* 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] Russian Journal of Applied Chemistry, 1996, vol. 69, # 12, p. 1841 - 1848
[2] Journal of the American Chemical Society, 2008, vol. 130, # 38, p. 12590 - 12591
[3] Journal of Materials Chemistry A, 2013, vol. 1, # 22, p. 6572 - 6578
[4] RSC Advances, 2018, vol. 8, # 26, p. 14623 - 14632
2
[ 629-27-6 ]
[ 17702-88-4 ]
Reference:
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 452
[2] Journal of the American Chemical Society, 1946, vol. 68, p. 452
[3] Journal of Organic Chemistry, 1976, vol. 41, # 21, p. 3491 - 3493
3
[ 629-27-6 ]
[ 64-17-5 ]
[ 201230-82-2 ]
[ 123-29-5 ]
Reference:
[1] Organic Letters, 2006, vol. 8, # 7, p. 1383 - 1386
[2] Chemistry - A European Journal, 2012, vol. 18, # 30, p. 9415 - 9422
[3] Tetrahedron Letters, 1991, vol. 32, # 36, p. 4733 - 4736
[4] Journal of the American Chemical Society, 1997, vol. 119, # 23, p. 5465 - 5466
4
[ 629-27-6 ]
[ 64-17-5 ]
[ 929-61-3 ]
[ 123-29-5 ]
Reference:
[1] Journal of Organic Chemistry, 1991, vol. 56, # 13, p. 4320 - 4322
EXAMPLE 6 STR23 4-(3-octyl-2-imidazolidinon-1-yl)benzenesulfonyl chloride To a 0 C. suspension of 5.00 g (30.8 mmol) <strong>[1848-69-7]1-phenylimidazolidin-2-one</strong> in 50 mL of dimethylformamide was added 1.48 g (37.0 mmol, 1.2 equiv) of sodium hydride (60% oil dispersion). After 45 minutes, 6.7 mL (8.88 g, 37.0 mmol, 1.2 equiv) of octyl iodide was added. The mixture was allowed to stir overnight with gradual warming to room temperature. TLC analysis indicated the presence of starting material. An additional 830 mg portion of sodium hydride was added. After 5 hours, TLC analysis again indicated the presence of starting material, so 0.5 g more sodium hydride and 6 mL of octyl iodide were added. After 2 hours, the reaction was complete as judged by TLC analysis. The mixture was concentrated in vacuo, and partitioned between 200 mL of ethyl acetate and 50 mL of water. The organic phase was washed sequentially with three 50-mL portions of water and one portion of brine, dried over magnesium sulfate, and concentrated in vacuo. Purification by flash chromatography (silica gel, 10-25% ethyl acetate/hexane) provided 3.97 g (47%) of 3-octyl-<strong>[1848-69-7]1-phenylimidazolidin-2-one</strong>.
With potassium carbonate; In acetone; for 30h;Heating / reflux;
5-Hydroxy-6, 7-(dioctyloxy) flavone (34); A mixture of 1 (81 mg, 0.3 mmol), 1-iodooctane (0.16 mL), and anhydrous K2CO3 (166 mg) in acetone (25 mL) was refluxed with stirring for 30 h. The reaction mixture was concentrated under reduced pressure, diluted with water (50 mL) and extracted with CH2C12 (50 mL x 3). The extract was washed with water and dried over MgS04, and the solvent was evaporated in vacuo. The residue was purified by flash chromatography on a column of silica gel and eluted with CH2C12/MeOH (100: 1 to 50: 1) to give compound 34 (122 mg, 82%) as a pale yellow powder. mp 85-86 C ;'H NMR (CDC13) 8 0.89, 0.90 (each t, 6H, H8a, H8b, J= 6.9 Hz), 1.31-1. 52 (m, 20H, H3a + H4a + H5a + H6a + H7a + H3b + H4b + H5b + H6b + H7b), 1.79, 1.89 (each t, 4H, H2a, H2b, J= 6.9 Hz), 4.03, 4.07 (each t, 4H, Hla, Hlb, J= 6. 9 Hz), 6.53 (s, 1H, H3), 6.64 (s, 1H, H8), 7.51 (m, 3H, H3'+ H4'+ H5'), 7.86 (m, 2H, H2'+ H6'), 12.45 (s, 1H, 50H) ; MS (EI) m/z 494 [M] +, 382,270 (base).
Synthesis Example 10 20 parts of <strong>[2523-42-4]2-iodofluorene</strong> was dissolved in a mixed solution of 114 parts of dimethyl sulfoxide (DMSO) and 23 parts of tetrahydrofuran (THF), and the thus obtained mixture was then stirred at 25C for 10 minutes. Thereafter, while stirring, 8.7 parts of potassium-tert-butoxide was added to the mixture. Twenty minutes later, 19.2 parts of n-octyl iodide was added to the mixture, and further twenty minutes later, 8.7 parts of potassium-tert-butoxide was added thereto. Further, twenty minutes later, 19.2 parts of n-octyl iodide was added thereto, and the obtained mixture was then stirred at 25C for 2 hours. After completion of the stirring, THF was distilled away from the reaction solution, and it was then extracted with toluene-water. The toluene phase was dried over magnesium sulfate, and the toluene was then distilled away, thereby obtaining a brown tarry solid. This brown tarry solid was separated and purified by column chromatography (hexane-ethyl acetate) to obtain 30 parts of 9,9-di-n-octyl-<strong>[2523-42-4]2-iodofluorene</strong> in the form of a colorless crystal.
With 2,2'-azobis-(2,4-dimethylvaleronitrile); sodium cyanoborohydride; In ethanol; at 70℃; for 0.166667h;Automated synthesizer; Flow reactor;
General procedure: A 50 mL EtOH solution of 1a (10 mmol, 2.4 g, 0.2 M), ethyl acrylate (16 mmol, 1.6 g, 1.6 equiv), V-65 (1 mmol, 248.3 mg, 10 mol %), and decane as an internal standard (400 mg) (solution A), and a 50 mL EtOH solution of NaBH3CN (30 mmol, 1.87 g, 3 equiv) (solution B) were prepared and placed in bottles A and B respectively. These two bottles were connected by PTFE tube to the automated microflow system, MiChS system X-1, equipped with a micromixer (MiChS -150, 150 m), a residence time unit (RTU, 1 mm i.d. and 3 m length) and an automated fraction collector. Four different conditions (residence time = 5, 10, 15, and 20 min at 70 C, relative flow rate: A:B = 1:1) were inputted through a touch panel and the program was run. The reaction mixtures for each condition were sampled (1 mL) automatically in vials containing 1 mL of H2O by a fraction collector. Products were extracted with Et2O (1 mL), and the yields were determined by GC analysis equipped with a flame ionization detector.
3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione[ No CAS ]
[ 629-27-6 ]
[ 1057401-08-7 ]
Yield
Reaction Conditions
Operation in experiment
58%
This compound was synthesized according to a literature procedure [41] 3,6-Di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (3) (0.45 g, 1.5 mmol) and K2CO3 (0.83 g, 6.0 mmol) were added to the reaction vessel. The reaction vessel was fitted with a silicon septum, evacuated, and back-filled with argon. This sequence was repeated twice. Anhydrous DMF (16 mL) was added under a stream of argon, and the resulting mixture was stirred at 120 C for 1 h. Then, 1-iodooctane (4a) (1.44 g, 6.0 mmol) was added in one portion, and the mixture was stirred at 120 C for 24 h. After cooling to room temperature, the reaction mixture was poured into ice-cold water (100 mL), and extracted with CH2Cl2 (4 x 25 ml). The organic fractions were collected, dried over Na2SO4, filtered, and concentrated at reduced pressure. The residue was purified by flash chromatography on silica gel with a mixture of CH2Cl2 and petroleum ether (1:1) as eluent. The chromatographic fractions containing the required compound were collected and concentrated at reduced pressure to give 1a as a dark pink solid (0.46 g, 58% yield): mp 141-143 C [Lit: mp 143 C] [41]. 1H NMR (400 MHz CDCl3) δ (ppm) 8.93 (dd, J = 3.9, 1.2 Hz, 2H), 7.63 (dd, J = 5.1, 1.2 Hz, 2H), 7.28 (dd, J = 5.1, 3.9 Hz, 2H), 4.07 (m, 4 H), 1.74 (m, 4 H), 1.33 (m, 20 H), 0.87 (t, J = 6.1 Hz, 6H). The spectral properties of this compound are in agreement with those previously reported [41].
[0228] [Comparative Example 1]; By the synthesis method shown below, the compound (C-l) shown below was obtained.5.12 g of purpurin (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 mL of Nu,Nu'-dimethylformamide, followed by addition of 2.76 g of potassium carbonate, and 4.80 g of iodooctane was added dropwise thereto. After performing a reaction at 70C for 7 hours and then ice-cooling to an inner temperature of 0C, 20 mL of diluted hydrochloric acid (2 mL concentrated hydrochloric acid diluted with 18 mL of water) was used for neutralization, and then 30 mL of water was added thereto to obtain a crude crystal. The obtained crude crystal was purified by silica gel chromatography with ethyl acetate to obtain 0.75 g of a desired compound (C-l).[0229] The obtained compound (C-l) was subjected to 1H-NMR measurement. The results are shown below.IHNMR (300 MHz, CDC13) 613.58 (s, IH), 13.49 (s, IH), 8.45 (dd, 2H), 7.80 (dd, 4H), 6-68 (s, IH), 4. 15 (t, 2H), 1.92 (m, 2H), 1.72-1.25 (m, 10H), 0.88 (t, 3H).
With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 0 - 20℃;
4-Hydroxy-3-(octyloxy)benzaldehyde (3)To the solution of <strong>[4049-39-2]4-(benzyloxy)-3-hydroxybenzaldehyde</strong> (190 mg, 0.83 mmol) in anhydrous DMF (2.0 mL) was added 60% NaH (40 mg, 1.00 mmol) at 0C followed by the addition of 1-iodooctane (300 mg, 1.25 mmol). The reaction mixture was stirred at room temperature (r.t.) overnight and NH4C1 solution was then added. The mixture was extracted with ethyl acetate 3 times and the combined organic layers were dried and concentrated under vacuum. The resulting residue was purified through flash column chromatography (Hexane: Ethyl Acetate = 10: 1) to yield 4-(benzyloxy)-3-(octyloxy)benzaldehyde (235 mg, 83%) as light yellow oil, which was subsequently subjected to hydrogenolysis in ethyl acetate in the presence of 10% Pd/C. After filtration and concentration, the crude residue was purified by column chromatography (Hexane: Ethyl Acetate = 5: 1) to give 3 (125 mg, 72%) as light yellow oil. 1H NMR (CDC13, 300 MHz) delta 9.80 (s, 1H), 7.36-7.42 (m, 2H), 7.03 (d, J = 8.6 Hz, 1H), 6.44 (s, 1H), 4.09 (t, J = 6.9 Hz, 2H), 1.82 (hexatet, J = 6.7 Hz, 2H), 1.20-1.50 (m, 10H), 0.87 (t, J- 6.8 Hz, 3H); 13C NMR (CDC13, 75 MHz) delta 191.09, 151.96, 146.70, 129.90, 127.42, 114.44, 109.68, 69.30, 31.86, 29.37, 29.28, 29.09, 26.03, 22.73, 14.17; ESI-HRMS for [M + H]+ Ci5H2303: calcd 251.1647, found 5251.1638.
In a four-necked 300 mL round bottomed flask, <strong>[4923-87-9]5-bromobenzo[b]thiophene</strong> (10.8 g, 50.7 mmol) was dissolved in anhydrous THF (120 mL). The reaction solution was cooled at -78 C. A 1.08M lithium diisopropylamide/hexane solution (56.0 mL, 60.5 mmol, 1.2 eq.) was added thereto, and the mixture solution was allowed to warm to 0 C. and stirred for an hour. After the reaction solution was cooled to -78 C. again, 1-iodo octane (18.0 mL, 99.7 mmol, 2.0 eq.) was added. Then, the mixture was allowed to warm to room temperature, and stirred at room temperature for a day. After completion of the reaction, water and ethyl acetate were added. An organic phase was extracted with ethyl acetate, and dried over magnesium sulfate. The resulting crude product was purified by column chromatography, whereby intermediate B1 was obtained (16.5 g, yield 100%).
With nickel(II) bromide dimethoxyethane; manganese; bathophenanthroline; lithium bromide; In N,N-dimethyl-formamide; at 20 - 40℃;Inert atmosphere;
General procedure: To a suspension of NiBr2·glyme (3.1 mg, 10 μmol), bathophenanthroline (3.9 mg, 12 μmol), manganese (22 mg, 0.40 mmol), and LiBr (26mg, 0.30 mmol) in DMF (0.4 mL) were added 2-naphthyl nonaflate (3a; 85.3 mg, 0.200 mmol) and 1-iodobutane (34.2 μL, 0.300 mmol) at r.t. After stirring for 14 h at 40 C, the mixture was cooled to r.t. and to this was added aqueous phosphate buffer (pH 7.4, ca. 2 mL). The mixturewas extracted with Et2O (3 × ca. 2 mL) and the combined organic extracts were dried (Na2SO4) and filtered. The filtrate was concentrated under reduced pressure. The residue was purified by chromatography (silica gel, n-hexane) to give 2a
With lithium tert-butylate; In methanol; water monomer; at 50℃; for 48h;Glovebox;
In a glove box, t-BuOLi (0.75 mmol, 1.5 equivalents, 60.1 mg), B2pin2 (1.5 mmol, 3 equivalents, 380.9 mg), 0.85 mL of solvent methanol, 10 μL of H2O were added to the vial containing the stirrer in turn.Iodo-n-octane (0.5 mmol). The capped vial was removed from the glove box and the reaction mixture was stirred at 50 C for 48 hours. After cooling to room temperature, the reaction mixture was transferred to a 100 mL flask by methanol, and then a small amount of silica gel was added thereto. After removing the solvent in vacuo, the residue was poured onto a silica gel column.And purified by column chromatography, the developing solvent is a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 50:1 to 30:1 to obtain the desired product n-octylboronic acid pinacol ester, the yield is 83%. The reaction was carried out in the same procedure using 0.5 mmol of bromo n-octane in a yield of 66%.
4-OAP was prepared using the Chichibabin reactionof 4-aminopyridine (4-AP) and sodium amide indry dioxane, followed by alkylation with octyl iodide[25]. 4-OAP was isolated from the reaction mixture viaextraction with hexane and recrystallized first fromhexane and then from acetone (99.9%, m.p. 64 ±0.2C). The molecular and structural formulas wereconfirmed via elemental analysis plus IR and 1HNMR spectroscopy. OAP chloride was prepared byshaking a 0.1 M solution of 4-OAP (100 mL) with 1 MHCl (100 mL). The organic phase was separated andfiltered through a paper filter. All chloroform wasevaporated under an air stream. The residue was driedat 60C. The yield was 95%. According to the datafrom potentiometric titration, the content of the mainsubstance was 99.8%.