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USD 0.00
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Structure of 112-29-8 * Storage: {[proInfo.prStorage]}
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of Organic Chemistry, 2008, vol. 73, # 3, p. 830 - 839
2
[ 112-29-8 ]
[ 143-15-7 ]
[ 2687-96-9 ]
Reference：
[1] Journal of Pharmaceutical Sciences, 1983, vol. 72, # 11, p. 1354 - 1356
3
[ 288-32-4 ]
[ 112-29-8 ]
[ 33529-02-1 ]
Yield
Reaction Conditions
Operation in experiment
94%
at 50℃; Microwave irradiation
In a wide-necked Erlenmeyer flask areintroduced 6.8g (0.1 mol) imidazole, 45.5g (0.1 mol)1-bromohexadecan, 2.4g (7.5mmol)tertiobutyllammoniumbromid (TBAB). The mixtureis adsorbed on mixture of potassium carbonate andpotassium hydroxide ratio 1:1 and then irradiatedin an open vessel in a domestic microwave oven300 Watt power for 3 min by period of 20 secondstill it changed to pasty.After dilution in dichloromethane followedby washing with water, the organic phase isseparated and dried over sodium sulfate. Afterfiltration, the solvent is evaporated under vacuum.
88.3%
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 after stirring until a clear solution, to which was added dropwise 2.21 g (10.0 mmol) of bromo decane, the reaction of about 4 ~ 6 h, the reaction was poured into 10 mL of water and extracted with chloroform 3 × 10 mL, washed with water The chloroform layer was 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- decyl-imidazole 1.84 g, yield 88.3percent.
86%
Stage #1: With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5 h; Inert atmosphere Stage #2: at 20℃; Inert atmosphere
General procedure: This compound was synthesized using a variation of the procedure previously reported [32]. Sodium hydride (60percent dispersion in mineral oil, 1.56 g, 39.0 mmol) was suspended in dry THF (50 mL) under Ar at 0 °C. Imidazole (2.16 g, 31.7 mmol) was dissolved in dry THF (20 mL) and added drop-wise. After 30 min, 1-bromodecane (5.41 g, 24.5 mmol) was added. The resulting reaction mixture was then stirred at room temperature overnight. After careful addition of a few drops of water to quench the remaining sodium hydride, the organic solvent was removed in vacuo, and diethyl ether (50 mL) was added. This solution was then washed with water (3 × 50 mL), dried over anhydrous MgSO4, filtered, concentrated, and then purified by flash chromatography (ethyl acetate/hexanes = 10/1 (v/v)) to give the product as a light yellow oil (yield: 4.38 g, 86percent). Spectroscopic and purity data matched those reported for this compound [32].
81.2%
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.
76%
Stage #1: With sodium hydroxide In dimethyl sulfoxide at 20℃; for 1.5 h; Stage #2: at 20℃;
General procedure: Imidazole (3)/benzimidazole(5) (10 mmol) was dissolved in 10 ml of DMSO and solid NaOH(15 mmol) was then added it. The resulting pale yellow suspensionwas stirred in air at room temperature for 1.5 h, after which, thealkyl bromides or benzyl chlorides (15 mmol) were added andallowed to react until completion (TLC). Water (50 ml) was thenadded and the products were extracted with ethyl acetate. Combinedorganic layers were washed several times with water, thenwith brine, dried over Na2SO4 and subjected to chromatographicpurification over silica (100–200 mesh) using MeOH: EtOAc 5:95(v/v) as the mobile phase. Compounds 4a-f were isolated as yellowoils whereas, the compounds 7a-e were white solid. Spectroscopic data of the N-alkyl imidazoles are in accord with earlier literatureand thus are not shown here [30].
Reference：
[1] Journal of Materials Chemistry, 2011, vol. 21, # 33, p. 12280 - 12287
[2] Oriental Journal of Chemistry, 2015, vol. 31, # 4, p. 2391 - 2394
[3] Patent: CN103951702, 2016, B, . Location in patent: Paragraph 0049; 0050
[4] Polymer, 2014, vol. 55, # 26, p. 6664 - 6671
[5] New Journal of Chemistry, 2007, vol. 31, # 6, p. 879 - 892
[6] Journal of Surfactants and Detergents, 2016, vol. 19, # 4, p. 681 - 691
[7] European Journal of Inorganic Chemistry, 2015, vol. 2015, # 3, p. 408 - 413
[8] Polyhedron, 2017, vol. 127, p. 68 - 83
[9] Russian Journal of Applied Chemistry, 1996, vol. 69, # 12, p. 1841 - 1848
[10] Organic Letters, 2009, vol. 11, # 8, p. 1757 - 1759
[11] Synthesis, 2009, # 19, p. 3219 - 3226
[12] Organic Letters, 2010, vol. 12, # 21, p. 4988 - 4991
[13] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 17, p. 2863 - 2865
[14] Polish Journal of Chemistry, 1995, vol. 69, # 3, p. 447 - 460
[15] Chemistry Letters, 2005, vol. 34, # 3, p. 442 - 443
[16] Journal of Chemical and Engineering Data, 2006, vol. 51, # 4, p. 1274 - 1279
[17] Electrochimica Acta, 2010, vol. 55, # 20, p. 5652 - 5658
[18] Physical Chemistry Chemical Physics, 2011, vol. 13, # 6, p. 2062 - 2068
[19] Dyes and Pigments, 2013, vol. 96, # 1, p. 16 - 24,9
[20] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 4, p. 423 - 427
[21] Journal of the Chinese Chemical Society, 2013, vol. 60, # 7, p. 745 - 754
[22] Chemical Biology and Drug Design, 2014, vol. 83, # 3, p. 278 - 288
[23] RSC Advances, 2015, vol. 5, # 4, p. 2869 - 2881
[24] RSC Advances, 2015, vol. 5, # 71, p. 57968 - 57974
[25] Langmuir, 2015, vol. 31, # 12, p. 3587 - 3595
[26] RSC Advances, 2015, vol. 5, # 28, p. 21865 - 21876
[27] Molecules, 2018, vol. 23, # 9,
Reference：
[1] Zhurnal Obshchei Khimii, 1951, vol. 21, p. 242,248;engl.Ausg.S.263,268
[2] Wear, 1957, vol. 1, p. 291,304
[3] Zhurnal Obshchei Khimii, 1950, vol. 20, p. 2085;engl.Ausg.S.2159
6
[ 112-29-8 ]
[ 1068-90-2 ]
[ 17702-88-4 ]
Reference：
[1] Bioorganic and Medicinal Chemistry, 2006, vol. 14, # 14, p. 4775 - 4780
7
[ 112-29-8 ]
[ 35237-37-7 ]
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 18, p. 2635 - 2637
[2] Liebigs Annalen der Chemie, 1990, # 12, p. 1175 - 1183
8
[ 112-30-1 ]
[ 112-29-8 ]
Yield
Reaction Conditions
Operation in experiment
90%
With polystyrene supported bromo diphenylphsophonium bromide In chloroform at 60℃; for 18 h;
General procedure: To asuspension of PSP Cl or PSP Br (6 equiv) in CHCl3 or DCE (20 mL) was added the appropriate substrate(s) e.g. alcohol/aldehyde/epoxide/oxime/carboxylicacid/amine (1 equiv). The mixture was heated at either 60°C (CHCl3 reactions) or 75°C (DCE reactions) for 18 h. The reaction mixture was filtered and the filter cake washed with CH2Cl2 (2 10 mL). The solvent was removed in vacuo to afford the corresponding products, which were either judged pure by 1H NMR analysis of the crude reaction product or were purified via normal phase silica gel flash column chromatography eluting with a Et2O/petroleum ether 40–60 solvent mixture. The recovered polymer could be reused without anyfurther manipulation.
Reference：
[1] Tetrahedron, 2003, vol. 59, # 13, p. 2253 - 2258
[2] Synthesis, 1983, # 4, p. 306 - 308
[3] Organic Process Research and Development, 2002, vol. 6, # 2, p. 190 - 191
[4] Tetrahedron Letters, 2003, vol. 44, # 44, p. 8143 - 8147
[5] Tetrahedron Letters, 2014, vol. 55, # 4, p. 799 - 802
[6] Chemistry - A European Journal, 2011, vol. 17, # 40, p. 11290 - 11295
[7] Chemical Communications, 2010, vol. 46, # 17, p. 3025 - 3027
[8] Journal of the American Chemical Society, 1928, vol. 50, p. 1477
[9] Journal of the American Chemical Society, 1928, vol. 50, p. 1506
[10] Bulletin de la Societe Chimique de France, 1946, p. 366
[11] Chemische Berichte, 1942, vol. 75, p. 670,671[12] Chemische Berichte, 1944, vol. 77/79, p. 78
[13] Journal of the American Chemical Society, 1942, vol. 64, p. 1802
[14] Journal fuer Praktische Chemie (Leipzig), 1932, vol. <2>135, p. 193,202
[15] Tetrahedron Letters, 1987, vol. 28, # 11, p. 1223 - 1224
[16] Molecular crystals and liquid crystals, 1982, vol. 88, # 1-4, p. 81 - 86
[17] Journal of Organometallic Chemistry, 1998, vol. 554, # 2, p. 135 - 137
[18] Journal of Organometallic Chemistry, 1998, vol. 557, # 2, p. 157 - 161
[19] Tetrahedron, 2007, vol. 63, # 32, p. 7696 - 7701
[20] Synthesis, 1987, # 5, p. 511 - 512
[21] Journal of Mass Spectrometry, 2008, vol. 43, # 9, p. 1224 - 1234
[22] Journal of Organic Chemistry, 2011, vol. 76, # 16, p. 6749 - 6767
9
[ 112-17-4 ]
[ 604-69-3 ]
[ 112-29-8 ]
[ 572-09-8 ]
Yield
Reaction Conditions
Operation in experiment
57%
at 20℃; Irradiation; Green chemistry
General procedure: Bromine (1.5 mmol, 0.08 mL) was added slowly to a magnetic stirring barand perfluorohexanes (4.0 mL) in a test tube (14 mmφ x 105 mm) with a septum and then 1-O-acetylsugar 1a (1 mmol, 392 mg) in ethyl acetate (2.0 mL) wasadded slowly, forming three layers. The test tube was stirring upon irradiationwith 15 W black light (at 352 nm, TOSHIBA EFD15BLB-T) at 30 C. The light source wasplaced away from the test tube. After 23 hours, the bromine layer disappearedand the fluorous layer recovered transparency. The ethyl acetate layer wastaken up with a pipette. Then, additional ethyl acetate (2 mL x 4) was placedon the residual FC-72 layer, followed by decanting off. The combined ethylacetate layer was washed with water (15 mL), aqueous sat. NaHCO3 (20mL), brine (20 mL) and, dried over Na2SO4, andconcentrated. Purification by chromatography on silica gel with hexane/AcOEt = 2/1gave glycosyl bromide 2a (0.91 mmol,374 mg) in 91percent yield
Reference：
[1] Journal of Molecular Catalysis A: Chemical, 2015, vol. 407, p. 60 - 66
11
[ 62871-09-4 ]
[ 112-29-8 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 12, p. 4417 - 4429
[2] Tetrahedron Letters, 2010, vol. 51, # 2, p. 439 - 441
12
[ 693-58-3 ]
[ 112-29-8 ]
Reference：
[1] Patent: US2007/281873, 2007, A1,
13
[ 98750-95-9 ]
[ 112-29-8 ]
Reference：
[1] Journal of the Chemical Society, Chemical Communications, 1985, # 9, p. 571 - 572
14
[ 4101-68-2 ]
[ 124-18-5 ]
[ 112-29-8 ]
Reference：
[1] Journal of Organic Chemistry, 1981, vol. 46, # 19, p. 3909 - 3911
15
[ 333-88-0 ]
[ 112-29-8 ]
Reference：
[1] Synthesis, 1987, # 5, p. 511 - 512
16
[ 41233-29-8 ]
[ 112-29-8 ]
Reference：
[1] Bulletin of the Chemical Society of Japan, 1988, vol. 61, # 12, p. 4371 - 4378
[2] Bulletin of the Chemical Society of Japan, 1988, vol. 61, # 12, p. 4371 - 4378
17
[ 112-30-1 ]
[ 1034-39-5 ]
[ 112-29-8 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1959, vol. 626, p. 26,33
18
[ 558-13-4 ]
[ 112-30-1 ]
[ 112-29-8 ]
[ 5451-52-5 ]
Reference：
[1] Journal of Organic Chemistry, 1997, vol. 62, # 20, p. 7061 - 7064
19
[ 112-29-8 ]
[ 1120-24-7 ]
[ 7173-51-5 ]
Reference：
[1] European Journal of Pharmaceutical Sciences, 2012, vol. 46, # 5, p. 336 - 345
20
[ 112-29-8 ]
[ 7173-51-5 ]
Reference：
[1] Langmuir, 2013, vol. 29, # 21, p. 6242 - 6252
[2] International Journal of Pharmaceutics, 2016, vol. 512, # 1, p. 273 - 281
21
[ 112-29-8 ]
[ 75-50-3 ]
[ 2082-84-0 ]
Reference：
[1] Journal of the American Chemical Society, 1943, vol. 65, p. 693
[2] Journal of pharmaceutical sciences, 1966, vol. 55, # 4, p. 414 - 417
[3] Journal of the American Chemical Society, 1970, vol. 92, p. 7393 - 7400
[4] Bulletin of the Chemical Society of Japan, 2011, vol. 84, # 3, p. 312 - 319
[5] Journal of Surfactants and Detergents, 2012, vol. 15, # 5, p. 587 - 592
22
[ 7758-89-6 ]
[ 112-29-8 ]
[ 106-37-6 ]
[ 106418-67-1 ]
Reference：
[1] Patent: US5716542, 1998, A,
23
[ 112-29-8 ]
[ 106418-67-1 ]
Reference：
[1] Journal of Materials Chemistry, 2001, vol. 11, # 4, p. 1063 - 1071
24
[ 872-31-1 ]
[ 112-29-8 ]
[ 65016-55-9 ]
Reference：
[1] Journal of Materials Chemistry C, 2015, vol. 3, # 32, p. 8351 - 8357
[2] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9700 - 9713
[3] Chemical Communications, 2011, vol. 47, # 33, p. 9471 - 9473
[4] Journal of Materials Chemistry, 2011, vol. 21, # 5, p. 1582 - 1592
[5] Macromolecules, 2011, vol. 44, # 16, p. 6370 - 6381
25
[ 872-31-1 ]
[ 112-29-8 ]
[ 3172-56-3 ]
[ 740804-46-0 ]
[ 65016-55-9 ]
Yield
Reaction Conditions
Operation in experiment
1.7 - 64.5 %Chromat.
Stage #1: With magnesium In tetrahydrofuran at 20℃; for 48 h; Stage #2: at 20℃;
EXAMPLE 16 (COMPARATIVE); 3-Bromothiophene (1 eq.) is combined in a flask with 1.1 mol of magnesium metal and 1.15 mol of 1-bromohexane in a 100percent THF solvent, and with 815 mg of a (1,3-bis (diphenylphosphino)propane)dichloro Nickel (II) catalyst in suspension. The Grignard reagent concentration in the solvent is 2.2 mol/L. The reactions were conducted at room temperature. Immediate gas chromatography of the reaction product showed 85.3percent 3-bromothiophene, 1.7percent 3-hexylthiophene and 0.5percent bis-thienyl side-product. GC after 48 hours showed 2.9percent 3-bromothiophene, 64.5percent 3-hexylthiophene, 9.8percent bis-thienyl side-product and 3.34percent 3-(1-methylpentyl)thiophene. This shows bad selectivity with a 100percent THF solvent.
86.7 %Chromat.
Stage #1: With magnesium In tetrahydrofuran; tert-butyl methyl ether at 20℃; for 15 h; Stage #2: at 20℃;
EXAMPLE 17 (COMPARATIVE); 3-Bromothiophene (1 eq.) is combined in a flask with 1.2 mol of magnesium metal and 1.2 mol of 1-bromohexane in a 50:50 THF/MTBE solvent, and with 600 mg of a (1,3-bis (diphenylphosphino)propane)dichloro Nickel (II) catalyst in suspension. The Grignard reagent concentration in the solvent is 1.3 mol/L. The reactions were conducted at room temperature. Gas chromatography of the reaction product after 15 hours showed 0.2percent 3-bromothiophene, 86.7percent 3-hexylthiophene, 5.6percent bis-thienyl side-product and 1.59percent 3-(1-methylpentyl)thiophene. This shows high bis-thienyl and 3-(1-methylpentyl)thiophene side-product formation with a 50:50 THF/MTBE solvent. Overall, the comparative examples show that the main input factor for the selectivity is the catalyst, secondly the temperature and solvent is responsible for the final completion of the selectivity. Expressed in numbers: 60percent, 30percent, 10percent responsibility. In methyl-THF, a Grignard reagent concentration of up to 4 mol/L is possible.
Reference：
[1] Chemistry - A European Journal, 2013, vol. 19, # 7, p. 2370 - 2383
29
[ 112-29-8 ]
[ 16433-88-8 ]
[ 175922-78-8 ]
Yield
Reaction Conditions
Operation in experiment
92.7%
With potassium hydroxide; potassium iodide In dimethyl sulfoxide at 0 - 20℃; for 4 h;
EXAMPLE 1 2,7-Dibromo-9,9-didecyifluorene A mixture of 2,7-dibromofluorene (64.8 g, 0.20 mol potassium iodide (3.0 g, 0.018 mol), finely powdered KOH (56.0 g, 1 mol), and DMSO (150 ML) was mechanically stirred under nitrogen in a three-necked round-bottom flask.. The flask was cooled in an ice water bath before adding four batches of the bromoalkyl (90 ML. 95.94 g, 0.434 mol).. After each addition, the internal temperature rose sharply.. Once the last aliquot was completed, the reaction was stirred for 4 hours at room temperature before water (200 ML) was added.. The solid was filtered off and dried in a desiccator equipped with P2O5 under vacuum for 16 hours.. The crude product was recrystallized from ethanol to produce 2,7-dibromo-9,9-didecylfluorene as white crystals (m.p. 40-41° C.) in 92.7percent yield.. Mass Spec. m/z 602,604,606 (M+), 461,463,465 (M-C10H21), 382,384 (461-Br). Anal. Calcd for C33H48Br2: C, 65.56percent; H, 8.00percent; Br, 26.44percent. Found: C, 64.99percent; H, 8.21percent; Br, 27.25percent.
92%
With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 4 h;
2.2.1 2,7-dibromo-9,9-didecylfluorene (1) 1-bromodecane (4.42 g, 20.0 mmol) was added by syringe to a mixture of 2,7-dibromofluorene (2.59 g, 8 mmol), tetrabutyl ammonium bromide (0.02 g, 0.064 mmol) and 2.50 mL of 50percent aqueous sodium hydroxide in dimethyl sulfoxide (50.0 mL). After stirring at room temperature for 4 h, the mixture was poured into water and extracted three times with dichloromethane. The solvent was removed under reduced pressure and the precipitate was purified by column chromatography on silica gel (eluent: petroleum ether) to afford 2,7-dibromo-9,9-didecylfluorene as a white powder (4.45 g, Yield 92percent). 1H NMR (500 MHz, CDCl3, δ): 7.51 (d, 2H, J = 8.70 Hz, Ar-H), 7.45 (m, 4H, Ar-H), 1.91 (m, 4H, CH2), 1.13 (m, 28H, CH2), 0.85 (t, 6H, J = 6.95 Hz, CH3), 0.58 (m, 4H, CH2). FT-IR (cm-1, KBr): ν = 2950, 2836 (s; CH), 1638, 1551 (w; Ar). Anal. Calcd. for C33H48Br2: C 65.56, H 8.00; Found: C 64.72, H 7.62.
90.7%
Stage #1: With potassium <i>tert</i>-butylate In tetrahydrofuranInert atmosphere Stage #2: for 5.5 h; Cooling with liquid nitrogen
To a 2 L three-necked round bottom flask equipped with mechanical stir, nitrogen inlet and outlet, 81.00 g (0.250 mol) 25 2,7-dibromo-9H-fluorence and 500 mL 11 THF were charged. After the 2,7-dibromofluorence was dissolved, 58.9 g (0.525 mol) 26 potassium t-butoxide was added in three batch. The mixture was turned from colorless to dark red immediately, 116.1 g (0.525 mol) of 27 1-bromodecane in 150 mL THF was added drop wise within 3.5 hrs. After addition completed, the mixture was stirred under nitrogen for 2 hrs. Potassium salts was removed through filtration. The filtrate was concentrated under vacuum to give yellow viscous oil. The final product was purified by silica gel chromatography using hexanes as eluent. 137.1 g 28 product was obtained as waxy crystals, 90.7percent isolated yield, m.p. 37.8-39.0° C.
Reference：
[1] Patent: US6730793, 2004, B1, . Location in patent: Page column 3
[2] Polymer, 2014, vol. 55, # 26, p. 6696 - 6707
[3] Patent: US2018/273524, 2018, A1, . Location in patent: Paragraph 0041
[4] Molecular Crystals and Liquid Crystals, 2013, vol. 578, # 1, p. 26 - 32
[5] Journal of Polymer Science, Part A: Polymer Chemistry, 2016, vol. 54, # 17, p. 2774 - 2784
In ethanol; at 65 - 142℃; for 1h;Conversion of starting material;
A 1-liter, creased, 4-necked round bottom Pyrex flask equipped with mechanical stirrer, 250-milliliter (ml) addition funnel, temperature probe, heating mantle, and water-cooled total reflux condenser was used. The flask was initially charged with 200 grams (1.08 mole) of ADMA-10 (decyldimethylamine, available from Albemarle Corporation, Baton Rouge, LA), and 239 grams (1.08 mole) decyl bromide was placed in the addition funnel. The stirrer was turned on and the reactor was heated to 65C. The decyl bromide was added dropwise to the ADMA-10 as the temperature of the reactor was allowed to rise from 65C to 142C. The addition funnel was then charged with 110 grams of methanol, and the methanol was added dropwise to the solution as the temperature of the reactor was allowed to fall to 90C. After the entire volume of the methanol was added to the reaction mixture, the heat and stirring were ceased and the intermediate quaternary ammonium (quat-Br) solution was allowed to cool.
In methanol; at 65 - 142℃; for 1 - 2.41667h;Conversion of starting material;
A 1-liter, creased, 4-necked round bottom Pyrex flask equipped with mechanical stirrer, 250-milliliter (ml) addition funnel, temperature probe, heating mantle, and water-cooled total reflux condenser was used. The flask was initially charged with 200 grams (1.08 mole) of ADMA-10 (decyldimethylamine, available from Albemarle Corporation, Baton Rouge, LA), and 239 grams (1.08 mole) decyl bromide was placed in the addition funnel. The stirrer was turned on and the reactor was heated to 65C. The decyl bromide was added dropwise to the ADMA-10 as the temperature of the reactor was allowed to rise from 65C to 142C. The addition funnel was then charged with 110 grams of methanol, and the methanol was added dropwise to the solution as the temperature of the reactor was allowed to fall to 90C. After the entire volume of the methanol was added to the reaction mixture, the heat and stirring were ceased and the intermediate quaternary ammonium (quat-Br) solution was allowed to cool.
In butan-1-ol; for 4h;Heating / reflux;Product distribution / selectivity;
EXAMPLE 1 - Preparation of Quaternary Ammonium Bromide Solution [0024] A dry 500 ml_ flask fitted with a condenser was charged with a mixture of 93g (0.5 mol) of N,N-dimethyldecylamine, 111g (0.5 mol) of 1-bromodecane and 135 g of 1-butanol. The mixture was heated to reflux using an electric mantle. Heating was turned off after 4 hrs. The clear light yellow solution of the quaternary ammonium bromide was analyzed, Analysis showed 12.7 wt% bromide, 0.19 wt% free amine and 59.4 wt% quaternary ammonium salt.[0025] A solution of 93.5g (0.5 mol) of decyldimethylamine in 65g of 2-butanol was taken in a flask and heated to 105 C and stirred magnetically. 1-Bromodecane (111.5g) was added in drops over 2 hrs and the mixture heated at 105 C for additional 4 hrs. The clear yellow solution (269g) was analyzed and found to have 70.6 wt% quaternary salt, 13.27 wt% bromide and 0.88 wt% free amine.
In iso-butanol; at 105℃; for 6h;Product distribution / selectivity;
EXAMPLE 1 - Preparation of Quaternary Ammonium Bromide Solution [0024] A dry 500 ml_ flask fitted with a condenser was charged with a mixture of 93g (0.5 mol) of N,N-dimethyldecylamine, 111g (0.5 mol) of 1-bromodecane and 135 g of 1-butanol. The mixture was heated to reflux using an electric mantle. Heating was turned off after 4 hrs. The clear light yellow solution of the quaternary ammonium bromide was analyzed, Analysis showed 12.7 wt% bromide, 0.19 wt% free amine and 59.4 wt% quaternary ammonium salt.[0025] A solution of 93.5g (0.5 mol) of decyldimethylamine in 65g of 2-butanol was taken in a flask and heated to 105 C and stirred magnetically. 1-Bromodecane (111.5g) was added in drops over 2 hrs and the mixture heated at 105 C for additional 4 hrs. The clear yellow solution (269g) was analyzed and found to have 70.6 wt% quaternary salt, 13.27 wt% bromide and 0.88 wt% free amine.
In acetonitrile; at 90℃; for 12h;
A dry flask (1 L), equipped with a magnetic stir bar, was charged with a solution of 1-decylbromide (33.17 g, 150 mmol) in acetonitrile (300 mL) and dimethyldecylamine (27.08 g, 150 mmol). The reaction mixture was stirred for 12 h at 90 C. The resulting solution was concentrated under vacuum to give the product. The product was dissolved in water (51 g/100 mL) and ethanol (10 mL) was added to this solution. The aqueous layer was washed with 3 x 50 mL of hexane (eliminated fractions) and 3 x 25 mL of chloroform. The chloroform layers were concentrated under vacuum to give the [DiC10][Br]. An aqueous solution of [DiC10][Br] was eluted on an hydroxide ion exchange resin. The aqueous solution of [DiC10][OH] was neutralized with an aqueous HCl under dry argon. The [DiC10][Cl] was dried and store under dry nitrogen.
With potassium hydroxide; In 2,2,4-trimethylpentane; ethanol; water;
(1) Production of 3-fluoro-4-decyloxybenzoic acid (1) STR25 A mixture of 1 g of <strong>[350-29-8]3-fluoro-4-hydroxybenzoic acid</strong>, 1.5 g of decyl bromide, 0.8 g of potassium hydroxide and 100 ml of ethanol was stirred under reflux for 6 hours. Two-hundred milliliters of water were added, and the mixture was further stirred under reflux for 2 hours. The reaction mixture was cooled, acidified with hydrochloric acid and then extracted with dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was then evaporated. To the residue was added 100 ml of isooctane, and the mixture was cooled. The precipitated crystals were filtered, and dried to obtain 0.7 g of a final product (1).
With potassium hydroxide; potassium iodide; In dimethyl sulfoxide;
EXAMPLE 3 2-Bromo-7-iodo-9,9-didecylfluorene To a mechanically stirred mixture of 7-iodo-2-bromofluorene (from example 2; 41.34 g, 0.1114 mol), DMSO (100 mL), potassium iodide (1.7 g), and powdered potassium hydroxide (28 g) cooled in a cold water bath, 1-bromodecane (53 mL) was added dropwise, and the mixture was stirred for 24 hours. The oil that separated on dilution with water, was extracted with toluene. Toluene extract was washed with water, dried and concentrated. The residual oil was passed through a column of 300 g alumina. Elution with 900 mL hexanes gave the product as an oil, 65 g This was left in 200 mL of isopropanol, when the product solidified, 58.63 g (81% yield), m.p. 43-45 C. Mass Spec.: m/z 698 (M+diiodo), 650,652 (M+).
81%
With potassium hydroxide; potassium iodide; In dimethyl sulfoxide; for 24h;
EXAMPLE 8 2-Bromo-7-iodo-9,9-didecylfluorene To a mechanically stirred mixture of 7-iodo-2-bromofluorene (example 2; 41.34 g, 0.1 114 mol), DMSO (100 ML), potassium iodide (1.79 g), and powdered potassium hydroxide (28 g) cooled in a cold water bath, 1-bromodecane (53 ML) was added dropwise, and the mixture was stirred for 24 hours.. The oil that separated on dilution with water, was extracted with toluene.. toluene extract was washed with water, dried and concentrated.. The residual oil was passed through a column of 300 g alumina.. Elution with 900 ML hexanes gave the product as an oil, 65 g.. This was left in 200 ML of isopropanola when the product solidified, 58.63 g (81% yield), m.p. 43-45 C. Mass Spec. (m/z): 698 (M+ diiodo), 650, 652 (M+).
A 1-liter, creased, 4-necked round bottom Pyrex flask equipped with mechanical stirrer, 250-milliliter (ml) addition funnel, temperature probe, heating mantle, and water-cooled total reflux condenser was used. The flask was initially charged with 200 grams (1.08 mole) of ADMA-10 (decyldimethylamine, available from Albemarle Corporation, Baton Rouge, LA), and 239 grams (1.08 mole) decyl bromide was placed in the addition funnel. The stirrer was turned on and the reactor was heated to 65C. The decyl bromide was added dropwise to the ADMA-10 as the temperature of the reactor was allowed to rise from 65C to 142C. The addition funnel was then charged with 110 grams of methanol, and the methanol was added dropwise to the solution as the temperature of the reactor was allowed to fall to 90C. After the entire volume of the methanol was added to the reaction mixture, the heat and stirring were ceased and the intermediate quaternary ammonium (quat-Br) solution was allowed to cool.
With sodium hydroxide; at 65 - 142℃;Product distribution / selectivity;
A 1-liter, creased, 4-necked round bottom Pyrex flask equipped with mechanical stirrer, 250-milliliter (ml) addition funnel, temperature probe, heating mantle, and water-cooled total reflux condenser was used. The flask was initially charged with 200 grams (1.08 mole) of ADMA-10 (decyldimethylamine, available from Albemarle Corporation, Baton Rouge, LA), and 239 grams (1.08 mole) decyl bromide was placed in the addition funnel. The stirrer was turned on and the reactor was heated to 65C. The decyl bromide was added dropwise to the ADMA-10 as the temperature of the reactor was allowed to rise from 65C to 142C. The addition funnel was then charged with 110 grams of methanol, and the methanol was added dropwise to the solution as the temperature of the reactor was allowed to fall to 90C. After the entire volume of the methanol was added to the reaction mixture, the heat and stirring were ceased and the intermediate quaternary ammonium (quat-Br) solution was allowed to cool.
EXAMPLE 16 (COMPARATIVE); 3-Bromothiophene (1 eq.) is combined in a flask with 1.1 mol of magnesium metal and 1.15 mol of 1-bromohexane in a 100% THF solvent, and with 815 mg of a (1,3-bis (diphenylphosphino)propane)dichloro Nickel (II) catalyst in suspension. The Grignard reagent concentration in the solvent is 2.2 mol/L. The reactions were conducted at room temperature. Immediate gas chromatography of the reaction product showed 85.3% 3-bromothiophene, 1.7% 3-hexylthiophene and 0.5% bis-thienyl side-product. GC after 48 hours showed 2.9% 3-bromothiophene, 64.5% 3-hexylthiophene, 9.8% bis-thienyl side-product and 3.34% 3-(1-methylpentyl)thiophene. This shows bad selectivity with a 100% THF solvent.
5.6%Chromat.; 1.59%Chromat.; 86.7%Chromat.
EXAMPLE 17 (COMPARATIVE); 3-Bromothiophene (1 eq.) is combined in a flask with 1.2 mol of magnesium metal and 1.2 mol of 1-bromohexane in a 50:50 THF/MTBE solvent, and with 600 mg of a (1,3-bis (diphenylphosphino)propane)dichloro Nickel (II) catalyst in suspension. The Grignard reagent concentration in the solvent is 1.3 mol/L. The reactions were conducted at room temperature. Gas chromatography of the reaction product after 15 hours showed 0.2% 3-bromothiophene, 86.7% 3-hexylthiophene, 5.6% bis-thienyl side-product and 1.59% 3-(1-methylpentyl)thiophene. This shows high bis-thienyl and 3-(1-methylpentyl)thiophene side-product formation with a 50:50 THF/MTBE solvent. Overall, the comparative examples show that the main input factor for the selectivity is the catalyst, secondly the temperature and solvent is responsible for the final completion of the selectivity. Expressed in numbers: 60%, 30%, 10% responsibility. In methyl-THF, a Grignard reagent concentration of up to 4 mol/L is possible.
With N,N,N,N,-tetramethylethylenediamine; iodine; In tetrahydrofuran; nitrogen; benzene;
1 Synthesis of 4-Decylbromobenzene: In a reaction flask were charged 10.2 g of metallic magnesium, 100 ml of THF, and a small amount of iodine in a nitrogen stream, and a part of 500 ml of a THF solution containing 100 g of 1,4-dibromobenzene was added thereto dropwise to initiate reaction. Then, the rest of the solution was added dropwise at 25 to 30 C. over a 2-hour period, and the mixture was allowed to react at 40 C. for 1 hour, followed by cooling to prepare a Grignard reagent. Separately, 187 g of decyl bromide, 500 ml of benzene, 98.3 g of N,N,N',N'-tetramethylethylenediamine, and 2.1 g of copper (I) chloride were put in a reaction flask, and the atmosphere was displaced with nitrogen. The mixture was heated to 50 C., and the above prepared Grignard reagent was added thereto dropwise at that temperature over 30 minutes. The reaction mixture was allowed to react for 24 hours, cooled, and poured into a saturated aqueous ammonium solution, and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate to recover 107 g of a crude product. The crude product was distilled in a Claisen flask equipped with a Vigreaux tube cylinder to obtain 43.7 g of the title compound.
With sodium hydroxide; In N-methyl-acetamide; water;
(c) Preparation of 1-decyl-<strong>[7343-34-2]3,5-dimethyl-1,2,4-triazole</strong> A mixture of <strong>[7343-34-2]3,5-dimethyl-1,2,4-triazole</strong> (6.0 parts; 0.062 mol ex (b) above) and 1-bromodecane (14.4 parts; 0.065 mol) in dimethylformamide (16 ml) was heated together at 120° C. for 23 hours. The cooled reaction mixture was diluted with water (100 ml), a solution of sodium hydroxide (2.62 parts; 0.065 mol) in water (100 ml) added, and the product extracted into ether (3*50 ml). After drying over magnesium sulphate the solution was evaporated to yield a pale yellow oil (3.3 parts; 22percent theory). Infra red analysis: vmax (film): 2923, 2853, 1515, 1341, 701cm-1. Proton NMR: delta(CDCl3; 0.9(t,3H); 1.2-1.4(m,14H); 1.7-1.9(m,2H); 2.3(s,3H); 2.4(s,3H); 4.0(t,2H)ppm. Mass spec: m/z(Br): 238(M+H+, 100percent).
(A) 1-Decyl-1,2,3,4-tetrahydro-8-quinolinol A mixture of 499.2 mg (3.35 mmol) of 1,2,3,4-tetrahydro-8-quinolinol (see Example 7A), 425 mg (5.05 mmol, 1.5 eq.) of sodium bicarbonate, and 780 mul (3.69 mmol, 1.1 eq.) of 98% 1-bromodecane in 10 ml of hexamethylphosphoric triamide under argon was stirred for three hours at room temperature, followed by 44 hours at 50 C. The reaction was diluted with 80 ml of 1:1 ether:petroleum ether and the organic layer was washed with five 40 ml portions of water and 40 ml of brine, dried over sodium sulfate and evaporated to yield 1.04 g of a brown oil. Purification by flash chromatography on 110 g of silica, eluted with 5:95 ethyl acetate:petroleum ether afforded 624.4 mg of the title compound as a colorless oil.
1-decyl-3-[2,4-dichloro-beta-(2,4-dichlorobenzyloxy)phenethyl]imidazolium bromide; mp. 90°-94° C., by the reaction of 1-[2,4-dichloro-beta-(2,4-dichlorobenzyloxy)phenethyl]imidazole and n-decyl bromide after an overnight reflux.
Decyl Methanethiosulfonate The mixture of 1-bromodecane (2.095 g, 0.00947 mol), <strong>[1950-85-2]sodium methanethiosulfonate</strong> and dry DMF (6 mL) was heated at 60 C. for 2 hr. At room temperature, water (15 mL) was added and the mixture was extracted with ether (3*30 mL). The ether extracts were washed with brine, dried, concentrated and the residue was subjected to flash column chromatography on silica gel with EtOAc-hexanes (1:4) to afford a white solid (2.063 g, 94%). It was recrystallized from 95% EtOH. mp: 28.0-29.5 C. IR (CDCl3 cast): 2954 (m), 2921 (st), 2852 (st), 1469 (m), 1305 (st), 1128 (st), 965 (m), 758 (m) and 720 cm-1 (m); 1H NMR (200 MHz, CDCl3): delta 3.32 (s, 3H, CH3SO2S), 3.17 (t, J=7.4 Hz, 2H, SCH2CH2), 1.77 (m, 2H, SCH2CH2), 1.50-1.20 (m, 14H, -(CH2)7-), 0.88 (m, 3H, CH2CH3); 13C NMR (50 MHz, CDCl3): delta 50.64, 36.49, 31.84, 29.45 (two carbons), 29.37, 29.23, 28.94, 28.57, 22.64, 14.08.
With potassium carbonate; In N,N-dimethyl-formamide; at 70℃; for 41h;
(1) Synthesis of 3,5-Didecyloxybenzyl Alcohol In a 100-ml eggplant flask was placed 3.95 g (20.5 mmol) of potassium carbonate. After purging the flask with nitrogen, 15 ml of DMF was added. Next, 1.00 g (7.13 mmol) of 3,5-dihydroxybenzyl alcohol and 3.3 ml (15.0 mmol) of 1-bromodecane were added, followed by stirring at 70 C. for 41 hours. The reaction mixture was allowed to cool to room temperature, from which insoluble matter was removed by filtration through Celite, and the filtrate was washed with methylene chloride. The solvent was distilled off on a rotary evaporator, and the residue was dissolved in diethyl ether and washed with a saturated aqueous sodium hydrogen carbonate solution and with a saturated aqueous sodium chloride solution. The washed solution was dried over magnesium sulfate, filtrated, and concentrated while distilling off the solvent on a rotary evaporator. The resulting crude product was purified by silica gel chromatography (hexane/AcOEt=70/30) and thereby yielded 1.54 g of the target compound in a yield of 51%. 1H NMR (CDCl3, 200 MHz): 6.47 (d, J=2, 2H), 6.36 (t, J=4, 1H), 4.56 (br, s 2H), 3.94 (t, J=8.6, 4H), 1.78 (m, 4H), 1.41 (m, 28H), 0.87 (t J=6.6, 6H).
3-(4-tert-butylphenyl)-3-decanoxy-1-(4-methoxyphenyl)prop-2-ene-1-one[ No CAS ]
[ 828911-23-5 ]
Yield
Reaction Conditions
Operation in experiment
34%; ~ 36%
1-(4-Methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione (Parsol 1789) [CAS: 70356-09-1] (16.11×10-3 mol; 5.00 g) is dissolved in aqueous 75 w/w % tetrabutylammonium fluoride (TBAF) (24.60×10-3 mol; 9 ml; 1.5 eq.). The mixture is then evaporated on a rotary evaporator at 80 C. for 3 hours, to give a viscous bright yellow mixture. The medium is then dissolved in 40 ml of anhydrous THF to which is added the alkylating agent 1-bromodecane (C10H21,Br) (33.0×10-3 mol; 7.46 g; 7 ml; 2 eq.). The reaction medium is refluxed with magnetic stirring for 8 hours. A viscous orange residue is obtained after filtration and evaporation of the solvent. A succession of open columns is then prepared in order to remove the excess reagents (alkylating agent C10H21,Br and TBAF) and to separate the three molecules present in the medium: the unreacted starting molecule, the molecule having for R5 the saturated linear acyclic carbon-based chain containing 10 carbon atoms and an H for R1, R'1, R2, R'2, R3, R'3, R4, R'4 and R'5, and the molecule having for R'5 the saturated linear acyclic carbon-based chain containing 10 carbon atoms and an H for R1, R'1, R2, R'2, R3, R'3, R4, R'4 and R5. The open columns are prepared in the same manner as before. Separation by HPLC; C18 column; eluent: 5% water/95% acetonitrile; flow rate: 6 ml/minute. 5.00 g of Parsol 1789 give 2.59 g of compound C10 and 2.47 g of compound 010, i.e. respective yields of 34% and 36%.
21%; ~ 14%
1-(4-Methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione (Parsol 1789) [CAS: 70356-09-1] (1.60×10-3 mol; 0.50 g) is dissolved in tetrabutylammonium fluoride (TBAF) as a 1M solution in tetrahydrofuran (THF) (3.20×10-3 mol; 3 ml; 2 eq.). The mixture is stirred magnetically for 3 hours at room temperature. The alkylating agent, 1-bromodecane (C10H21Br) (3.20×10-3 mol; 0.71 g; 0.7 ml; 2 eq.), which is itself dissolved in 2 ml of anhydrous THF, is then added to the mixture. The reaction medium is maintained at room temperature with magnetic stirring for 26 hours. A viscous orange residue is obtained after filtration and evaporation of the solvent. A succession of open columns is then prepared in order to remove the excess reagents (alkylating agent, C10H21,Br, and TBAF) and to separate the three molecules present in the medium: the unreacted starting molecule, the molecule having for R5 the saturated linear acyclic carbon-based chain containing 10 carbon atoms and an H for R1, R'1, R2, R'2, R3, R'3, R4, R'4 and R'5, and the molecule having for R'5 the saturated linear acyclic carbon-based chain containing 10 carbon atoms and an H for R1, R'1, R2, R'2, R3, R'3, R4, R'4 and R5. The open columns are prepared with about 40 g of silica 60 gel (0.063-0.200 mm) for 1.0 to 1.5 g of crude product to be separated, the eluent being dichloromethane. 0.50 g of Parsol 1789 gives 0.15 g of compound C10 and 0.10 g of compound O10, i.e. respective yields of 21% and 14%.
With sodium hydroxide; sodium dithionite; In water;
Step 2 <strong>[633-70-5]2,6-dibromoanthraquinone</strong> (30 g, 0.0819 moles), sodium dithionite (31 g, 0.18 moles), sodium hydroxide 12 g, 0.3 moles), Tetrabutylammoniumiodide (7.2 g, 0.00324 moles), demineralised water (30 ml) & cyclohexanone (500 ml), were heated under reflux at 97 C. for 5 hours under a nitrogen atmosphere. The reaction mixture turned from purple to dark brown, and a precipitate of the anthraquinone disodium salt appeared. A solution of 1-bromo-decane (37.5 ml, 0.180 moles) was added at 60 C. to the reaction mixture, together with an additional 50 mls of demineralised water, to redissolve the disodium salt. The reaction mixture was then heated at reflux for a further 24 hours. The crude product was isolated by conventional extraction and aqueous workup to yield 26 g of material. The crude material was purified by recrystallisation from ethyl acetate, to yield pure 2,6-dibromo-9,10-didecoxyanthracene as a pale yellow solid.
With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 110℃; for 48h;
A mixture of <strong>[487-70-7]2,4,6-trihydroxybenzaldehyde</strong> (3.00 g, 19.5 mmol), 1-bromodecane (25.87 g, 117.0 mmol), K2CO3 (8.07 g, 58.4 mmol), and KI (549 mg, 3.3 mmol) in DMF (150 mL) was stirred for 24 h at 110 C. and then one more portion of 1-bromodecane (5.0 g, 22.6 mmol) was added and continued stirring for another 24 h. The reaction mixture was cooled to 20 C. and extracted with CH2Cl2. The organic phase was washed with brine, dried (Na2SO4), and evaporated. Column chromatography (silica gel, hexane/CH2Cl2, 1:1, v/v) afforded the product (9.86 g, 88%) as yellow oil. 1H NMR (400 MHz, CDCl3) delta 10.38 (s, 1H), 6.02 (s, 2H), 3.98 (m, 6H), 1.98-1.66 (m, 6H), 1.44 (m, 6H), 1.40-1.12 (m, 36H), 0.87 (m, 9H). 13C NMR (101 MHz, CDCl3) delta 187.9, 165.8, 163.7, 109.2, 91.5, 69.1, 68.4, 32.1, 29.8, 29.6, 29.6, 29.3, 29.2, 26.2, 22.9, 14.4; HR-MS (ESI): calcd. for C37H66O4 [M+H+]: 575.5034. Found: 575.5033.
A Grignard reagent of 1-(magnesiumbromide) decane, prepared by the reaction of 1-bromodecane (17.3 g, 0.78 mol) with magnesium (5 g, 0.21 mol) in 50 mL of tetrahydrofuran (THF) was added drop wise into solution of <strong>[18791-79-2]5-bromothiophene-3-carbaldehyde</strong> (9.1 g, 0.048 mol) in 150 mL of THF at 0 C. After stirring at room temperature for 10 min, the reaction mixture was treatment with water and 2 N HCl, stirred for 2 h. After evaporation of solvent, the mixture was extracted by dichloromethane. The organic phase was washed with water, dried over anhydrous MgSO4 and removed solvent. The pure product was obtained by a silica gel using a mixed solvent hexane and ethyl acetate (1:20, v/v) as eluent, with yield of 63 % (10 g).
4,4'-bisdecyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With potassium iodide; potassium hydroxide; In dimethyl sulfoxide; at 0℃; for 72h;
A portion of 2 g of 4H-cyclopenta[2,1-b : 3,4-b]dithiophene (11.2 mmol) was dissolved in 50 ml of DMSO in a 100 ml double-neck round-bottom flask under magnetic stirring. The resulting solution was degassed, and decyl bromide (4.3 g, 22.4 mmol) followed with KI (50 mg) were added. The reaction mixture was cooled to 0 C and 2 g of grounded KOH were added in small portions. The reaction mixture was stirred for 3 days. Then 100 ml of water were added and the product was extracted with diethyl ether. The organic phase was washed tree times with the NaCl solution and three times with water and then dried over anhydrous MgSO4. The dried solution was concentrated in vacuo to produce yellow-orange oil which was further purified by column chromatography in light petroleum. The purified product was obtained as a colourless oil (3.84 g) in 85% yield. 1H NMR (CDCl3, 600 MHz) delta: 7.14 (d, 2 H), 6.93 (d, 2 H), 1.84 (m, 4 H), 1.14 (m, 20 H), 0.94 (m, 4 H), 0.84 (t, 6 H).
General procedure: To a solution of 2-(2-fluorophenyl)-2,3-dihydroquinolin-4(1H)-one (4), 2-(3-fluorophenyl)-2,3-dihydroquinolin-4(1H)-one (5), and <strong>[155370-03-9]2-(4-fluorophenyl)-2,3-dihydroquinolin-4(1H)-one</strong> (6) (2.41 g, 0.01 mol for each) in DMF (10mL each) was added KOH (1.12 g, 0.02 mol each) and the resulting mixture was stirred at room temperature for 1 h. Then alkyl bromide (0.03 mol each) was added dropwise, and the reaction mixture was stirred overnight at room temperature. Then the reaction mixture was poured into 20 mL of water. The resulting mixture was extracted with CH2Cl2 (2 x 20 mL). The combined organic layer was washed with brine, dried over Na2SO4 , filtered, and concentrated in a vacuum to give crude products 7a-k, 8a-k, and 9a-k, which were purified by column chromatography using a mixture of n-hexane-chloroform (8.5:0.5) as eluent (yields are in Tables 1, 4, and 7).
To a solution of tris(2-dimethylaminoethyl)amine (0.426 g, 1.85mmol) in acetonitrile (4 mL) was added 1-bromodecane (1.27 g, 5.73 mmol). Theresulting mixture was heated at reflux with stirring for 18 hours. After cooling, and the addition of hexanes (5 mL), a white solid precipitated, which was filtered with a Buchner funnel, transferring with a cold hexanes/acetone mixture (15 mL, 1:1). The solid was rinsed with a cold hexanes/acetone mixture (2O mL, 1:1), resulting in T10 10,10,10 (1.16 g, 70%) as a white powder; mp=223-248 C; ?H NMR (300 MHz,CDC13) oe 4.11-4.02 (m, 6H), 3.62-3.53 (m, 6H), 3.41-3.27 (m, 24H), 1.72-1.62 (m, 6H), 1.38-1.14 (m, 42H), 0.85-0.78 (m, 9H); ?3C NMR (75 MHz, CD3OD) oe 65.4,61.1, 50.2, 46.9, 31.6, 29.2, 29.0, 28.9, 26.1, 22.4, 22.3, 13.0; high resolution mass spectrum (ESI) m/z 217.9095 ([Mj3 calculated for [C42H93N4j3: 217.9128). See alsoYoshimura et al., 2012, Langmuir 28:9322-9331. ?H and ?3C NMR spectra of compound T-10,10,10 can be found in Figure 50.
General procedure: To a round-bottom flask attached to a reflux condenser was added K2CO3 (276 mg, 2 mM) and 3,30-sulfonyldianiline(248 mg, 1 mM) in 25 mL acetone; the mixture was stirred for 40 min at 80 C. Either 1-bromotetradecane (0.29 mL,1 mM for DAP-T) or 1-bromodecane (0.2 mL, 1 mM forDAP-D) was then added, and the reaction mixture was refluxed for a further 8 h at 80 C. The reaction was monitored with thin-layer chromatography (TLC) usingethyl acetate and n-hexane (4:6, v/v) as the solvent system.Upon completion of the reaction, the reaction mixture was cooled to room temperature and excess acetone was evaporated under reduced pressure using a rotary evaporator. The mixture was washed with water, filtered, dried,and subjected to silica gel column chromatography to obtain pure solid products using ethyl acetate and n-hexane(1.5:8.5, v/v) as the solvent system. Yields 81% and 77% for DAP-T and DAP-T,respectively.
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;
Benzylamine (3) (4 g), <strong>[6294-17-3]1-chloro-6-bromohexane</strong> (7.4 g), 1-bromodecane (8.3 g) and DMF (40 ml) were placed in a single-necked bottle, and potassium carbonate (6 g) was added. The reaction was stirred at room temperature overnight, and then the mixture was evaporated to ethyl ether (yield: ethyl acetate: n-hexane = 1:10). After the reaction was completed, filtered and concentrated to remove most of the DMF, and then extracted with 50 mL of ethyl acetate and 50 ml of water. Dry with sodium sulfate and concentrate the solvent to give an oil.Column chromatography (eluent: ethyl acetate: n-hexane = 1 : 50) gave 3.14 g of oil.
methyl 3-(decyloxy)isoxazole-5-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
With potassium carbonate; potassium iodide; In acetone; for 10h;Reflux;
1 g (6.99 mmol) of <strong>[10068-07-2]methyl 3-hydroxyisoxazole-5-carboxylate</strong> was dissolved in 20 mL of acetone.Add 1.93 g (13.98 mmol) of potassium carbonate, 50 mg of potassium iodide, and 1.85 g (8.39 mmol) of bromodecane.The temperature was raised to reflux for 10 h and cooled to room temperature.The reaction solution was filtered, and the filter cake was washed three times with dichloromethane.Column chromatography purification (petroleum ether: ethyl acetate = 8:1)A white solid was obtained in 1.88 g, yield 95%.The obtained product was dissolved in 10 mL of methanol, and 20 mL of a 1.76 M potassium hydroxyamine solution in methanol was added.Stir at room temperature for 6 h under nitrogen atmosphere, add 15% aqueous HCl solution to adjust to acidity.Precipitating product 3-(decyloxy)-N-hydroxyisoxazole-5-carboxamide,It was 1.0 g as a white solid, yield 87.8%.
Add 2.0g to 50mL DMF solventPhthalic acid (0.012 mol) and 4.8 g potassium hydrogencarbonate (0.048 mol),Stir at room temperature to form a potassium salt.6.64 g of n-bromodecane (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 (24/1) as eluent.
Compound A 1.23 g and compound B 2.20 g were added to a round bottom flask.The reaction was carried out in a constant temperature oil bath at 80 C for 1 h; 20 mL of isopropanol was added as a solvent to the round bottom flask, and the reaction was continued for 18 h; after the reaction was completed, the solvent was evaporated under reduced pressure at 40 C to give a white solid, using tetrahydrofuran. Wash several times and dry in a vacuum oven to obtain intermediate I (quaternary ammonium salt)The alcohol was stored in a bottle for use, the yield of the intermediate was 93%,
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.
(E)-3-decyl-1-([(5′-nitrofuran-2′-yl)methylene]amino)imidazolidine-2,4-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
General procedure: <strong>[67-20-9]Nitrofurantoin</strong>, 1, (2.94mmol, 0.7g) was dissolved in 10mL of anhydrous dimethyl formamide (DMF), and trimethylamine (TEA, 4.41mmol, 1.5eq.) was added. The solution was stirred at room temperature for 15min. To resulting yellow solution, the appropriate n-alkyl or benzyl bromide (4.41mmol, 1.5eq) was added. The reaction was stirred at room temperature and monitored by TLC eluting with DCM:MeOH (19:1, v/v). Upon completion, the reaction was quenched with 20mL water and extracted with ethyl acetate (3X20mL). The organic layer was washed once with saturated NH4Cl and once with water. The solution was concentrated in vacuo. The resulting paste was purified by recrystallization in ethanol/water) to afford the desired analogue (Scheme 1 ).
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