 mL of water and extracted with chloroform 3 × 10 mL, and then washed with water The chloroform layer was washed 4 to 5 times, and then dried over anhydrous MgSO 4, filtered to obtain a filtrate, the chloroform was removed to give a pale yellow liquid N- dodecyl imidazole 2.08 g, yield 88.1percent.
86%
Stage #1: With sodium hydroxide In tetrahydrofuran; water at 20℃; for 1 h; Stage #2: at 55℃; for 24 h;
imidazole in an eggplant-shaped flask (2.05g, 30mmol) was dissolved in tetrahydrofuran (15mL), there sodium hydroxide solution (sodium hydroxide 2.47g, 62 mmol, water 5g) was added and stirred for 1 hour at room temperature.Here bromo dodecane (7.48 g, 30 mmol) was added and stirred for 1 day at 55 ° C..After the reaction solution was washed with ethyl acetate, neutralized with hydrochloric acid, it was subjected to three washes with subsequent water.The organic layer was dried over anhydrous magnesium sulfate, filtration using a filter paper and evaporated after removing the magnesium sulfate SiO2and purified by (1, Rf value 0.52 chloroform: methanol = 9) column chromatography .Thereafter, filtered through a syringe filter, an object of the 1-by distilling off the solvent againto obtain a dodecyl imidazole 1 (Yield: 6.10g, 25.8mmol, 86percent yield).
81%
With sodium hydroxide In tetrahydrofuran for 72 h; Reflux
General procedure: N-Dodecylimidazole was obtained following the procedure ofliterature [45]. To a solution of imidazole (0.7 g, 10 mmol) in NaOH(50percent) solution (1.0 g, 11 mmol), a solution of 1-bromododecane(2.5 g, 10 mmol) in THF (10 mL) was added dropwise. The obtainedmixture was refluxed for three days. After cooling, THF wasremoved by a rotary evaporator. The residue was extracted withdichloromethane three times. The combined organic layer waswashed with water and then dried over anhydrous Na2SO4. The fil-trate was concentrated and purified by a column chromatographyto produce clear yellow oil (2.0 g, 81percent).1H NMR (CDCl3): (ppm) = 0.83 (t, J = 5.1 Hz, 3H, CH3), 1.10–1.21(m, 18H, CH2), 1.69 (br, J = 7.0 Hz, 2H, CH2), 3.84 (t, J = 6.2 Hz, 2H,CH2), 6.89 (s, 1H, ImH), 7.04 (s, 1H, ImH), 7.44 (s, 1H, ImH).13C NMR(CDCl3): (ppm) = 13.7, 22.3, 26.1, 28.7, 28.9, 29.0, 29.2, 20.7, 31.5,46.5, 118.3, 128.2, 136.6
80%
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.
80.5%
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.
Reference：
[1] Russian Journal of Organic Chemistry, 2013, vol. 49, # 9, p. 1291 - 1299[2] Zh. Org. Khim., 2013, vol. 49, # 9, p. 1308 - 1316,9
[3] Patent: CN106188014, 2016, A, . Location in patent: Paragraph 0016
[4] Patent: CN103951702, 2016, B, . Location in patent: Paragraph 0059; 0060
[5] Tetrahedron, 2010, vol. 66, # 35, p. 7077 - 7082
[6] Journal of Physical Chemistry B, 2010, vol. 114, # 21, p. 7312 - 7319
[7] Macromolecules, 2012, vol. 45, # 9, p. 3974 - 3985
[8] Tetrahedron, 2016, vol. 72, # 27-28, p. 4117 - 4122
[9] Patent: JP2016/98194, 2016, A, . Location in patent: Paragraph 0035
[10] New Journal of Chemistry, 2007, vol. 31, # 6, p. 879 - 892
[11] Journal of Molecular Catalysis A: Chemical, 2016, vol. 411, p. 34 - 39
[12] Carbohydrate Research, 2015, vol. 412, p. 28 - 33
[13] Journal of Surfactants and Detergents, 2016, vol. 19, # 4, p. 681 - 691
[14] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 17, p. 2863 - 2865
[15] Green Chemistry, 2014, vol. 16, # 6, p. 3117 - 3124
[16] Synthesis, 2009, # 19, p. 3219 - 3226
[17] Helvetica Chimica Acta, 2004, vol. 87, # 11, p. 2742 - 2749
[18] Angewandte Chemie - International Edition, 2013, vol. 52, # 1, p. 455 - 458[19] Angew. Chem., 2013, vol. 125, # 1, p. 473 - 476,4
[20] Polish Journal of Chemistry, 1995, vol. 69, # 3, p. 447 - 460
[21] Journal of Chemical and Engineering Data, 2006, vol. 51, # 4, p. 1274 - 1279
[22] Journal of Materials Chemistry, 2011, vol. 21, # 33, p. 12280 - 12287
[23] Catalysis Communications, 2012, vol. 18, p. 11 - 15
[24] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 4, p. 423 - 427
[25] Journal of the Chinese Chemical Society, 2013, vol. 60, # 7, p. 745 - 754
[26] Chemical Biology and Drug Design, 2014, vol. 83, # 3, p. 278 - 288
[27] Chinese Journal of Catalysis, 2013, vol. 34, # 12, p. 2236 - 2244
[28] Bulletin of the Korean Chemical Society, 2014, vol. 35, # 6, p. 1675 - 1680
[29] RSC Advances, 2015, vol. 5, # 4, p. 2869 - 2881
[30] RSC Advances, 2015, vol. 5, # 71, p. 57968 - 57974
[31] RSC Advances, 2015, vol. 5, # 78, p. 63732 - 63737
[32] Langmuir, 2015, vol. 31, # 12, p. 3587 - 3595
[33] RSC Advances, 2015, vol. 5, # 28, p. 21865 - 21876
[34] RSC Advances, 2016, vol. 6, # 33, p. 27370 - 27377
[35] RSC Advances, 2017, vol. 7, # 75, p. 47335 - 47352
[36] Chinese Chemical Letters, 2016, vol. 27, # 2, p. 226 - 230
[37] Dalton Transactions, 2018, vol. 47, # 40, p. 14241 - 14253
Reference：
[1] Bioorganic and Medicinal Chemistry, 2006, vol. 14, # 14, p. 4775 - 4780
13
[ 143-15-7 ]
[ 126930-72-1 ]
Reference：
[1] Journal of Materials Chemistry, 2001, vol. 11, # 4, p. 1063 - 1071
14
[ 143-15-7 ]
[ 108-46-3 ]
[ 41662-92-4 ]
Reference：
[1] Langmuir, 2010, vol. 26, # 5, p. 3760 - 3765
[2] Chemistry - An Asian Journal, 2013, vol. 8, # 5, p. 956 - 962
[3] Journal of Porphyrins and Phthalocyanines, 2014, vol. 18, # 7, p. 569 - 578
[4] Journal of Porphyrins and Phthalocyanines, 2014, vol. 18, # 7, p. 569 - 578
[5] RSC Advances, 2016, vol. 6, # 91, p. 88531 - 88537
15
[ 143-15-7 ]
[ 108-46-3 ]
[ 79095-51-5 ]
[ 41662-92-4 ]
Reference：
[1] Journal of Medicinal Chemistry, 1992, vol. 35, # 9, p. 1650 - 1662
[2] Journal of Medicinal Chemistry, 1992, vol. 35, # 9, p. 1650 - 1662
16
[ 143-15-7 ]
[ 124-40-3 ]
[ 112-18-5 ]
[ 3282-73-3 ]
Yield
Reaction Conditions
Operation in experiment
40%
at 20 - 25℃; for 20 h;
A mixture of a 38percent aqueous solution of dimethylamine (12.5 mL, 93.8 mmol) and dodecyl bromide (11.7 g, 46.9 mmol) in benzene (15 mL) was stirred at 20—25 °C for 20 h. Then, a 50percent aqueous solution of NaOH (1.9 g, 46.9 mmol) was added to the reaction mixture, and the resulting mixture was evaporated in vacuo. The residue was dissolved in CHCl3 (20 mL), the formed precipitate was filtered off, and the filtrate was evaporated in vacuo. According to the 1H NMR spectral data, the isolated mixture contained amine 6a (4.1 g, 40percent), N,N-didodecyl-N,N-dimethylammonium bromide (4.9 g, 46percent), and unreacted dodecyl bromide (1.7 g, 14percent).
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
17
[ 112-18-5 ]
[ 143-15-7 ]
[ 3282-73-3 ]
Reference：
[1] Chemical Communications, 2006, # 44, p. 4575 - 4577
[2] Journal of Organic Chemistry, 1984, vol. 49, # 20, p. 3774 - 3778
[3] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1987, p. 541 - 546
[4] Journal of Physical Chemistry, 1983, vol. 87, # 4, p. 538 - 540
[5] Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 10, p. 1903 - 1910
[6] Patent: WO2005/97729, 2005, A2, . Location in patent: Page/Page column 49-50; 56-57
18
[ 143-15-7 ]
[ 683-10-3 ]
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
[3] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[4] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
19
[ 110-86-1 ]
[ 143-15-7 ]
[ 104-73-4 ]
Yield
Reaction Conditions
Operation in experiment
67%
at 80℃; for 17 h; Inert atmosphere
ILs were synthesized by direct alkylation of pyridine with an equimolar amount of the corresponding bromoalkane in a round-bottomed flask (with diameter of 5.4 cm and total volume of 60 mL) equipped with a reflux condenser, a magnetic stirrer (250 rpm) and heated in an oil bath. The mixture was stirred at 80°C during a certain time (3h to 17h) under N2 atmosphere, and during the reaction, a second, lower phase containing the ionic liquid appears. The reaction mixture was then cooled to room temperature. Specifications of syntheses for each bromoalkane are indicated below.n-butylpyridinium bromide. (Heating for 3h). After the excess of reagents was removed under reduced pressure, the obtained solid pyridinium was washed with ether and dried to give 17.3g of the desired salt [BuPy][Br] that corresponds to a chemical yield of 80percent. n-hexylpyridinium bromide. (Heating for 3h). After cooling, the white precipitate formed into c.a. 350 mL diethylether was filtered, washed, dried and led to 21.2 g of the [HePy][Br] IL; chemical yield: 87percent. n-octylpyridinium bromide. (Heating for 3h). 21.4g of [OcPy][Br] as a slightly brownish liquid (chemical yield: 79percent) was obtained.n-dodecylpyridinium bromide. (Heating for 17h). After cooling, the white precipitate formed into ether (100 mL) was filtered, washed, dried and led to 22.0 g of the [DoDePy][Br] IL; chemical yield 67percent.
Reference：
[1] Molecules, 2010, vol. 15, # 3, p. 1967 - 1972
[2] Tetrahedron Letters, 2012, vol. 53, # 27, p. 3474 - 3477
[3] Journal of Physical Chemistry, 1986, vol. 90, # 4, p. 641 - 644
[4] Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie, 1952, vol. 291, p. 1,4
[5] Journal of the Chemical Society, 1938, p. 682
[6] Bulletin of the Chemical Society of Japan, 1959, vol. 32, p. 267,268
[7] Journal of Polymer Science, 1951, vol. 6, p. 649,651
[8] Journal of Physical Chemistry, 1987, vol. 91, # 23, p. 5928 - 5930
[9] Tetrahedron, 2010, vol. 66, # 6, p. 1352 - 1356
[10] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2012, vol. 51, # 4, p. 611 - 616
[11] Journal of Surfactants and Detergents, 2012, vol. 15, # 5, p. 587 - 592
[12] Bulletin of the Chemical Society of Japan, 2016, vol. 89, # 9, p. 1106 - 1128
[13] Green Chemistry, 2017, vol. 19, # 23, p. 5674 - 5682
20
[ 110-18-9 ]
[ 143-15-7 ]
[ 18464-23-8 ]
Yield
Reaction Conditions
Operation in experiment
94%
at 20℃; for 2 h; Reflux
To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL)was added N,N,N’,N’-tetramethylethylenediamine(0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux withstirring for 2 h, during which time a pale-yellow solid was observed. To thewarm reaction mixture was added cold acetone (~9 mL), and the reaction mixturewas cooled to 0 °C, which led to a white precipitate. Filtration through aBuchner funnel furnished a white powder, which was washed with cold acetone (~4mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 94percent) as a whitepowder: mp= 189.0-194.0 °C; 1H NMR (300 MHz, CDCl3) δ4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J = 6.3 Hz, 6H); 13CNMR (75 MHz, CDCl3) δ 65.87, 56.75, 51.28, 31.99, 29.78, 29.75,29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum(ESI) m/z 227.5 [M2+; calcd for C30H66N2:227.26].
92%
for 2 h; Reflux
Comparative compound (12,2,12) bromide To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL) was added N,N,N',N'-tetramethylethylenediamine (0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux with stirring for 2 h, during which time a pale-yellow solid was observed. To the warm reaction mixture was added cold acetone (~9 mL), and the reaction mixture was cooled to 0 °C, which led to a white precipitate. Filtration through a Buchner funnel furnished a white powder, which was washed with cold acetone (~4 mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 92percent) as a white powder: mp 189.0-194.0 °C; 1H NMR (300 MHz, CDC13) δ 4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J= 6.3 Hz, 6H); 13C NMR (75 MHz, CDC13) δ 65.87, 56.75, 51.28, 31.99, 29.78, 29.75, 29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum (ESI) m/z 227.5 M2+; calcd for C30H66N2: 227.26].
82%
for 12 h; Reflux
General procedure: A magnetically stirred solution of N,N,N0,N0-tetramethylethylenediamine(4.64 g, 40 mmol) and 1-bromodecane(17.68 g, 80 mmol) in 200 mL of acetone was refluxed for 12 h. Then the mixture was cooled and was left for 12 h in cold conditions. The crude product was precipitated in the form of white crystals. It was recrystallized two times from acetone then filtered and dried in air, yielding 10.4 g of white crystals (47 percent).
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2014, vol. 24, # 1, p. 99 - 102
[2] Patent: WO2015/69760, 2015, A1, . Location in patent: Paragraph 0098; 0099
[3] Langmuir, 2015, vol. 31, # 1, p. 120 - 124
[4] Molecules, 2011, vol. 16, # 1, p. 319 - 335
[5] Journal of Surfactants and Detergents, 2016, vol. 19, # 4, p. 663 - 671
[6] Journal of the American Chemical Society, 2006, vol. 128, # 2, p. 492 - 501
[7] Langmuir, 2011, vol. 27, # 12, p. 7549 - 7557
[8] DRP/DRBP Org.Chem.,
[9] Pharmaceutical Chemistry Journal, 1968, # 5, p. 247 - 250[10] Khimiko-Farmatsevticheskii Zhurnal, 1968, # 5, p. 15 - 18
[11] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2010, vol. 75, # 2, p. 671 - 677
[12] Langmuir, 2010, vol. 26, # 2, p. 678 - 683
[13] Journal of Molecular Catalysis A: Chemical, 2010, vol. 328, # 1-2, p. 88 - 92
[14] Langmuir, 2010, vol. 26, # 22, p. 17119 - 17125
[15] Langmuir, 2012, vol. 28, # 5, p. 2476 - 2484
[16] Journal of Surfactants and Detergents, 2012, vol. 15, # 1, p. 33 - 40
[17] Journal of Surfactants and Detergents, 2012, vol. 15, # 1, p. 107 - 115
[18] Journal of Surfactants and Detergents, 2013, vol. 16, # 5, p. 693 - 707
[19] Journal of Surfactants and Detergents, 2014, vol. 17, # 5, p. 951 - 957
[20] Journal of Chemical and Engineering Data, 2016, vol. 61, # 1, p. 142 - 150
[21] Journal of Molecular Liquids, 2017, vol. 242, p. 1066 - 1074
[22] Patent: US2113606, 1935, ,
[23] Patent: FR790279, 1936, ,
To a 250 mL row1d bottom f1ask \vas added a solution of 1-bromododecane 222a (5 g,20 06 mmol, 1.00 equiv.) in ethanol (40 mL) and a solution ofNa2S03 (5.2 g, 2.00 equiv.) inwater (40 mL) The resulting mixture was heated at 80°C overnight. After cooling to roomtemperature, the mixture was extracted with ethyl acetate (100 mL x 2). The combinedorganic extracts were washed with brine (30 mL x 2), dried over anhydrous sodium sulfate15 and concentrated to a residue which was triturated ·with hex:mes (20 mL x 3) to give sodiumdodecane-1-sulfonate 222b (5 2 g, 92percent) as a white solid.
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
[3] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[4] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
25
[ 13468-02-5 ]
[ 143-15-7 ]
[ 538-71-6 ]
Reference：
[1] Patent: GB607222, 1948, ,
26
[ 693-98-1 ]
[ 100-44-7 ]
[ 143-15-7 ]
[ 21054-72-8 ]
Reference：
[1] Journal of Materials Chemistry A, 2015, vol. 3, # 16, p. 8559 - 8565
27
[ 143-15-7 ]
[ 148256-63-7 ]
Reference：
[1] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 18, p. 3942 - 3949
[2] Bulletin of the Korean Chemical Society, 2012, vol. 33, # 5, p. 1659 - 1663
28
[ 872-31-1 ]
[ 143-15-7 ]
[ 104934-52-3 ]
Yield
Reaction Conditions
Operation in experiment
88%
Stage #1: With iodine; magnesium In tetrahydrofuran at 70℃; for 2 h; Inert atmosphere Stage #2: With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran at 20℃;
Under N2 atmosphere,To the possession of magnesium tablets(3.28 g, 0.135 mol),Anhydrous THF (30 mL)withA small amount of iodine mixture250 mL three-necked flask was added slowly1-bromododecane (28.75 g, 26.9 mL, 0.13 mol)In anhydrous THF (45 mL).The mixture was refluxed at 70 ° C for 2 hours,The system was cooled to room temperature with ice water,First Ni (dppp) Cl2 (0.54 g,1.00 mmol) was added,A solution of 3-bromothiophene (16.31 g, 0.10 mol) in dry THF (40 mL) was slowly added.The mixed solution was stirred overnight at room temperature,The reaction was quenched by the addition of cold HCl (1.50 mol / L) aqueous solution.The crude product was extracted with dichloromethane,Dried over anhydrous magnesium sulfate,And further purified by a column separation and purification method (n-hexane as an eluent)To clarify the liquid (22.18 g, 88percent).
Reference：
[1] Patent: CN106588867, 2017, A, . Location in patent: Paragraph 0022; 0023; 0024
[2] Journal of Physical Chemistry B, 2001, vol. 105, # 45, p. 11106 - 11113
[3] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 18, p. 3942 - 3949
[4] Bulletin of the Korean Chemical Society, 2012, vol. 33, # 5, p. 1659 - 1663
[5] Angewandte Chemie - International Edition, 2018, vol. 57, # 24, p. 7034 - 7039[6] Angew. Chem., 2018, vol. 130, p. 7152 - 7157,6
[7] European Journal of Organic Chemistry, 2015, vol. 2015, # 24, p. 5448 - 5452
[8] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1993, # 3, p. 489 - 494
[9] Journal of Materials Chemistry, 1996, vol. 6, # 8, p. 1319 - 1324
[10] Patent: US4730005, 1988, A,
[11] Macromolecules, 2011, vol. 44, # 16, p. 6370 - 6381
[12] RSC Advances, 2016, vol. 6, # 5, p. 4070 - 4076
[13] Canadian Journal of Chemistry, 2016, vol. 94, # 6, p. 553 - 558
29
[ 143-15-7 ]
[ 139100-06-4 ]
Reference：
[1] RSC Advances, 2016, vol. 6, # 5, p. 4070 - 4076
[2] Patent: CN106588867, 2017, A,
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 24, p. 7034 - 7039[4] Angew. Chem., 2018, vol. 130, p. 7152 - 7157,6
30
[ 16433-88-8 ]
[ 143-15-7 ]
[ 286438-45-7 ]
Yield
Reaction Conditions
Operation in experiment
86.6%
With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 80℃; for 24 h; Inert atmosphere
Dissolve fluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.Stop the reaction and pour the mixed solution into aqueous Na2S2O3 solution.Extract with dichloromethane (15 mL × 3), combine the organic layers with deionized water (25 mL × 3) and saturated brine (20 mL), dry the organic layer over anhydrous magnesium sulfate, and remove the solvent using a rotary evaporator.The crude product is recrystallized from absolute ethanol solution.A white solid of 2,7-dibromo-fluorene (7.04 g, 72.2percent) was obtained;2,7-Dibromo-fluorene (6.40 g, 19.75 mmol) and tetrabutylammonium bromide (0.10 g, 0.31 mmol) obtained from the previous reactionDissolve 1-bromododecane (10 mL, 41.65 mmol) in 60 mL of toluene and 25 mL of 50 wtpercent NaOH aqueous solution, and argon at 80 °C for 24 hours under reflux.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated by a chromatography column (petroleum ether:dichloromethane=4:1) to give 2,7-dibromo-9,9-didodecyl-fluoreneas a pale yellow solid (11.30 g, 86.6percent). );Finally, the resulting 2,7-dibromo-9,9-didodecyl-fluorene (2.00 g, 3.03 mmol) was reacted in the previous step.Dissolve in 60 mL of dichloromethane, add 10 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (4.98 g, 9.08 mmol) was added in portions to the above mixed solution and the reaction was stirred for 1 hour.Stop the reaction by adding 50 mL of deionized water and extract with dichloromethane (15 mL x 3).The organic phase was washed with deionized water (25 mL×3) and saturated brine (20 mL), respectively.Dry the organic layer by adding anhydrous magnesium sulfate,The solvent was removed using a rotary evaporator and the crude product was separated on a chromatography column (petroleum ether: dichloromethane = 4:1).The orange-yellow product 2,7-dibromo-9,9-didoceyl-1,6-dinitrofluorene (1.7 g, 74.56percent) was obtained.
Reference：
[1] Chemistry - A European Journal, 2010, vol. 16, # 48, p. 14256 - 14260
[2] Journal of Materials Chemistry C, 2014, vol. 2, # 28, p. 5540 - 5552
[3] Patent: CN107686448, 2018, A, . Location in patent: Paragraph 0014; 0016; 0017
[4] Macromolecules, 2015, vol. 48, # 15, p. 5155 - 5161
[5] Chemical Communications, 2013, vol. 49, # 57, p. 6388 - 6390
[6] Journal of Materials Chemistry C, 2018, vol. 6, # 22, p. 6023 - 6032
[7] Journal of Materials Chemistry C, 2018, vol. 6, # 42, p. 11416 - 11426
[8] RSC Advances, 2017, vol. 7, # 85, p. 53785 - 53796
[9] Chemistry - A European Journal, 2016, vol. 22, # 41, p. 14560 - 14566
[10] Chemical Communications, 2011, vol. 47, # 43, p. 11990 - 11992
[11] Polymer, 2010, vol. 51, # 22, p. 5078 - 5086
[12] Asian Journal of Chemistry, 2013, vol. 25, # 13, p. 7499 - 7504
[13] Dyes and Pigments, 2018, vol. 155, p. 225 - 232
31
[ 143-15-7 ]
[ 286438-45-7 ]
Reference：
[1] New Journal of Chemistry, 2001, vol. 25, # 9, p. 1175 - 1181
32
[ 143-15-7 ]
[ 1313876-00-4 ]
Reference：
[1] New Journal of Chemistry, 2011, vol. 35, # 6, p. 1327 - 1334
[2] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 20, p. 4387 - 4397
[3] Dyes and Pigments, 2012, vol. 95, # 3, p. 600 - 605
To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL)was added N,N,N?,N?-tetramethylethylenediamine(0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux withstirring for 2 h, during which time a pale-yellow solid was observed. To thewarm reaction mixture was added cold acetone (~9 mL), and the reaction mixturewas cooled to 0 C, which led to a white precipitate. Filtration through aBuchner funnel furnished a white powder, which was washed with cold acetone (~4mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 94%) as a whitepowder: mp= 189.0-194.0 C; 1H NMR (300 MHz, CDCl3) delta4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J = 6.3 Hz, 6H); 13CNMR (75 MHz, CDCl3) delta 65.87, 56.75, 51.28, 31.99, 29.78, 29.75,29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum(ESI) m/z 227.5 [M2+; calcd for C30H66N2:227.26].
92%
In acetonitrile; for 2h;Reflux;
Comparative compound (12,2,12) bromideTo a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL) was added N,N,N',N'-tetramethylethylenediamine (0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux with stirring for 2 h, during which time a pale-yellow solid was observed. To the warm reaction mixture was added cold acetone (~9 mL), and the reaction mixture was cooled to 0 C, which led to a white precipitate. Filtration through a Buchner funnel furnished a white powder, which was washed with cold acetone (~4 mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 92%) as a white powder: mp 189.0-194.0 C; 1H NMR (300 MHz, CDC13) delta 4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J= 6.3 Hz, 6H); 13C NMR (75 MHz, CDC13) delta 65.87, 56.75, 51.28, 31.99, 29.78, 29.75, 29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum (ESI) m/z 227.5 M2+; calcd for C30H66N2: 227.26].
82%
In acetone; for 12h;Reflux;
General procedure: A magnetically stirred solution of N,N,N0,N0-tetramethylethylenediamine(4.64 g, 40 mmol) and 1-bromodecane(17.68 g, 80 mmol) in 200 mL of acetone was refluxed for 12 h. Then the mixture was cooled and was left for 12 h in cold conditions. The crude product was precipitated in the form of white crystals. It was recrystallized two times from acetone then filtered and dried in air, yielding 10.4 g of white crystals (47 %).
In ethanol; acetone; at 74.99℃; for 48h;
Gemini surfactant i.e. ethanediyl-1,2-bis(dimethyldodecylammonium bromide) was prepared by followingthe well established procedure (Scheme 1) reported in literature [23,24]. Mixture of N, N, N, N-tetramethyl ethylene diamine (TEMED) and1-bromododecane (molar ratio of 1:2) in 10 ml of ethyl alcohol wastaken in round bottom flask then 5 ml of acetone was added to removeturbidity and get clear solution. This solution was then refluxed at348.15 K for approximately 48 h until the entire volume of TEMEDwas consumed. After removal of the solvent by evaporation, the preparedwaxy compound was allowed to cool at room temperature and washed with mixture of ethyl acetate and acetone in 1:1 ratio. Thewashing was repeated 6-7 times to eliminate excess of alkyl bromide.The resulting white product was crystallized twice in dry acetone anddried in vacuum oven at 323.15 K.
EXAMPLE 1 A 1l reactor is charged with 34 g (0.3 mole) of azacycloheptane-2-one, 112 g (0.45 mole) of dodecyl bromide, 300 g of toluene, 3.4 g (3.3 mole percent based on the azacycloheptane-2-one) of crystalline tetrabutylammonium hydrogensulfate (TBAHS) and 90 g (2.25 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. After the mixture was cooled to 40° C., 135 g of water was added to the mixture, followed by stirring at 40° C. for 30 minutes. The oil layer was separated and the oil layer thus obtained was subjected to distillation, giving 84.0 g of 1-dodecylazacycloheptane-2-one having a boiling point of 195° to 200° C./3 mmHg (yield of 99.6percent based on the azacycloheptane-2-one), and also 0.8 g of dodecyl ether (yield of 1.0percent based on the dodecyl bromide).
95.0%
With sodium hydroxide; In toluene;
EXAMPLE 3 A 1l reactor was charged with 57 g (0.5 mole) of azacycloheptane-2-one, 125 g (0.5 mole) of dodecyl bromide, 182 g of toluene, 3.2 g (2 mole percent) of crystalline tetrabutylammonium bromide (TBAB) and 60 g (1.5 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. The same aftertreatment as in Example 1 was repeated, giving 133.5 g of 1-dodecylazacycloheptane-2-one (yield of 95.0percent) and 0.7 g of dodecyl ether (yield of 0.8percent)
92.8%
With sodium hydroxide; tetrabutylammomium bromide; potassium carbonate; In cyclohexane;
EXAMPLE 1 Preparation of 1-n-dodecylazacycloheptan-2-one at a bath temperature of 55° C. 117 g of caprolactam (1.033 mole), 10 g of tetrabutylammonium bromide (0.03 mole), 100 g of anhydrous potassium carbonate (0.7 mole, dried for 2 hrs at 120 C.), 100 g of pulverized sodium hydroxide (2.5 mole), and 1 L of cyclohexane were placed in a flask equipped with a funnel, reflux condenser and a mechanical stirrer. To this mixture were added dropwise a solution of 250 ml of 1-bromododecane (1.033 mole) and 250 ml of cyclohexane with vigorous stirring over one-half hour at a bath temperature of 55° C. The stirring was continued; in the meanwhile thin-layer chromatography was used to monitor the course of the reaction, and it was found that the reaction was completed after 7 hours. The reaction mixture was then cooled to room temperature and filtered. The filtrate was washed with water (3*500 ml) to remove remaining caprolactam. The organic phase was dried over anhydrous magnesium sulfate. The filtrate was evaporated using a rotary film evaporator to remove cyclohexane (which can be used again), and the residue was distilled at reduced pressure to yield 270 g of colorless, odorless, transparent liquid product (yield: 92.8percent), b,p.200-201 C/0.7 mmHg.
With potassium carbonate; In acetone; for 7h;Reflux;
Imidazole 1 (0.68 g, 10 mmol), bromododecane (2.5 g, 10 mmol)Anhydrous potassium carbonate (2.76 g, 20 mmol) was placed in a 50 mL round-bottomed flask and dissolved in 20 mL of acetone.The combined solution was heated at reflux for 7 h. The acetone solvent was removed by rotary evaporation and subjected to column chromatography(Ethyl acetate as eluent), the ethyl acetate solvent was removed by rotary distillation under reduced pressure, and dried in vacuo,The yield of purified N-dodecylimidazole was 90%.
88.1%
With sodium hydroxide; In dimethyl sulfoxide; at 20 - 25℃;Inert atmosphere;
Equipped with a stirrer, a thermometer, a three-necked flask was added 0.440 g (11.0 mmol) NaOH, 0.714 g (10.5 mmol) of imidazole and 10 mL of dimethyl sulfoxide (DMSO), at 20 C ~ 25 C under nitrogen atmosphere stir until a clear solution, to which was added dropwise 2.49 g (10.0 mmol) of bromo dodecane, reacted for about 4 ~ 6 h, the reaction was poured into 10 mL of water and extracted with chloroform 3 × 10 mL, and then washed with water The chloroform layer was washed 4 to 5 times, and then dried over anhydrous MgSO 4, filtered to obtain a filtrate, the chloroform was removed to give a pale yellow liquid N- dodecyl imidazole 2.08 g, yield 88.1%.
86%
imidazole in an eggplant-shaped flask (2.05g, 30mmol) was dissolved in tetrahydrofuran (15mL), there sodium hydroxide solution (sodium hydroxide 2.47g, 62 mmol, water 5g) was added and stirred for 1 hour at room temperature.Here bromo dodecane (7.48 g, 30 mmol) was added and stirred for 1 day at 55 C..After the reaction solution was washed with ethyl acetate, neutralized with hydrochloric acid, it was subjected to three washes with subsequent water.The organic layer was dried over anhydrous magnesium sulfate, filtration using a filter paper and evaporated after removing the magnesium sulfate SiO2and purified by (1, Rf value 0.52 chloroform: methanol = 9) column chromatography .Thereafter, filtered through a syringe filter, an object of the 1-by distilling off the solvent againto obtain a dodecyl imidazole 1 (Yield: 6.10g, 25.8mmol, 86% yield).
81%
With sodium hydroxide; In tetrahydrofuran; for 72h;Reflux;
General procedure: N-Dodecylimidazole was obtained following the procedure ofliterature [45]. To a solution of imidazole (0.7 g, 10 mmol) in NaOH(50%) solution (1.0 g, 11 mmol), a solution of 1-bromododecane(2.5 g, 10 mmol) in THF (10 mL) was added dropwise. The obtainedmixture was refluxed for three days. After cooling, THF wasremoved by a rotary evaporator. The residue was extracted withdichloromethane three times. The combined organic layer waswashed with water and then dried over anhydrous Na2SO4. The fil-trate was concentrated and purified by a column chromatographyto produce clear yellow oil (2.0 g, 81%).1H NMR (CDCl3): (ppm) = 0.83 (t, J = 5.1 Hz, 3H, CH3), 1.10-1.21(m, 18H, CH2), 1.69 (br, J = 7.0 Hz, 2H, CH2), 3.84 (t, J = 6.2 Hz, 2H,CH2), 6.89 (s, 1H, ImH), 7.04 (s, 1H, ImH), 7.44 (s, 1H, ImH).13C NMR(CDCl3): (ppm) = 13.7, 22.3, 26.1, 28.7, 28.9, 29.0, 29.2, 20.7, 31.5,46.5, 118.3, 128.2, 136.6
80%
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.
80.5%
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 %.
74%
Add imidazole (1.2 g, 18 mmol), sodium hydroxide (0.7 g, 18 mmol), DMSO (10 mL) to a three-neck flask, and react at room temperature for 2 hours., cool to 0 C, slowly add bromododecane (3.7 g, 15 mmol),After reacting for 5 hours, pour into 20 mL of water, extract with dichloromethane, and steam.A light yellow transparent oily liquid was obtained with a yield of about 74%.
52%
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 24h;
1-Dodecylimidazole: To a solution of 1-bromododecane (10.0 g, 40.1 mmol) in DMF (20.0 mL) was added imidazole (2.73 g, 40.1 mmol) and K2CO3 (16.6 g, 120 mmol) at room temperature, respectively. The reaction mixture was stirred at room temperature for 24 h. Then, water (100 mL) was added and the mixture was extracted with ethyl acetate (3 * 100 mL). The combined organic layer was dried over sodium sulfate anhydrous. The solvent was removed by using rotary evaporator. The residue was concentrated under reduced pressure and purified by column chromatography (SiO2, 10-100 % ethyl acetate/n-hexane) to give the 1-dodecylimidazole as a pale yellow oil; 4.9294 g, yield 52%;
With sodium hydride; In N,N-dimethyl-formamide; at 60℃; for 6h;
The synthesis of N-dodecylimidazole was used as an example. N-dodecyl bromide (7 g, 28 mmol) was dissolved in dimethylformamide (DMF, 25 mL) and then added to a solution of the sodium salt of imidazole, which was formed by the reaction of imidazole (2.3 g, 33.9 mmol) with sodium hydride (1.4 g, 62 mmol) in DMF (25 mL). The mixture was heated at 60 C for 6 h, cooled, and then filtered. The filtrate 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.
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.
The synthetic process of [C3SO3HDoim]HSO4 was shown in Scheme 1 . First, imidazole (6.8g, 0.1mol) was dissolved in 100mL of ethanol sodium ethoxide. The mixture was heated to 70C and kept at this temperature with stirring for 8h under reflux [22]. Then an equal mole of 1-bromododecane was added and the system was allowed to stir for 8h under reflux. The white precipitate was filtered off and the filtrate was extracted three times by diethyl ether followed by vacuum distillation to remove organic solvents to obtain N-dodecyl imidazole, a yellow viscous liquid at room temperature. N-Dodecyl imidazole was characterized by LC/MS.
With hydrogen; triethylamine; In tetrahydrofuran; at 65℃; under 760.051 Torr; for 24h;Inert atmosphere; Green chemistry;
General procedure: A 25 mL, three-necked round-bottom flask equipped with a refluxcondenser and a magnetic stir bar was charged sequentially withSiO2?P?RhCl(PPh3)2 (16 mg, 0.006 mmol), disulfide or diselenide(0.2 mmol), alkyl halide (0.44 mmol), THF (1.0 mL), and Et3N(0.2 mL) under argon. Then hydrogen was introduced to the resultingsuspension. The mixture was stirred at 65 °C for 24 h. After beingcooled to room temperature, the mixture was diluted with Et2O (10 mL)and filtered. The SiO2?P?RhCl(PPh3)2 complex was washed withTHF (2 × 5 mL) and Et2O (2 × 5 mL) and reused in the next run. Theether solution was concentrated under a reduced pressure, and theresidue was purified by preparative TLC (hexane) to afford the desiredproduct.
To a solution of 1,1,4,7,10,10-hexamethyl triethylenetetraamine (0.601 g, 2.61 mmol) in acetonitrile (0.50 mL) was added 1-bromododecane (1.30 g, 5.23 mmol). The resulting colorless solution was heated at reflux for 19 h. The reaction mixture was concentrated under reduced pressure, washed with warm hexanes, and concentrated under reduced pressure to afford a sticky copper solid (1.76 g, 93% yield);
With sodium hydroxide; tetrabutylammomium bromide;
COMPARATIVE EXAMPLE 6 Preparation of N-dodecylcaprolactam in the presence of methyl tert-butyl ether as solvent. 81 g of methyl tert-butyl ether, 17.8 g (0.157 mol) of caprolactam, 18.9 g (0.47 mol) of pearl sodium hydroxide, 2.03 g (0.006 mol) of tetrabutylammonium bromide and 37.4 g (0.15 mol) of dodecyl bromide are introduced into a 250-ml reactor equipped and treated as in Example 1. The mixture is stirred and heated at 60° C. for 9 hours 30 min. It is then treated as in Comparative Examples 2 and 3. 34.5 g of crude N-dodecylcaprolactam are obtained with a purity of 86percent. The chemical yield of N-dodecylcaprolactam is 72percent.
(b) 2-Dodecyltetrazoleacetic acid, ethyl ester The tetrazoleacetic acid, ethyl ester (50 g, 0.26 tool) obtained in (a) was suspended in acetonitrile (600 mL) and triethylamine (52.4 g, 0.52 tool)was added in one portion. The solution was heated at reflux for 5 minutes, cooled to 24 C., and then treated dropwise with 1-bromododecane (64.5 g, 0.26 mol). The solution was refluxed overnight, cooled, and the solvent concentrated in vacuo. The residue was triturated with ethyl acetate (300 mL), filtered, and the filtrate was washed with aqueous HCl (1M), brine, dried (MgSO4), and filtered. The filtrate was concentrated in vacuo leaving a viscous liquid. The 2-isomer was separated from the crude mixture using silica gel chromatography (elution with 25% EtOAc/75% hexane), isolating 2-dodecyltetrazoleacetic acid, ethyl ester (41.8 g, 49%) as a pale yellow liquid.
With potassium hydroxide; In water; at 65℃; for 16h;
The resulting product of step 5A-1, triphenylen-2,3,6,7,10,11-hexanol (10 mmol)Bromododecyl (60 mmol) andPotassium hydroxide (306 mmol) was added to distilled water (50 mL)And the mixture was refluxed at 65 ° C for 16 hours to obtain 2,3,6,7,10,11-hexakis (dodecyloxy) triphenylene (3, Compound 51) (yield: 74percent).
74%
With potassium hydroxide; In water; at 65℃; for 16h;
Triphenylene-2,3,6,7, 10,11 -hexanol (10 mmol) obtained from Step 5A- 1 was added to a solution in which bromododecyl (60 mmol) and potassium hydroxide (306 mmol) were dissolved in distilled water (50 ml), and the mixture was refluxed at 65° C. for 16 hours to obtain 2,3,6,7,10,11-hexakis (dodecyloxy) triphenylene (3, compound 51) (yield: 74percent). 10400] 2,3,6,7,10,11 -hexakis (dodecyloxy) triphenylene:H NMR (600 MHz, CDC13) oe 7.92 (s, 6H), 4.16 (t, 8H),1.76 (m, 8H), 1.43-1.26 (m, 72H), 0.88 (t, 12H)10401] FIG. 22 is a ?H-NMR spectrum of 2,3,6,7,10,11-hexakis (dodecyloxy) triphenylene according to PreparationExample 5A measured in a CDC13 solvent.
35%
With potassium carbonate; In N,N-dimethyl-formamide; at 60℃;
In a 100 ml double-necked flask, <strong>[4877-80-9]2,3,6,7,10,11-hexahydroxytriphenylene</strong> (50 mg, 0.15 mmol) was dissolved in dry DMF (5 ml) in a nitrogen stream. To the solution were added finely ground potassium carbonate (0.13 g, 6.0 eq.) and dodecyl bromide (246.7 mg, 6.6 eq.) and the resultant mixture was stirred overnight at 60° C. There was added 200 ml of distilled water and the precipitate was collected by filtration and washed with methanol. The crude product was dissolved in chloroform and purified by column chromatography (silica gel; hexane: chloroform=2:1) to give compound 3 as white solid (70 mg/35percent). The product was identified by MALDI-TOF-MS, elemental analysis and 1H-NMR (see Table 2). MALDI-TOF-MS (CHCA): m/z 1334.82 (Calcd for [M+H]+1334.50); Anal. Calcd for C90H156O6.0.75CHCl3: C, 76.56; H, 11.10percent. Found: C, 76.45; H, 11.52percent. TABLE 2 1H-NMR(RT, CDCl3, 600MHz, TMS standard) split integral theoretical delta (J/Hz) ratio ratio assignment 0.86 t 20.0 18Ha(CH3) 1.20-1.55 m 196.3 108H b(CH2) 1.97 m 18.2 12Hc(OCH2CH2) 4.23 q 13.9 12Hd(OCH2) 7.83 s 6.0 12H e
EXAMPLE 5 N-Dodecyl Imidazole A stirred mixture of 9.96 g. of dodecyl bromide (40 mM), 5.44 g. of imidazole (80 mM), 100 ml. of 0.97N NaOH (97 mM), 100 ml. of PhH, and 336 mg. of Aliquat 336 (1 mM; methyltricaprylylammonium chloride) was refluxed for 23 h. The benzene layer was separated, washed with brine containing a little NaOH, and evaporated. The residue was purified of a little front-running and some origin impurities by quick chromatography on 150 g. of silica gel with 1:1 CH2 Cl2 --EtOAc (Rf 0.35), affording 7.48 g. of single-spot material which was distilled at ca. 0.5 Torr (bp 144° C.) to give 6.97 g. of pure product (74percent): NMR 7.5 (s, 1H), 7.1 (br s, 1H), 6.95 (br s, 1H), 3.95 (t, J=7 Hz, 2H), 1.85 (m, 2H), 1.3 (s, 18H), 1.0 ppm (m, 3H).
EXAMPLE 3 N-n-dodecylcaprolactam 3.1 g (0.05 mol) of sodium oxide (Na2 O) are suspended in 150 ml of 1,2-dimethoxyethane, and then 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are added. The reaction mixture is stirred at 50° C. for two hours, during which the voluminous precipitate of the sodium salt of the caprolactam forms. Then 24.9 g (0.1 mol) of n-dodecyl bromide are added, and the mixture is stirred and heated under reflux for 20 hours. The working-up is carried out as indicated in Example 1. Boiling point (0.15 mm) 175°-176° C.; yield 20.8 g.
EXAMPLE I Preparation of 1-dodecylazacycloheptan-2-one The operation was carried out under nitrogen. In a 5 liter 3-neck flask equipped with an efficient condenser, an additional funnel and a mechanical stirrer was placed 91.8 g (1.91 M) of 50percent sodium hydride (dispersed in mineral oil). This was mixed with 600 ml of pet. ether (30-60), the mixture was momentarily stirred and then sodium hydride was allowed to settle. Most of the petroleum ether was pipetted out and 1500 ml of toluene was added to the NaH. To this was added under stirring and dropwise a solution of 180 g (1.59 M) of azacycloheptan-2-one in 800 ml of toluene. Foaming, hydrogen evaluation and formation of sodium salt took place. After the addition, the reaction mixture was refluxed for two hours and then cooled to room temperature. A solution of 398 g (1.59 M) of 1-bromododecane in 100 ml of toluene was added dropwise under stirring. Upon completion of the addition, the reaction mixture was refluxed for 45 hours. After cooling, the contents were filtered through celite and the filtrate was concentrated to a yellow oil. This was distilled at 155° to 160°/100mu to give 402 g (89percent) of a clear colorless oil. Redistillation at 155° to 160°/100mu gave 396 g (88.5percent) of pure 1-dodecylazacycloheptan-2-one.
EXAMPLE 3 Preparation of 1-dodecylazacycloheptan-2-one with tricaprylylmethylammonium chloride (aliquat 336.(R).) as catalyst. To a solution of 2.5 g (22.09 millimole) of azacycloheptan-2-one and 10 ml (41.64 millimole) of 1-bromododecane in 50 ml of toluene was added 50 ml of 50percent sodium hydroxide solution followed by 0.45 g (1.1 millimole) (0.05 mole percent) of tricaprylylmethylammonium chloride (Aliquat 336.(R).). The mixture was vigorously stirred with a mechanical stirrer at 40°-50° C. for 120 hrs. After cooling to room temperature the organic layer was separated, the aqueous layer was extracted with 2*100 ml of ether and the combined organic solution was washed twice with a saturated sodium chloride solution. After drying over anhydrous magnesium sulfate the filtrate was concentrated and the residue was fractionally distilled. 3.62 g forerun was excess 1-bromododecane (which can be recycled). The desired compound, 1-dodecylazacycloheptan-2-one distilled at 145°-155°/0.2 mm. Yield 6.15 g (99.2percent).
COMPARISON EXAMPLE 2 A 46.0 g quantity of 1-dodecylazacycloheptane-2-one (yield of 54.6percent based on the azacycloheptane-2-one) and 5.0 g of dodecyl ether (yield of 6.3percent based on the dodecyl bromide) were produced by conducting the same reaction and the same aftertreatment as in Comparison Example 1 with the exception of changing the reaction time of COMPARISON EXAMPLE 1 to 10 hours.
41
[ 105-60-2 ]
sodium hydride-mineral oil[ No CAS ]
[ 143-15-7 ]
[ 59227-89-3 ]
Yield
Reaction Conditions
Operation in experiment
60 g (80%)
STR23 Following Example 10, 15.3 g of 50percent sodium hydride-mineral oil dispersion (7.65 g NaH, 0.319M), 30 g (0.266M) of azacycloheptan-2-one and 66.1 g (0.265M) of 1-bromododecane on 20 hours reflux gave 60 g (80percent) of colorless product; b.p. 175°-180°/0.3 mm.
Example 3 Preparation of 2,2--[2-dodecylthio-1,3,5-triazine-4,6-diylbis-(thio)]bis dodecanoic acid. A stirred solution of KOH (5.6 g; 0.1 mole) in ethanol (100 ml) is cooled to 5-10C and treated with trithiocyanuric acid (4.42 g; 0.025 mole). After stirring for 30 minutes, the reaction mixture is treated with 2-bromododecanoic acid (13.9 g; 0.05 mole) in small portions over 10-15 minutes. The resulting white suspension is stirred for a further 30 minutes at 10C and is then allowed to warm to ambient temperature. Upon reaching ambient temperature, the reaction mixture is heated to reflux and maintained at this temperature for 3 hours. The reaction mixture is then cooled to 5C and treated with a solution of KOH (1.4 g; 0.025 mole) in ethanol (50 ml) followed by dodecyl bromide (6.2 g; 0.025 mole). The reaction mixture is allowed to warm to ambient temperature and is then heated to reflux and maintained at this temperature for 2 hours. The reaction mixture is cooled to ambient temperature and the solvent removed under reduced pressure. The residue is suspended in water (100 ml and acidified with concentrated HCl to pH 3. The acidified aqueous suspension is then extracted with either (200 ml) and the ether extract is washed with water (3 x 50 ml). The extract is dried over MgSO4, filtered, then evaporated to yield 14.7 g (79 %) of a yellow viscous oil.
In a three-necked 2,000 mL glass flask equipped with a reflux tube and a dropping funnel, 58.3 g of a ground magnesium metal was put, and dried sufficiently. A gas in the flask was displaced with a nitrogen gas, and there was put therein 400 mL of purified tetrahydrofuran as a solvent with a syringe at ordinary temperature and atmospheric pressure. There was further added dropwise 192 mL of dodecyl bromide manufactured by Kanto Chemical Co., Inc. with the dropping funnel over one hour to the mixture in the flask cooled with ice, and then, the reaction was continued for two hours under the cooling with ice. To the obtained mixture cooled with ice, 120.6 mL of <strong>[54458-61-6]2,3,4,5-tetramethyl-2-cyclopenten-1-one</strong> manufactured by Kanto Chemical Co., Inc. and 100 mL of purified tetrahydrofuran as a solvent were added dropwise over one hour with the dropping funnel, and then, the reaction was continued for fifteen hours while raising gradually the temperature of the mixture in the flask up to room temperature. After completion of the reaction, 100 mL of tetrahydrofuran was added thereto, and then, 300 mL of a hydrochloric acid having a concentration of 0.5 mol/L was added gradually to the mixture under cooling said mixture with ice in order to inhibit a sudden reaction. The organic and water layers thereof were separated from each other, and the organic layer was washed with 200 mL of water. The solvent contained in the washed layer was distilled away under reduced pressure, thereby obtaining an organic component. The organic component was added dropwise with a dropping funnel to 1.0 L of hot water boiling at 60 to 80 C. under a reduced pressure, thereby azeotropically distilling away unreacted materials together with water. When an amount of the distillate was over 500 mL, the azeotropic distillation was stopped, and 500 mL of water was further added thereto, and the azeotropic distillation was started again, thereby obtaining the remaining organic component. The remaining organic component was mixed with 50 mL of saturated brine, and the organic and water layers thereof were separated from each other. The organic layer was dried over anhydrous magnesium sulfate. The mixture was filtered, and the separated solid containing mainly the above-mentioned magnesium sulfate was washed with hexane. The solvent contained in the hexane solution was distilled away under reduced pressure, said hexane solution being a combination of (1) the filtrate obtained in the above-mentioned filtration with (2) hexane obtained in the above-mentioned washing with hexane. The remainder was dried at 40 C. for two hours under reduced pressure, thereby obtaining 228 g of dodecyl(tetramethyl)cyclopentadiene. Gas chromatography analysis showed that purity of the obtained dodecyl(tetramethyl)cyclopentadiene was 64% by weight. 1H NMR analysis thereof showed: 0.83 to 0.89 ppm (the terminal methyl group in the alkyl chain), 0.95 to 1.02 ppm (the methyl group), 1.15 to 1.45 ppm (the methylene in the alkyl chain), 1.05 to 1.90 ppm (the methyl group), 2.00 to 2.36 ppm (the base methylene in the alkyl chain), and 2.40 to 2.67 ppm (the methyne on the 5-membered ring). The above-mentioned gas chromatography analysis was conducted under the following conditions: measuring instrument: GC-17A manufactured by Shimadzu Corporation, column temperature: 100 C. up to 300 C. at a temperature-raising rate of 5 C./minute, column: DB-5MS having a length of 30 m, a radius of 0.25 mm, and a wall-thickness of 1 mum, and sample concentration: 0.05 mL/mL. The above-mentioned 1H NMR analysis and the below-mentioned 13C NMR analysis were conducted under the following conditions: measuring instrument: 400 MHz NMR manufactured by JEOL LTD, measuring temperature: 23 C., solvent: chloroform-d (for analysis of the polymer, and for ligand analysis of the transition metal compound), and toluene-d8 (for analysis of the transition metal compound), and sample concentration: 20 mg/mL.
The compound dithiophene cyclopentene (2.00 g, 11.22 mmol), KI (55.9 mg, 336.57 mumol) and KOH (2.01 g, 35.90 mmol) were dissolved in dimethyl sulfoxide (52 mL), stirred at room temperature for 1 hour, add the compound bromododecane (5.87 g, 23.56 mmol), stirred at room temperature overnight. The system was poured into a large amount of water and quenched, extracted with diethyl ether, separated, washed with water and dried over anhydrous magnesium sulfate. After removing the solvent under reduced pressure, it was separated on a silica gel column (eluent: petroleum ether) to obtain a pale yellow color viscous liquid 8 (5.15 g, yield: 89%).
1,1'-(2-(2,4-difluorophenyl)-2-hydroxypropane-1,3-diyl)bis(4-dodecyl-1H-1,2,4-triazol-4-ium) bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80.4%
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.
(b) 4-(dodecyloxymethyl)cyclopent-1-ene (0166) (0167) To a suspension of excess NaH in dry 100 ml dry THF al -78 C. was added compound cyclopent-3-enylmethanol (0.3720 g, 3.79 mmol) and stirred for 1 h. Temperature was gradually increased to -40 C. and bromododecane (1.3828 g, 5.68 mmol, 1.5eq) was added drop wise over 0.5 h. The mixture was mildly refluxed overnight. THF was distilled off under vacuum and the mixture was diluted with DCM. The organic solution was filtered and washed with H2O (6×50 mL), saturated NH4Cl (3×50 mL), and H2O (2×50 mL), dried over MgSO4, and purified with silica Hex:EtOAc (2:8) to afford a clear oil solid (2.95 mmol, MW 266.46 g/mol, 78%). 1H NMR (700 MHz, CDCl3): delta 0.89-0.91; (t, 3H, J=7.04), 1.29-1.35; (m), 1.56-1.59; (dd, 2H, J=13.35, 6.06 Hz), 2.09-2.12; (dd, 2H, J=14.07, 4.72 Hz), 2.47-2.5 (dd, 2H, J=14.14, 8.75 Hz), 2.57-2.60; (tt, 1H, J=8.39,4.13 Hz), 3.32-3.33; (d, 2H, J=7.41 Hz), 3.42-3.44; (t, 2H, J=6.72 Hz), 5.63; (s, 1H).
Step 1 In a three-necked flask equipped with 17.73 g of trimercaptotriazine, 50.0 g of bromododecane was slowly added dropwise, 9 g of sodium hydroxide was added as an antibiotic, overnight, 6 g of propylene oxide was added and the reaction was continued until the reaction was complete to give DSEP 45.76 g as a yellow oil in 80.5% yield;
tert-butyl 4-(2-(didodecylamino)ethyl)piperazine-1-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
18%
With potassium carbonate; In acetonitrile; at 20℃; for 12h;
Step 1 : fert-Butyl 4-(2-(didodecylamino)ethyl)piperazine-l -carboxylate Chemical Formula: C35H71N3O2 Molecular Weight: 565.97 [00570] A mixture of 1 -bromododecane (1.1 mL, 4.6 mmol), 4-(2-aminoethyl)-l -boc- piperazine (1.0 g, 4.4 mmol), K2CO3 (0.61 g, 4.4 mmol), in 10 mL MeCN was allowed to stir at rt for 12 h. After this time the reaction was filtered and concentrated. The crude material was purified by silica gel chromatography (0-20percent MeOH in DCM with 1percent NH4OH to afford tert- butyl 4-(2-(didodecylamino)ethyl)piperazine-l-carboxylate (450 mg, 0.80 mmol, 18percent). UPLC/ELSD: RT = 2.87 min. MS (ES): m/z (MH+) 566.655 for C35H71N3O2 (1296) XH NMR (400 MHz, CDCI3) delta: ppm 3.40 (m, 4H); 2.56 (m, 2H); 2.40 (m, 10H); 1.44 (s, 9H); 1.40-1.24 (m, 40H); 0.86 (t, 6H).
18%
With potassium carbonate; In acetonitrile; at 20℃; for 12h;
A mixture of 1 -bromododecane (1.1 mL, 4.6 mmol), 4-(2-aminoethyl)-1-boc-piperazine (1.0 g, 4.4 mmol), K2CO3 (0.61 g, 4.4 mmol), in 10 mL MeCN was allowed to stir at rt for 12 h. After this time the reaction was filtered and concentrated. The crude material was purified by silica gel chromatography (0-20percent MeOH in DCM with 1percent NH4OH to afford tert- butyl 4-(2-(didodecylamino)ethyl)piperazine-l-carboxylate (450 mg, 0.80 mmol, 18percent).UPLC/ELSD: RT = 2.87 min. MS (ES): m/z (MH+) 566.655 for C35H71N3O21H NMR (400 MHz, CDCl3) delta: ppm 3.40 (m, 4H); 2.56 (m, 2H); 2.40 (m, 10H); 1.44 (s, 9H); 1.40-1.24 (m, 40H); 0.86 (t, 6H).
<strong>[1047-16-1]Quinacridone</strong> (1.5616 g, 5 mmol), cesium carbonate (3.258 g, 10 mmol) and tetrabutylammonium bromide (TBAB) (0.323 mg, 1 mmol) was dissolved in 30 mL of DMSO, and after being stirred at room temperature for 4 h, 1-bromo-dodecane was slowly added dropwise.(6.231 g, 25 mmol). The reaction was stirred at room temperature for 20 h and then stirred at 90 C for 6 h to stop the reaction. To be opposed After the solution was cooled, it was poured into 100 mL of saturated saline until the red solid precipitated completely and was filtered. The cake was washed with distilled water in that order. Ethanol wash. The filter cake was dissolved in 20 mL of methylene chloride, filtered again to remove insolubles, and the filtrate was dried over anhydrous magnesium sulfate and removed. Solvent, solid was recrystallized from ethyl acetate to give compound III as an orange-red solid, with a yield of about 84% (substance of compound). Meter).
With sodium hydrogencarbonate; In acetonitrile; at 20℃; for 18h;Reflux; Inert atmosphere;
General procedure: In 100 ml round-bottom flask, a suspension of 0.01 mol amino acid ethyl ester hydrochloride (II) and 0.05Mole of NaHCO3 in 40 ml freshly distilled acetonitrile was stirred at room temperature during dropwise addition of 0.015 mol 1-bromododecane (III). After complete addition,the mixture was refluxed for 18 h under nitrogen atmosphere. After cooling to room temperature, acetonitrile was removed under vacuum and thewhite residue of ethyl dodecyl amino acid surfactant (IV) is dissolved in 30ml dichloromethane. It was washed with 0.1M HCl (25ml× 3) and distilled water (25 ml × 2). Dichloromethane was evaporated to give the pure product (V) in 66-92% yield. The product obtained is dissolved in 30 ml of absolute ethanol and 3 ml of 3.0 M NaOH is added dropwise to the solution. The reaction mixture stirred at room temperature for 6 h. The precipitate sodium dodecyl amino acid surfactant (VI) was filtered-off and washed twice with absolute ethanol in poor yield (22-46% yield). The reactions are represented in Scheme1.
Add 3g to 50mL DMF solvent<strong>[23351-91-9]5-bromoisophthalic acid</strong> (0.012 mol) and 4.8 g potassium hydrogencarbonate (0.048 mol),Stir at room temperature to form a potassium salt.7.48g of n-bromodedodecane (0.03mol) 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.Column chromatography with petroleum ether/ethyl acetate (15/1) as eluentIsolation gave a white solid.
Add 3 g of <strong>[23351-91-9]5-bromoisophthalic acid</strong> (0.012 mol) and 4.8 g of potassium bicarbonate to 50 mL of DMF solvent.(0.048 mol), stirred at room temperature to form a potassium salt. 6.64g of n-bromodecane (0.03mol) was added to the mixed solution and stirred at 90 CReaction for 12 hours. The reaction was stopped, the solution was cooled to room temperature, poured into 300 mL of water and extracted with ethyl acetate. noDrying with sodium sulfate, filtering and drying the solvent. The crude product was subjected to column chromatography using petroleum ether/ethyl acetate (15/1) as eluent.Leave to give a white solid.
With N-butylammonium bromide; potassium hydroxide; In water; toluene; at 65℃; for 2h;
General procedure: N-butylammonium bromide (2.9 mmol, 0.9 g), potassium hydroxide (143.8 mmol,8.1 g) was dissolved in 8 mL of water and heated to 65 C in an oil bath. 2-Iodo-9H-indole (14.4 mmol, 4.2 g) and 1-bromo alkane (86.1 mmol) were dissolved in 15 mL of toluene, and then a toluene solution was added to the above aqueous solution and reacted at 65 C for 2 hours. After the completion of the reaction, the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, and concentrated under reduced pressure on a rotary evaporator, and the residue was purified by column chromatography (petroleum ether).
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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