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CAS No. : | 4292-19-7 | MDL No. : | MFCD00001088 |
Formula : | C12H25I | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GCDPERPXPREHJF-UHFFFAOYSA-N |
M.W : | 296.23 | Pubchem ID : | 20282 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P302+P352+P332+P313+P362+P364-P305+P351+P338+P337+P313 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | for 6h; Reflux; | |
85% | In toluene at 120℃; for 12h; | 1.3 (3) Synthesis of 1-dodecyl-4-methylpyridine iodonium salt: 10mmol 4-methylpyridine (1mL) and 10mmol 1-iodododecane (2.96g) were dissolved in 20mL of toluene. When pale yellow powder precipitated, the mixture was heated at 120°C for 12 hours. After the reaction, the product was added to dichloromethane to dissolve completely. Then, a large amount of petroleum ether was poured into the mixture to generate a large amount of white solid, and the yield was 85%. |
64% | for 6h; Heating; |
at 100℃; | ||
In ethanol for 24h; Reflux; | 1 1-dodecyl-4-methylpyridin-1-ium iodide 4-methyl-pyridine (2mL, 20mmol) and 1-iodo-dodecane were mixed in ethyl alcohol, heated under reflux.After 24 hours the reaction was completed, ethanol was distilled off in vacuo to give the crude product.Then washed three times with ethanol, washing three times with petroleum ether, to give the final product. | |
In ethanol Reflux; | ||
In methanol | ||
In methanol | ||
In ethanol at 20℃; | ||
In ethanol for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | With phosphorus; iodine at 150℃; for 5h; | |
99% | With 1H-imidazole; iodine; triphenylphosphine In dichloromethane at 20℃; for 1.5h; Inert atmosphere; | 1.A Dodecan-1-ol (10.0 g, 53.7 mmol, 1.00 eq) was added to a 1 L flask with a stir bar. Diluted with DCM (268 mL), and the resulting solution was stirred vigorously at room temperature. After addition of imidazole (4.75 g, 69.8 mmol, 1.30 eq), triphenylphosphine (18.3 g, 69.8 mmol, 1.30 eq), and iodine (17.7 g, 69.8 mmol, 1.30 eq) in succession, the resulting reaction mixture was stirred vigorously at room temperature under argon (Ar). Reaction progress was monitored by TLC. After 1.5 hrs, TLC indicated conversion of starting material to one major spot. The reaction mixture was quenched with 150 mL saturated aqueous sodium thiosulfate. The resulting organic layer was diluted with 200 mL hexanes, the small amount of precipitate was filtered, and the mother liquor was evaporated under reduced pressure to yield white solid. After addition of 400 mL hexanes, the resulting slurry was stirred vigorously overnight under Ar. In the next morning, the slurry was filtered, and the mother liquor was evaporated under reduced pressure to yield a yellow oil. The crude material was purified via silica plug eluting with 100% hexanes to yield a clear oil with a small amount of yellow solid remaining. This crude material was taken up in 100% pentane, filtered, and the mother liquor was evaporated under reduced pressure to yield a clear oil, which corresponded to the product 1-iodododecane (15.7 g, 53.0 mmol, 99% yield). |
99% | With 1H-imidazole; iodine; triphenylphosphine In dichloromethane at 20℃; for 1.5h; Inert atmosphere; |
91% | With iodoform; sodium iodide In N,N-dimethyl-formamide for 3h; Irradiation; | |
89% | With iodine In acetonitrile at 120℃; for 0.0666667h; Microwave irradiation; chemoselective reaction; | 4. 2. Typical Procedure for Iodinationof Alcohol General procedure: To a suspension of polymer-bound triphenylphosphine (1.2 mmol) in anhydrous acetonitrile (10 mL) were added iodine (1 mmol) and 1,6-hexanediol diol (1mmol). The reaction mixture was irradiated in microwave reactor at 120 °C for 3 min. The reaction mixture was filtered over a filter paper and washed with chloroform.The filtrate was extracted with aqueous sodium thiosulfate solution and dried with anhydrous sodium sulfate.The reafter, solvent was removed under reduced pressure to obtain 6-iodohexan-1-ol (30) in 93% |
89% | With iodine; triphenylphosphine In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran at 20℃; for 1.5h; chemoselective reaction; | 2.2 General procedure for the iodination of alcohols General procedure: To a stirred solution of triphenylphosphine (1.5 mmol) in dry dichloromethane was added iodine (1.5 mmol)and polymer supported 4-DMAP (0.4 mmol, 40 mol%). Stirring was continued for 2 min; alcohol (1mmol) was then added. The reaction was monitored by TLC. After complete conversion of the alcohol (as indicated byTLC), the reaction was quenched with an aqueous solution of sodium thiosulfate (20 mL). The organic solventswere removed and the aqueous solution extracted with ethylacetate (50 mL). The combined organic layers weredried using sodium sulfate (anhydrous), filtered and concentrated. The residue was purified by column chromatography (2% EtOAc in hexane) to get the desired iodide product. |
86% | With tetra-(n-butyl)ammonium iodide; triphenylphosphine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; | |
81% | With phosphorus; hydrogen iodide In water; toluene at 80℃; for 20h; Inert atmosphere; | |
76% | With 1H-imidazole; iodine; triphenylphosphine In toluene at 20℃; for 2h; Reflux; | |
73% | Stage #1: 1-dodecyl alcohol With copper(II) bis(trifluoromethanesulfonate); diisopropyl-carbodiimide at 20℃; for 1h; Stage #2: With N-iodo-succinimide In tetrahydrofuran at 150℃; for 0.0833333h; microwave irradiation; | |
With phosphorus; iodine at 150℃; | ||
With hydrogen iodide | ||
With phosphorus; iodine at 170℃; | ||
(i) Me3SiCl, Py, (ii) Me3SiI, CHCl3; Multistep reaction; | ||
91 %Spectr. | With 1-pyrrolidinecarboxaldehyde; 2,6-Dichlorobenzoyl chloride; sodium iodide In acetone at 80℃; for 20h; | 4.9.3.3 Synthesis of Dodecyl iodide (1033) General procedure: As described in general procedure VIII (chapter 4.9.1) dodecanol was converted to dodecyl iodide1033 with 2,6-CI2BzCI (1.2 equiv) in the presence of 10 mol% FPyr at 80 °C within 20 h in 91% yield.Besides, 2% of starting material and 2% of dodecyl 2,6-dichlorobenzoate (1033/333 98:2) wasobtained. |
With 1H-imidazole; iodine; triphenylphosphine In dichloromethane at 0 - 26℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With trimethylsilylazide; tetrabutyl ammonium fluoride In tetrahydrofuran for 24h; Ambient temperature; | |
92% | With sodium azide In N,N-dimethyl-formamide at 60℃; for 20h; | |
With methanol; sodium azide at 90℃; |
With sodium azide | ||
With trimethylsilylazide; tetrabutyl ammonium fluoride at 20℃; for 24h; | ||
With sodium azide In N,N-dimethyl-formamide at 80℃; for 3.5h; | 4.5.3. ethyl (S)-3-phosphoryl-2-((1-dodecyl-1H-1,2,3-triazol-4-yl)methoxy)propanoate (20) General procedure: To a solution of 1-iodododecane (5.0 mL, 20 mol) in anhydrousDMF (63 mL) was added NaN3 (4.0 g, 61 mol). The mixture wasstirred at 80 C for 3.5 h, and then concentrated under reducepressure. The residuewas extracted with Et2O and H2O. The organicphase was dried over MgSO4, filtered, and concentrated underreduced pressure to give a pale yellow oil. The crude azide productwas used in the next step without further purification.A mixture of compound 19 (2.0 g, 7.4 mmol), CuSO4 (240 mg,1.5 mmol), sodium ascorbate (0.88 g, 4.5 mmol) and the abovepreparedazide compound (1.7 g, 8.2 mmol) in t-BuOH/H2O (5:2,170 mL) was stirred at room temperature for 2 h, and thenconcentrated under reduced pressure. The residue was extractedwith EtOAc and brine. The combined organic phase was dried overMgSO4, filtered, and concentrated under reduced pressure. Thecrude product was purified by silica gel chromatography (CH2Cl2/acetone 9:1 to 1:1) to afford a triazole compound (3.2 g, 90%).To a solution of the above-prepared triazole compound (0.74 g,1.6 mmol) in CH2Cl2 (16 mL) was added trimethylsilyl bromide(0.82 mL, 6.2 mmol) at 0 C. The mixture was stirred at room temperaturefor 1.5 h, and then concentrated under reduced pressure.The residue was quenched with EtOH (99.5%, 5.0 mL) for 30 min,and then concentrated under reduced pressure. The residue waspurified by column chromatography (RP-18 column; loaded samplewith saturated NaHCO3(aq); eluted with MeOH/H2O 1:1 to 3:2) toafford compound 20 (0.56 g, 81%). C20H38N3O6P; white foam; TLC(i-PrOH/H2O/NH4OH 10:2:3) Rf 0.55; [a]D26 17.7 (c 1.0,MeOH); IR ymax (neat) 3312, 2929, 2855, 2360, 2337, 1778, 1541,1526, 1017 cm1; 1H NMR (400 MHz, CD3OD) d 8.05 (1H, s), 4.74(2H, dd, J 12, 31.2 Hz), 4.41e4.37 (3H, m), 4.19 (2H, q, J 7.2 Hz),2.13e2.06 (2H, m), 1.93e1.88 (2H, m), 1.32e1.25 (21H, m), 0.89 (3H,t, J 6.8 Hz); 13C NMR (100 MHz, CD3OD) d 174.4 (d, Jc-p 12.1 Hz),145.6, 125.3, 77.1, 64.7, 62.4, 51.5, 33.5 (d, Jc-p 133 Hz), 33.2, 31.4,30.9 (2 ), 30.8, 30.7, 30.6, 30.3, 27.6, 23.9, 14.6 (2 ); 31P NMR(162 MHz, CD3OD) d 19.0; ESI-HRMS (positive mode) calcd forC20H39N3O6P: 448.2576, found m/z 448.2588 [M H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium aluminium tetrahydride Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 3-(tetrahydropyran-2'-yloxy)propyne With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at -78 - -30℃; for 0.75h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran at -30 - 20℃; Inert atmosphere; | 1.A 2-(2-Propynyloxy)tetrahydro-2H-pyran (4.77 g, 34.0 mmol, 1.00 eq) was added to a 250 mL oven-dried flame-dried flask equipped with a stir bar, diluted with 40 mL THF and hexamethylphosphoramide (20.7 mL, 119 mmol, 3.50 eq), cooled to -78 °C, and stirred vigorously under Ar. After addition of n-butyllithium (2.5 M in hexane, 15.0 mL, 34.0 mmol, 1.00 eq) dropwise via syringe pump at a rate of 17 mL/hr, the resulting reaction mixture was stirred vigorously at -78 °C under Ar for 10 min, before warming to -30 °C and stirring for an additional 45 min. After addition of a solution of 1-iodododecane (10.1 g, 34.0 mmol, 1.00 eq) in 14 mL THF dropwise via syringe pump at a rate of 17 mL/hr, the resulting reaction mixture was allowed to slowly warm to room temperature and was stirred vigorously under Ar overnight. In the next morning, TLC indicated complete conversion of alkyl iodide and alkyne starting materials to one spot (stained with PMA). The reaction was quenched dropwise with saturated ammonium chloride, and the resulting aqueous layer was extracted 3 times with EtOAc. Combined organic layers were dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to yield 22.6 g of a yellow oil, which was purified via column chromatography eluting with 1:12 EtOAc to hexanes to yield a slightly yellow oil (8.40 g, 27.2 mmol, 80% yield). |
80% | Stage #1: 3-(tetrahydropyran-2'-yloxy)propyne With n-butyllithium In tetrahydrofuran; hexane at -78 - -30℃; for 0.916667h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran; hexane at -30 - 20℃; Inert atmosphere; | |
With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 7% 2: 88% | With chromium dichloride; benzaldehyde In N,N-dimethyl-formamide at 30℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 88% 2: 7% | With chromium dichloride In N,N-dimethyl-formamide at 30℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 1,3 dithiane With n-butyllithium In tetrahydrofuran at -40℃; for 2h; Stage #2: 1-Iodododecane In tetrahydrofuran at -40℃; for 3h; | |
47% | Stage #1: 1,3 dithiane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran; hexane at -78 - 0℃; for 2.5h; Inert atmosphere; | 2-Dodecyl-1,3-dithiane 1,3-dithiane (600 mg, 5.0 mmol) is dissolved in absolute THF (8 mL) and cooled to -78 °C. A 1.6 M solution of n-BuLi in hexane (3.1 ml, 5.0 mMol) was added dropwise. A clear solution was obtained, from which a solid precipitated. After 2 h of stirring at -78 °C, a solution of dodecyl iodide (1.50 g, 5.1 mMol) in THF (3 mL) was added dropwise. The mixture was stirred at -78 °C for another 30 min, then at 0 °C for 2 h. TLC in petrol ether / ethyl acetate (10:1) indicated did not show residual starting material. After reaching room temperature the mixture was diluted with 400 ml of water and extracted with ether (3x 150 ml). The combined ether layers were extracted with water (1x) and saturated NaCl (1x). The solvents were removed at the rotary evaporator and the residue was chromatographed on silica using petrol ether / ethyl acetate (40:1) to yield 673 mg (47%) of dithiane 16.ESI-MS: 289.2 (M•H+), 577.1 (2M•H+); negative MS: 575.1 (2M-H-).HPLC: RT = 24.4 min (80%, ELSD). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With (trimethylsilyl)methylmagnesium chloride In diethyl ether at 35℃; for 3h; | |
57% | With Co(1,3-bis(diphenylphosphino)hexane)Cl2; (trimethylsilyl)methylmagnesium chloride In diethyl ether at 35℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 78% 2: 15% | With nickel(II) iodide; samarium diiodide; Mischmetall powd In tetrahydrofuran at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With sodium hydride In tetrahydrofuran for 4h; Heating; | |
With sodium hydride In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With silver(I) nitrite In dimethyl sulfoxide; toluene at 70℃; for 4h; Darkness; | 1-Nitrododecane (4): Silver nitrite (2.0 g, 13 mmol) was dissolved in DMSO/toluene (1:1, 4 mL) followedby 1-iodododecane (1 g, 3.3. mmol). The reaction flask was then protected from light by wrappingin aluminum foil and then heated (oil bath) while stirring (70°C, 4 h). The crude reaction mixture was directlyapplied to a silica gel column and eluted (hexanes/EtOAc) to give the nitroalkane 4 as a colorless oil(0.44 g, 61%) which exhibited spectral properties which agree with those previously reported [25]. |
21% | With poly(N-butyl-4-vinylpyridinium)nitrite In hexane at 20℃; for 72h; | |
With silver(I) nitrite In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium hydride In N,N-dimethyl-formamide at 20℃; for 16h; | |
98% | With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; | 7.1 (1) Allyl 2,3-di-O-dodecyl-4,6-O-isopropylidene-α-D-glucopyranoside Allyl 4,6-O-isopropylidene-α-D-glucopyranoside (2.90 g, 11.14 mmol) was dissolved in DMF (29 mL). Dodecyl iodide (8.00 g, 27.00 mmol) and sodium hydride (55% dispersion in oil, 2.36 g, 54.00 mmol) were added to the solution under ice cooling, and the mixture was stirred at room temperature overnight. After completion of the reaction, the reaction solution was diluted with ethyl acetate, washed with ice water and saturated brine, dried over magnesium sulfate, filtrated and concentrated in vacuo. The resulting residue was purified by silica gel column chromatography (eluent: cyclohexane/ethyl acetate=9/1) to give the title compound (6.49 g, yield 98%). 400 MHz 1H NMR (CDCl3) δ 0.88 (6H, t, J=6.6 Hz), 1.26 (36H, bs), 1.41 (3H, s), 1.48 (3H, s), 1.50-1.60 (4H, m), 3.30 (1H, m), 3.49-3.74 (8H, m), 3.83 (1H, m), 4.08 (1H, dd, J=6.6, 13.3 Hz), 4.18 (1H, dd, J=5.1, 13.3 Hz), 4.90 (1H, d, J=3.7 Hz), 5.22 (1H, m), 5.32 (1H, m), 5.92 (1H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With air; triethyl borane; Bu2Ge(OEt)H In tetrahydrofuran; hexane at 20℃; | |
76% | With 2,6-dimethylpyridine; air; phenylsilane In ethanol at 20℃; for 1.5h; | |
With 2,2'-azobis(isobutyronitrile); sodium cyanoborohydride In <i>tert</i>-butyl alcohol for 3h; Inert atmosphere; Sealed tube; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 1,8-diazabicyclo[2.2.2.]octane In tetrahydrofuran; diethyl ether; toluene at 25℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With sodium hydride In N,N-dimethyl-formamide at 80℃; for 60h; | |
28% | Stage #1: N,N,N',N'-tetramethyl L-tartramide With sodium hydride In N,N-dimethyl-formamide at 20℃; for 1.5h; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide at 20 - 80℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 22h; | |
90% | With 2,4,5,6‐tetra‐9H‐carbazol‐9‐yl‐1,3‐benzenedicarbonitrile; [CoCl2(dmgH)2(pyridine)]; potassium carbonate; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 16h; Inert atmosphere; Sealed tube; Irradiation; | |
Multi-step reaction with 3 steps 1: 80 percent / NaOMe / methanol / 1) room temp., 0.5 h; 2) reflux, 2 h 2: 1) N-Chlorosuccinimide; 2) 10percent NaOH / 1) CH3OH, CH2Cl2, 0 degC, 30 min; 2) 5 min 3: 55 percent / benzene / Heating |
16.8 %Spectr. | With sodium t-butanolate In water at 50℃; for 2h; Sealed tube; UV-irradiation; | General protocol for the reaction and the method to determine the reaction yield: General procedure: For the reaction with UV: 1 mmol alkyl bromide or alkyl iodide was added into a 10 mL Quartz tube, which was followed by the addition of 1 mmol NaOtBu. Then 1 mL distilled water was added to get a biphase mixture. After sealing the tube, it was posed into a pre-heated 50 0C water bath and irradiated by a 350 watts UV lamp for 2 hours.When the reaction was stopped, 1 mL CDCl3 was employed to extract the organic compounds. After the extraction, 10 mLbenzyl alcohol, as the internal standard was added into the NMR tube. By using the integration, the conversion ratio of the starting material and the production of the elimination product can be calibrated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.33 g (96%) | 3-(N-dodecyl-N-methylamino)propanol A solution of 3-(methylamino)propanol (5.71 g, 64.0 mmol, S. Koepke, R. Kupper, and C. J. Michejda, J. Org. Chem., 44, 2718,1979)), and iodododecane (7.58 g, 25.6 mmol) was reacted as described in example 1 to give 6.33 g (96percent) of the title material as an oil, b.p. 100-105° C./0.04 torr. | |
6.33 g (96%) | 3-(N-dodecyl-N-methylamino)propanol A solution of 3-(methylamino)propanol (5.71 g, 64.0 mmol, S. Koepke, R. Kupper, and C. J. Michejda, J. Org. Chem., 44, 2718, 1979)), and iodododecane (7.58 g, 25.6 mmol) was reacted as described in example 1 to give 6.33 g (96percent) of the title material as an oil, b.p. 100-105° C./0.04 torr. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 1-Iodododecane With ammonia In water; N,N-dimethyl-formamide at 60℃; for 72h; Stage #2: With 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione; ammonia In water; N,N-dimethyl-formamide at 60℃; for 4h; | |
75% | Stage #1: 1-Iodododecane With ammonia In water; N,N-dimethyl-formamide at 60℃; for 72h; Stage #2: With ammonia; iodine In water; N,N-dimethyl-formamide at 60℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; In butanone; for 16h;Reflux; | 4-Bromo-4'-(dodecyloxy)biphenyl A mixture of 4'-bromobiphenyl-4-ol (8.41 g, 33.8 mmol), 1-iodododecane (10 g, 33.8 mmol) and K2CO3 (18.64 g, 135 mmol) in butanone (100 mL) was heated at reflux. After 16 h the mixture was poured into water (200 mL), extracted with DCM (3 x 100 mL), washed with NaOH (2 M, 100 mL), dried (MgSO4) and the solvent removed under reduced pressure. The residue was washed with hot MeOH to give the title compound (13.37 g, 95 %) as a colourless powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With n-butyllithium In tetrahydrofuran; hexane; water | 3 Preparation of 2-dodecylthieno[3,4-b]thiophene 5-Dodecyl-Thiophene-2,3-dicarboxylic acid (12). To a solution of thiophene-2,3-dicarboxylic acid (2, 10 g, 58.1 mmol), in anhydrous THF (500 mL), at -78° C. was added a 2.5 M solution of n-BuLi in hexane (77 mL, 192 mmol) over a period of 30 mins. The reaction was allowed to stir at -78° C. for another 90 mins. After 90 mins, dodecyl iodide (21.5 mL, 87.15 mmol) was added drop-wise and the reaction continued for another 8 hrs at room temperature. The reaction was quenched by adding 10 mL of water. Approx. 80% THF was removed and made the aqueous layer basic by dilute NaOH solution (color: Orangish). The aqueous layer was extracted twice with diethyl ether to remove excess dodecyl iodide, which is soluble in ether. The aqueous layer was acidified with dilute HCl (color: Yellowish Cloudy) and extracted with diethyl ether until the aqueous layer became clear. The organic layer was washed with sufficient water to remove excess HCl. The combined organic layers were dried over MgSO4 and concentrated to a crude orange solid 12 (15.8 g, 80% yield) confirmed by 1H-NMR. No purification was required in this step. |
79% | Stage #1: thiophene-2,3-dicarboxylic acid With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: 1-Iodododecane In tetrahydrofuran; hexane at -78 - 20℃; | |
Stage #1: thiophene-2,3-dicarboxylic acid With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: 1-Iodododecane In tetrahydrofuran; hexane at 20℃; for 8h; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane | 3 To a solution of thiophene-2,3-dicarboxylic acid (2, 10 g, 58.1 mmol), in anhydrous THF (500 mL), at -78° C. was added a 2.5 M solution of n-BuLi in hexane (77 mL, 192 mmol) over a period of 30 mins. The reaction was allowed to stir at -78° C. for another 90 mins. After 90 mins, dodecyl iodide (21.5 mL, 87.15 mmol) was added drop-wise and the reaction continued for another 8 hrs at room temperature. The reaction was quenched by adding 10 mL of water. Approx. 80% THF was removed and made the aqueous layer basic by dilute NaOH solution (color: Orangish). The aqueous layer was extracted twice with diethyl ether to remove excess dodecyl iodide, which is soluble in ether. The aqueous layer was acidified with dilute HCl (color: Yellowish Cloudy) and extracted with diethyl ether until the aqueous layer became clear. The organic layer was washed with sufficient water to remove excess HCl. The combined organic layers were dried over MgSO4 and concentrated to a crude orange solid 12 (15.8 g, 80% yield) confirmed by 1H-NMR. No purification was required in this step |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: 3-Bromophenol With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide for 18h; Inert atmosphere; | |
94% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 18.08h; Inert atmosphere; | 2.1 EXAMPLE 2; Synthesis of Compound 3 of Formula Step 1: Synthesis of Compound (3a) Potassium carbonate (1.20 g, 8.70 mmol) is added to a solution of 3-bromophenol (1.00 g, 5.78 mmol) in anhydrous dimethylformamide (60 ml) in an inert atmosphere at ambient temperature. After 5 minutes of stirring, iododecane (2.57 g, 8.70 mmol) is added. After 18 h, the reaction mixture is filtered. The filtrate is diluted in water (15 ml) and extracted with ethyl acetate (3×30 ml). The organic phases are combined, washed with a saturated sodium chloride solution, and concentrated at a reduced pressure. The residue obtained is purified by chromatography in a silica gel column (eluent: hexane), yielding 1.86 g (94%) of the bromoether 3a in the form of a colourless oil.IR (film, cm-1): 3067, 2924, 2853, 1590, 1573, 1467, 1228, 680. NMR 1H (250 MHz, CDCl3) δ (ppm): 7.19-7.07 (m, 3H), 6.85 (dd, 1H), 3.96 (t, 1H), 1.78 (q, 2H), 1.47-1.30 (m, 18H), 0.91 (t, 3H). NMR 13C (63 MHz, CDCl3) δ (ppm): 160.0, 130.5, 123.5, 117.7, 113.6, 122.8, 68.3, 31.9, 29.7-29.1, 26.0, 22.7, 14.1. MS (DCl/NH3) m/z: 358-360 (M+NH4), 340-342 (M+). |
Yield | Reaction Conditions | Operation in experiment |
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70% | Stage #1: 3-Bromothiophenol With potassium carbonate In N,N-dimethyl-formamide for 0.0833333h; Inert atmosphere; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide at 20℃; for 16h; | 8.1 EXAMPLE 8; Synthesis of 1-[3-(dodecylthio)phenyl]-1-hydroxy-1,2-dihydro-3H-pyrrolo[3,4-c]pyridin-3-one (9) Step 1: Synthesis of 1-bromo-3-(dodecylthio)benzene (9a) Potassium carbonate (1.6 g; 11.8 mmol) is added to a solution of 3-bromobenzene thiol (1.50 g; 7.9 mmol) in dimethylformamide (90 ml) and the system is left in an inert atmosphere for 5 minutes with stirring, and subsequently 1-iododecane (3.5 g; 11.8 mmol) is introduced. After 16 h of reaction at ambient temperature, 50 ml of water are added, the reaction medium is extracted with ethyl acetate (3×30 ml), and the organic phases are recovered, dried over sodium sulphate and concentrated in a vacuum. The product obtained 9a, in the form of a colourless oil (4.5 g), is purified by chromatography in a silica gel column (eluent: cyclohexane), yielding 1.9 g (70%).IR (cm-1): 2921 (C-H), 2851 (C-H), 1576 (CC), 1458 (C-S), 1068, 753, 676 (C-Br); NMR 1H (250 MHz, CDCl3) δ (ppm): 7.46 (dd, 1H, J=6.7 Hz and 1.6 Hz); 7.23-7.32 (m, 2H, H4); 7.16 (dd, 1H, J=12.0 Hz and 7.8 Hz); 2.97 (t, 2H, J=7.2 Hz); 1.65 (t, 2H, J=7.3 Hz); 1.29 (m, 18H); 0.91 (t, J=6.6 Hz, 3H). NMR 13C (63 MHz, CDCl3) δ (ppm): 139.8 (C); 130.7 (CH); 130.0 (CH); 128.5 (CH); 126.9 (C); 122.8 (C); 33.3 (CH2); 31.9 (CH2); 29.7-28.8 (8×CH2); 22.7 (CH2); 14.1 (CH3). MS (DCl/CH4) m/z: 357 (M+H+); 385 (M+C2H5+). HR-MS: for C18H30SBr: theoretical mass: 357.1236; calculated mass: 357.1252. |
Yield | Reaction Conditions | Operation in experiment |
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75% | Stage #1: ethane-1,2-dithiol With sodium hydroxide In ethanol at 20℃; for 0.166667h; Inert atmosphere; Stage #2: 1-Iodododecane In ethanol for 2h; Inert atmosphere; Reflux; Stage #3: With ammonium chloride In ethanol Inert atmosphere; | 2-(Dodecylthio)ethanethiol 20 To a mixture of ethanol (10 mL) and 3 N NaOH (2.6 mL, 7.8 mMol) ethanedithiol (705 mg, 641 µL, 7.5 mMol) was added. The mixture was stirred at room temperature for 10 min. Dodecyl iodide (1.48 g, 1.23 ml, 5.0 mmol) was added and the mixture was stirred at mild reflux for 2 h. Quenching and workup similar to 15 was followed by silica chromatography using petrol ether / ethyl acetate (20:1), yielding thioether 20 (981 mg, 75%), which was used in the next step without further characterization. |
Yield | Reaction Conditions | Operation in experiment |
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93% | Stage #1: N-hydroxyphthalimide With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide; mineral oil at 70℃; for 21h; Inert atmosphere; | (Z)-Ethyl 3-(3-(dodecyloxyiminomethyl)phenyl)acrylate (cis-12d) To a solution of NaH (60% in oil, 536 mg, 13.5 mmol) in DMF (12 mL) was added dropwise a solution of N-hydroxyphthalimide (2.0 g, 12.8 mmol) in DMF (8 mL) at 0 °C under an argon atmosphere. After 30 min of stirring, a solution of 1-iodododecane (7.28 g, 24.6 mmol) in DMF (8 mL) was added dropwise and the resulting mixture was stirred at 70 °C for 21 h. After the mixture was cooled to room temperature, the solvent was removed in vacuo. The residue was diluted with CHCl3 and H2O and extracted with CHCl3. The organic layer was washed with aqueous 10% NaHCO3, H2O and brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane, 20:80) to afford N-dodecyloxyphthalimide (10d, 3.76 g, 11.4 mmol, 93%) as a colorless oil. To a solution of 10d (1.66 g, 5.0 mmol) in EtOH (5 mL) was added dropwise a solution of hydrazine monohydrate (0.37 mL, 7.5 mmol) in EtOH (5 mL) at room temperature under an argon atmosphere and refluxed for 21 h. After being cooled down to room temperature, the mixture was diluted with Et2O, filtered and concentrated. The resultant crude solution was submitted to the next reaction without further purification. The crude dodecyloxyamine (256 mg, 1.27 mmol) was added to a solution of cis-8 (200 mg, 0.98 mmol) in dry EtOH (5 mL) at room temperature and the mixture was stirred at 50 °C for 22 h. The reaction mixture was concentrated. The crude product was purified by silica gel column chromatography (EtOAc/hexane, 3:97) to give cis-12d (367 mg, 0.94 mmol, 96%) as a colorless oil. |
57% | Stage #1: N-hydroxyphthalimide With sodium hydride In hexane; N,N-dimethyl-formamide; mineral oil at 20℃; for 0.25h; Inert atmosphere; Stage #2: 1-Iodododecane In hexane; N,N-dimethyl-formamide; mineral oil at 70℃; for 30h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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83% | With potassium tert-butylate; In tetrahydrofuran; at 20℃; for 21h; | To a solution of tert-butyl N-(3-bromophenyl) carbamate (3.24 g, 12 mmol) in THF (60 mL) was added potassium tert-butoxide (1.47 g, 13 mmol) and iodododecane (7.11 g, 24 mmol). The reaction proceeded at room temperature with stirring for 21 h. The mixture was extracted by ethyl acetate (3 x 25 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (hexane/ethyl acetate 7:1) to afford 4.37 g of the title compound as a yellow oil.Yield 83%. TLC Rf: 0.34 (cyclohexane/ethyl acetate 7:1). IR (cm-1 ): 2923, 2853, 1701, 1590, 1569, 1447, 1389, 1365, 1306, 1250, 1147, 870, 766, 692. 1H NMR (250 MHz, CDCl3) delta (ppm): 7.39-7.11 (m, 4 H); 3.59 (t, J = 7.4 Hz, 2 H); 1.54-1.49 (m, 2H); 1.44 (s, 9H); 1.30-1.20 (m, 18H); 0.93 (t, J = 6.2 Hz, 3H).13C NMR (63 MHz, CDCl3) delta (ppm): 155.0 (C); 144.0 (C); 130.1 (CH); 129.8 (CH); 128.9 (CH); 125.7 (CH); 121.9 (C); 80.4 (C); 49.9 (CH2); 31.9 (CH2); 29.6-28.4 (7 x CH2); 28.3 (3 x CH3); 26.7 (CH2); 22.7 (CH2); 14.1 (CH3). MS (DCI/NH3) m/z: 457/459 [M+NH4+], 440/442 [M + H+]. |
Yield | Reaction Conditions | Operation in experiment |
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72% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 20℃; | 4.2. General procedure for the formation of alkylated sulfones 7a-j General procedure: To fluorosulfone 10, dissolved in dry THF (0.07 M), alkylhalide (1.2 equiv.) and DBU (1.4 equiv.) were consecutively added dropwise. The reaction mixture was stirred at 20 °C, then quenched with saturated aqueous NH4Cl and extracted with CH2Cl2. The combined organic layers were washed with brine and dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography, and all compounds were obtained as solids after dissolution in CH2Cl2, followed by slow evaporation of the solvent. |
Yield | Reaction Conditions | Operation in experiment |
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100% | Stage #1: 1-Iodododecane; 3-(bis(3-(N,N-dimethylamino)propyl)carbamoyl)propanoic acid In N,N-dimethyl-formamide at 20℃; for 12h; Inert atmosphere; Stage #2: With amberlite IRA-400(Cl) In water for 1h; Inert atmosphere; | |
100% | Stage #1: 1-Iodododecane; 3-(bis(3-(N,N-dimethylamino)propyl)carbamoyl)propanoic acid In N,N-dimethyl-formamide at 20℃; for 12h; Inert atmosphere; Schlenk technique; Stage #2: With Amberlite IRA-400(Cl) In water; N,N-dimethyl-formamide for 1h; Inert atmosphere; Schlenk technique; | 1.a.i Step b (i,ii): Synthesis of [3-{bis(3-(N-dodecyl-N,N-dimethylamino)propyl) carbamoyl}propanoic acid]2+ Step b (i,ii):Synthesis of [3-{bis(3-(N-dodecyl-N,N-dimethylamino)propyl) carbamoyl}propanoic acid]2+:A round-bottom flask was charged with the product from step a, 3-(bis(3-(N,N-dimethylamino)propyl)carbamoyl) propanoic acid, (800.0 mg, 2.785 mmol) and 1-iodododecane (2.063 g, 1.720 mL, 6.933 mmol) in DMF (20 mL) to form a yellow homogeneous solution. After 12 h of stirring at ambient temperature, the solvent was removed under vacuum and the residue washed several times with diethyl ether to remove the excess iodododecane. The sample was dried yielding an orange oily substance that was dissolved in 10 mL of distilled water and 2.5 equivalents of Amberlite IRA-400(Cl) (2.400 g, 6.933 mmol) was added to the solution. After stirring for 1 h, Amberlite resin was removed by filtration and washed with water. An orange, oily substance was obtained in almost quantitative yield after removing excess water by freeze-drying. 1H NMR (500 MHz, CDCl3) δ 3.62 (m, 2H), 3.54 (m, 4H), 3.43-3.34 (m, 6H), 3.18 (s, 6H, NMe2), 3.13 (s, 6H, NMe2), 2.74-2.67 (m, 4H), 2.20 (m, 2H), 2.62 (m, 2H), 1.81 (m, 4H), 1.41-1.30 (m, 36H), 0.90 (t, 6H). ESI-MS m/z calculated for C38H79N3O32+; 312.8063 [M-2Cl]2+. found 312.7 [M-2Cl]2+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
< 10 %Spectr. | Stage #1: 1-Iodododecane With Ni{N(SiMe3)(C6H3-2,6-Pri2)}2 In tetrahydrofuran at -35℃; for 0.333333h; Inert atmosphere; Stage #2: methylmagnesium bromide In tetrahydrofuran at 20℃; for 0.75h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: 1,3-benzothiazol-2-ylhydrazine With lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -20℃; for 1h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran; n-heptane; ethylbenzene at 20℃; for 5h; Inert atmosphere; | 6 (Example 6) Production of a compound represented by the formula (C-6) 9.7 mL of lithium diisopropylamide (1.5 mol/L tetrahydrofuran/ethylbenzene/heptane solution) was added to the reaction vessel under a nitrogen atmosphere.The mixture was cooled to -20 ° C, and a solution obtained by dissolving 2.00 g of the compound represented by the formula (C-6-1) in 20 mL of tetrahydrofuran was added dropwise thereto, followed by stirring for 1 hour.A solution obtained by dissolving 3.94 g of the compound represented by the formula (C-6-2) in 8 mL of tetrahydrofuran was added dropwise.After stirring at room temperature for 5 hours, it was diluted with 100 mL of dichloromethane and poured into water.The organic layer was washed with brine and dried over sodium sulfate, and the solvent was evaporated.Purification by column chromatography (alumina, dichloromethane) gave 2.95 g of the compound of formula (C-6).The yield of the compound represented by the formula (C-6-1) was 73%.The reaction solution after the reaction showed a light coloration. |
73% | Stage #1: 1,3-benzothiazol-2-ylhydrazine With lithium diisopropyl amide In tetrahydrofuran; n-heptane at -20℃; for 1h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran; n-heptane at 20℃; for 5h; Inert atmosphere; | 6 (Example 6) Production of Compound Represented by Formula (C-6) In a nitrogen atmosphere, 9.7 mL of lithium diisopropylamide (1.5 mol/L tetrahydrofuran/ethylbenzene/heptane solution) was added into a reactor. The solution was cooled to -20° C., and a solution prepared by dissolving 2.00 g of a compound represented by formula (C-6-1) in 20 mL of tetrahydrofuran was added thereto dropwise, followed by stirring for 1 hour. A solution prepared by dissolving 3.94 g of a compound represented by formula (C-6-2) in 8 mL of tetrahydrofuran was added thereto dropwise. After the resulting mixture was stirred for 5 hours at room temperature, the mixture was diluted with 100 mL of dichloromethane and was poured into water. The organic layer was washed with brine and dried over sodium sulfate, and the solvent was distilled away. Purification was performed by column chromatography (alumina, dichloromethane) so as to obtain 2.95 g of a compound represented by formula (C-6). The yield from the compound represented by formula (C-6-1) was 73%. The reaction solution after the reaction had slight coloration. |
48.3% | With caesium carbonate In N,N-dimethyl-formamide at 25℃; for 20h; Inert atmosphere; | 34.1 Step 1: Synthesis of Intermediate F1 A four-necked reactor equipped with a thermometer was charged with 3.00 g (18.2 mmol) of 2-hydrazinobenzothiazole and 45 ml of DMF under a nitrogen stream to prepare a solution. After the addition of 11.9 g (36.4 mmol) of cesium carbonate and 6.45 g (21.8 mmol) of 1-iododecane to the solution, the mixture was stirred at 25° C. for 20 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, and extracted with 300 ml of ethyl acetate. After drying the ethyl acetate layer over anhydrous sodium sulfate, sodium sulfate was separated by filtration. Ethyl acetate was evaporated from the filtrate under reduced pressure using a rotary evaporator to obtain a yellow solid. The yellow solid was purified by silica gel column chromatography (toluene:ethyl acetate=95:5) to obtain 2.93 g of an intermediate F1 as a white solid (yield: 48.3%). [0454] The structure of the target product was identified by 1H-NMR. [0455] 1H-NMR (500 MHz, CDCl3, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.53 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz), 7.06 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz), 4.22 (s, 2H), 3.74 (t, 2H, J=7.5 Hz), 1.73 (tt, 2H, J=7.5 Hz, 7.5 Hz), 1.41-1.25 (m, 18H), 0.88 (t, 3H, J=7.0 Hz) |
48.3% | With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 20h; Inert atmosphere; | 8 Comparative Example 8Synthesis of Compound 3 A four-necked reactor equipped with a thermometer was charged with 3.00 g (18.2 mmol) of 2-hy- drazinobenzothiazole and 45 ml of N,N-dimethylformamideunder a nitrogen stream to prepare a solution. Afier the addition of 11.9 g (36.4 mmol) of cesium carbonate and 6.45 g (21.8 mmol) of 1-iodododecane to the solution, the mixture was stirred at room temperature for 20 hours. After completion of the reaction, the reaction mixture was added to 200 ml of water, followed by extraction with 300 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. Ethyl acetate was evaporated from the filtrate under reduced pressure using a rotary evaporator to obtain a yellow solid. The yellow solid was purified by silica gel column chromatography (toluene:ethyl acetate=95:5) to obtain 2.93 g of the compound 3 as a white solid (conversion rate: 89.0%, reaction selectivity: 72.2%, yield: 48.3%). |
48.3% | With caesium carbonate In N,N-dimethyl-formamide at 25℃; for 2h; Inert atmosphere; | 2 Synthesis of Compound 3 In Comparative Example 1, 20.71 g (151.30 mmol) of potassium carbonate was added to 19.72 g (60.52 mmol) of cesium carbonate, and 7.77 g (36.35 mmol) of 1-iodohexane was added to 10.77 g of 1-iodododecane ), The reaction was carried out in the same manner as in Comparative Example 1. After completion of the reaction, 50 g of distilled water was added to the reaction liquid, and the aqueous layer was removed. After concentrating the organic layer with a rotary evaporator, a yellow solid was obtained. This solid was purified by silica gel chromatography (n-hexane: ethyl acetate = 75: 25) to obtain 4.87 g of compound 3 as white crystals. The results are summarized in Table 1. |
2.9 g | With caesium carbonate In N,N-dimethyl-formamide at 25℃; for 20h; Inert atmosphere; | 6 (Comparative Example 6) Production of Compound Represented by Formula (C-6R) by Method Described in PTL 1 Under a nitrogen atmosphere, 3.00 g of the compound represented by Formula (C-6R-1), 45 mL of N,N-dimethylformamide, 11.9 g of cesium carbonate, 6.5 g of the compound represented by Formula (C-6R-2) were added to a reaction container, and the mixture was stirred at 25° C. for 20 hours. The resultant was poured into 200 mL of water and extracted with 300 mL of ethyl acetate. After drying over sodium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel) to obtain 2.9 g of a compound represented by Formula (C-6R). |
Yield | Reaction Conditions | Operation in experiment |
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94% | Stage #1: C10H17NO With potassium hydride In tetrahydrofuran; Petroleum ether at 0℃; for 4.5h; Inert atmosphere; Stage #2: 1-Iodododecane In tetrahydrofuran; Petroleum ether at -78℃; for 40h; Inert atmosphere; | (E)-3-(2,2-dimethylhydrazono)-2-methyl-2-octylcyclohexan-1-one (S1): General procedure: KH (30% dispersionin oil, 0.20 g, 1.50 mmol, 1.50 equiv) was washed free of oil with petroleum ether and suspended in anhydrous THF (3.0 mL). The suspension was transferred to a flame-dried, 10mL round bottomed flask under an atmosphere of N2, and the suspension was cooled to -78 °C.hydrazone 4 (0.25 g, 1.50 mmol, 1.50 equiv) was dissolved in THF (1.0 mL) and added dropwise to the KH suspension. The resulting solution was warmed to 0 °C and stirred 4.5 h.The reaction was re-cooled to -78 °C, and 1-iodooctane (0.18 mL, 1.00 mmol, 1.00 equiv) was added dropwise. The mixture was allowed to stir overnight, allowing the reaction to slowly warm to rt as the dry ice bath evaporated. After 14 h, the reaction was quenched via addition of saturated NH4Cl (aq.) (4.0 mL), and the mixture was partitioned in a separatory funnel. The organic layer was separated, and the aqueous layer was extracted with ether (3 x 10 mL). The combined organic extracts were washed with brine (10 mL), dried with magnesium sulfate and concentrated in vacuo. The product was purified via flash chromatography (80:20 to 70:30hexanes:EtOAc) to afford the product ketohydrazone (0.25 g, 91% yield) as a yellow oil |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | Stage #1: 4,7-Dimethyl-1,10-phenanthroline With lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: 1-Iodododecane In tetrahydrofuran; n-heptane; ethylbenzene at -78 - 20℃; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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88% | With potassium carbonate In N,N-dimethyl-formamide at 65℃; for 24h; | 1 1-Dodecyl-6-bromobenz[cd]indol-2(1H)-one (2) was synthesized according to the procedures described in U.S. Pat. No. 6,667,393, but with the following modifications. Specifically, a 500-mL Schlenk flask was charged with 6-bromobenz[cd]indol-2(1H)-one (1, 4.85 g, 19.6 mmol, 1.0 equiv.), potassium carbonate (27.0 g, 196 mmol, 10 equiv.), DMF (200 mL) and 1-iodododecane (8.69 g, 29.3 mmol, 1.5 equiv.). The reaction vessel was placed in an oil bath set at 65° C. and stirred for 24 hours. The mixture was cooled to room temperature and diluted with water (200 mL) and ether (500 mL). The organic layer was separated and washed with water (2×300 mL) and brine (200 mL), and then was dried with MgSO4. The solution was concentrated, and the residue was subjected to recrystallization from methanol (400 mL) to give the title compound as yellow needle-like crystals (7.22 g, 88%). 11-INMR (400 MHz, CDCl3) δ 8.15 (1H, d, J=8.3 Hz), 8.09 (1H, d, J=7.0 Hz), 7.84-7.76 (1H, m), 7.66 (1H, d, J=7.5 Hz), 6.76 (1H, d, J=7.5 Hz), 3.89 (2H, t, J=7.2 Hz), 1.82-1.70 (2H, m), 1.43-1.16 (18H, m), 0.87 (3H, t, J=6.8 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With C17H21N3NiO3; lithium hexamethyldisilazane; lithium tert-butoxide In toluene at 150℃; for 16h; Inert atmosphere; Glovebox; | |
93% | With C17H21N3NiO3; lithium hexamethyldisilazane; lithium tert-butoxide In toluene at 150℃; for 16h; | 5.c c) 2-Dodecyl-5-methyl-l-(pyridin-2-yl)-lH-indole (5bf): (0094) The representative procedure was followed using, 5-methyl-l-(pyridine-2-yl)-lH- indole (3b; 0.062 g, 0.3 mmol) and iodide 4f (0.178 g, 0.6 mmol), and the reaction mixture was stirred for 16 h. Purification by column chromatography on neutral alumina (Pet ether/EtOAc/Et3N: 20/1/0.5) yielded 5bf (0.105 g, 93%) a light yellow liquid. ^ NMR (500 MHz, CDC1 ): δ = 8.67 (dd, = 5.0, 1.5 Hz, 1H, Ar-H), 7.87 (td, =7.6, 1.9 Hz, 1H, Ar-H), 7.42 (d, = 8.0 Hz, 1H, Ar-H), 7.37 (s, 1H, Ar-H), 7.31-29 (m, 1H, Ar-H), 7.24 (d, = 8.4 Hz, 1H, Ar-H), 6.96 (dd, = 8.3, 1.1 Hz, 1H, Ar-H), 6.38 (s, 1H, Ar-H), 2.84 (t, = 7.6 Hz, 2H, CH2), 2.45 (s, 3H, CH3), 1.59-1.53 (m, 2H, CH2), 1.34-1.23 (m, 18H, CH2), 0.91 (t, = 6.9 Hz, 3H, CH3). ^C^Hj-NMR (125 MHz, CDC1 ): 152.0 (Cq), 149.7 (CH), 142.0 (Cq), 138.3 (CH), 135.8 (Cq), 129.9 (Cq), 129.1 (Cq), 123.1 (CH), 121.9 (CH), 121.1 (CH), 119.8 (CH), 109.9 (CH), 101.9 (CH), 32.1 (CH2), 29.8 (CH2), 29.8 (CH2), 29.8 (CH2), 29.7 (CH2), 29.5 (2C, CH2), 29.5 (CH2), 28.8 (CH2), 27.7 (CH2), 22.9 (CH2), 21.5 (CH3), 14.3 (CH3). HRMS (ESI): m/z Calcd for C26H36N2+H+ [M+H]+ 377.2946; Found 377.2951. |
Yield | Reaction Conditions | Operation in experiment |
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84% | Stage #1: N-tert-Butoxycarbonyl-1-amino-3-propyne; propargyl bromide With sodium hydride In N,N-dimethyl-formamide; mineral oil for 0.25h; Inert atmosphere; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide; mineral oil at 20℃; for 15h; Inert atmosphere; | tert-Butyl dodecyl(prop-2-yn-1-yl)carbamate 1a General procedure: To a stirred solution of tert-Butyl prop-2-yn-1-ylcarbamate (300 mg, 1.93 mmol, 1 eq.) in dry DMF (1.93 mL) under nitrogen at 0 °C, was addedNaH (93 mg, 60 % in oil, 2.32 mmol, 1.2 eq.) in small portions. After stirring for 15 min, 1-iodododecane (570 μL, 2.32 mmol, 1.2 eq.) was added dropwise and the reaction was warmedup to room temperature for 15 hours. After completion of the reaction, water and brine wereadded and the aqueous layer was extracted with Et2O (three times). Then, the combinedorganic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude was purified by flash column chromatography on silica gel (cyclohexane/DCM: 50/50) to afford 1a(531 mg, 1.63 mmol, 84%) as a colorless oil. 1H NMR (300 MHz, CDCl3): δ 4.03 (br. s, 2H), 3.29 (t,J = 7.3 Hz, 2H), 2.17 (t, J = 2.4 Hz, 1H), 1.54 (m, 2H), 1.46 (s, 9H), 1.33-1.21 (m, 18H), 0.88 (t, J =6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 155.2 (br. s), 80.1, 80.0 (br. s), 71.3 (br. s), 46.6, 36.4and 35.9 (br. s, rot.), 32.0, 29.8, 29.74, 29.71 (2C), 29.5 (2C), 28.5 (3C), 28.0 (br. s), 26.9, 22.8,14.2. |
Yield | Reaction Conditions | Operation in experiment |
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90% | Under a nitrogen atmosphere, 9.06 g (0.06 mol) of 4-methyl-5-thiazole ethanol and 13.89 g (0.1 mol) of 1-iodopentane were placed in a 100 mL glass reactor equipped with a stirrer and a three- 07 mol), and the mixture was stirred at 60 C. for 24 hours. The reaction solution was cooled to room temperature and concentrated with a rotary evaporator. The obtained concentrate was washed three times with 10 g of hexane, then placed in a 100 mL glass reactor equipped with a stirring bar and a three-way cock, and 9.02 g of ion exchanged water and 9.02 g of lithium bis (trifluoromethanesulfonyl) imide (0.06 mol) of an aqueous solution (73.5% aqueous solution) was added thereto, and the mixture was stirred at room temperature for 3 hours. After stirring was completed, the mixture was separated into an aqueous layer and an organic layer, and the organic layer was separated from the reaction solution. This organic layer was washed three times with 10 g of ion exchanged water, then placed in a rotary evaporator, dried under reduced pressure,30.56 g of liquid 3-pentyl-5- (2-hydroxyethyl) -4-methylthiazolium bis (trifluoromethanesulfonyl) imide was obtained (yield: 90%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(tri-n-butyltin); In toluene; at 20℃; for 10h;Sealed tube; Inert atmosphere; Irradiation; | General procedure: TMDPO (3) (278.7 mg, 0.8 mmol), alkyl iodide 11 (0.2 mmol),1,1,1,2,2,2-hexabutyldistannane (4ga) (0.2 mmol, only for Scheme 10a), and dry, degassed toluene (0.6 mL, Scheme 10 a) or BTF [(1?,1?,1?-trifluoromethyl)benzene] (0.6 mL, Scheme 10 b] were placed in a sealed Pyrex NMR tube under an inert atmosphere, and the mixture was irradiated with a xenon lamp (500 W) for 6 h at r.t. Elemental sulfur (S8) (1 mmol) was added under an inert atmosphere, and the mixture was stirred for 6 h at 40 C. The reaction mixture was concentrated, and product 12 was isolated by gel permeation chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In acetone for 30h; Reflux; | 2.1 Synthesis of cationic surfactants General procedure: Cationic surfactants were prepared by reaction of different alkyl halides, notably, dodecyl bromide and dodecyl iodine respectively with appropriate amounts of 3,3 - Iminobis (N,N - dimethylpropylamine) with the molar ratio 2:1. The reactants were allowed to reflux in acetonitrile for 30h, following which the solution was left to cool down to room temperature. The products were crystallised from acetonitrile with the addition of diethyl ether and then dried over P4O10. The chemical structure of these compounds is presented in Fig. 1. |
85% | With sodium carbonate In acetonitrile for 28h; Reflux; | Preparation of compound (19) To a solution of 3,3′-Iminobis(N,N-dimethylpropylamine) (0.021 mol; 4 g) in acetonitrile (10 mL) wasadded n-iodododecane (0.042 mol; 18.7 g) and sodium carbonate (0.021 mol; 2.23 g). The reactionmixture was heated under reflux for 28 hours. The solvent was evaporated under reduced pressureand the residue was dried over P4O10 and then crystallized from acetonitrile. White solid, mp 174-176°C, yield 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 60℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With lithium tert-butoxide In methanol; water at 50℃; for 48h; Glovebox; | 5 Example 5 In a glove box, t-BuOLi (1 mmol, 2 equivalents, 80.1 mg), B2pin2 (2 mmol, 4 equivalents, 507.9 mg) was added to the vial containing the stirrer in turn.0.85 mL of solvent methanol, 10 μL of H 2 O, iodo-n-dodecane (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 to give a mixture of petroleum ether/ethyl acetate in a volume ratio of 100:1 to 35:1.The desired product, n-dodecylboronic acid pinacol ester was obtained in a yield of 80%. When 3 equivalents of B2pin2 and 1.5 equivalents of t-BuOLi were used, the yield was 68%. |
80% | With lithium tert-butoxide In methanol; water at 50℃; for 48h; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: 1-Iodododecane With tert.-butyl lithium In diethyl ether; pentane at -78 - 20℃; for 1h; Stage #2: (1S,5R,6R)-3,3-dimethyl-6-(triethylsilyloxy)-2,4-dioxabicyclo [3.3.1]non-7-en-9-one In tetrahydrofuran; diethyl ether; pentane at -78℃; for 0.75h; | 4.6. (1S,5R,6R,9S)-9-dodecyl-3,3-dimethyl-6-(triethylsilyloxy)-2,4-dioxabicyclo[3.3.1]non-7-en-9-ol (12) To a solution of 1-iodododecane (2.03 ml, 8.26 mmol) in Et2O(16.5 ml) was added t-BuLi (1.52 M in pentane, 11.4 ml, 17.3 mmol) at 78 °C. After 5 min of stirring, the mixture was gradually warmed to room temperature over 1 h. The mixture was cooled to -78° C, and a solution of 7 (492 mg, 1.65 mmol) in THF (82.5 ml) was added. After stirring for 45 min, sat. aq. NH4Cl was added and the mixture was extracted with Et2O/CH2Cl2 (2:1). The extract was dried over Na2SO4, filtered, and concentrated under reduced pressure.The residue was purified by SiO2 column chromatography (hexane/Et2O = 9:1) to afford 12 (623 mg, 1.33 mmol, 81%) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: N-(tert-butoxycarbonyl)-2-aminopyridine With n-butyllithium In tetrahydrofuran at -78 - 0℃; Stage #2: 1-Iodododecane In tetrahydrofuran at -78 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: C39H37N5S2 With sodium hydroxide In 1,4-dioxane for 1h; Cooling with ice; Stage #2: 1-Iodododecane In 1,4-dioxane at 80℃; | 3.3 (3) Add 4.90 mmol of compound (2) to a three-necked flask containing 100 mL of 1,4-dioxane under ice bath conditions, then add 19.60 mmol of sodium hydroxide and stir for 1 hour, then add 4.90 mmol of n-iodododecane and heating at 80°C, extraction after the reaction is complete, the organic phase was dried with anhydrous sodium sulfate for 20 minutes, filtered, and then rotary evaporated under reduced pressure, the residue was recrystallized with petroleum ether to obtain compound (3), The rate is 89%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With triethylamine In N,N-dimethyl-formamide at 70℃; for 48h; Inert atmosphere; | 2.2 Step No 2: The product E (0.460 g, 0.8 mmol) is dissolved in 50 ml of DMF, in a 100 ml round-bottomed flask under an inert atmosphere. Triethylamine (0.37 ml, 3 eq) is added to the reaction medium with stirring. Finally, 1-iodododecane (0.55 ml, 2.5 eq) is added to the solution. The reaction medium is stirred at 70° C. for 48 h. 40 ml of deionized water and 2 ml of 2M HCl aqueous solution are added and the aqueous phase is extracted three times with 30 ml of dichloromethane. The product is purified on a silica column (MeOH/DCM) and the fractions containing the desired product are combined and evaporated. The product F is obtained in the form of a brown powder (0.503 g, 82% synthesis yield). Characterization of the Liquid Crystal (0108) 1H NMR (400 MHz; MeOD; 300 K): δ ppm 8.7 (d, 1H); 8.0 (d, 1H); 7.9 (d, 1H); 7.5 (dd, 1H); 7.4 (dd, 1H); 6.6 (d, 1H); 3.2 (d, 2H); 3.0 (d, 2H); 1.6 (m, 4H); 1.4 (m, 36H); 0.88 (t, 6H) (0109) Its ATR 2-FTIR spectrum recorded on a Thermo Scientific Nicolet 6700 apparatus is represented in FIG. 4. (0110) For the SAXS analysis, the sample is placed between two kapton films under an inert atmosphere and measured on a SAXS line. A rotating copper anode and a Vantec 2000 detector are used. The signal obtained is a ring of equivalent density (thus the material is isotropic); after radial integration, the 2D spectrum represented in FIG. 5 is obtained. The organized state of this material is characterized by the presence of Bragg peaks. The spectrum of the product Ib is characteristic of a structure in the form of lamellae (ratio 1:2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tert.-butyl lithium In tetrahydrofuran; hexane at -20℃; for 0.00105556h; Flow reactor; | Halogen-Lithium Exchange of (Hetero)aryl Halides with tBuLi as Exchange Reagent; Typical Procedure 2 (TP2) Using a Vapourtec ESeries Integrated Flow Chemistry System General procedure: A tBuLi solution in hexane (0.40 M, 2.0 equiv) and a solution of 2-bromopyridine (5a; 32 mg, 0.20 M, 1.0 equiv) and hexamethylacetone (2j; 28 mg, 0.20 M, 1.0 equiv) in THF were prepared. The solutions were pumped from their flasks through a suction needle with a flowrate of 6.00 mL/min. After passing a PTFE tube (volpre = 1.00, T1 = -40 °C, residence time: 10 s) for precooling, the solutions were mixed in a T-mixer (PTFE, I.D. = 0.5 mm). The combined stream passed a PTFE reactor tube (VolR = 0.02 mL; residence time: t1 = 0.1 s, T1 = -40 °C) and was subsequently collected in an empty flask. The reaction mixture was quenched with sat. aq NH4Cl solution. The aqueous phase was extracted with EtOAc and the organic phases were combined, dried, and filtered. After removal of the solvent in vacuo, flash column chromatography (silica gel, isohexane:EtOAc = 95:5 → 9:1 → 8:2) afforded the title compound 7aj as a yellow solid (41 mg, 0.19 mmol, 93%). See below for full characterization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tetra-(n-butyl)ammonium iodide; potassium hydroxide In water; toluene at 80℃; for 1h; | 3.2. 1-(10-Dodecylphenothiazin-2-yl)Ethan-1-one (2) A mixture of 2-acetylphenothiazine (1) (1.4 g, 6 mmol), dodecyl iodide (5.3 g, 1.8 mmol), potassiumhydroxide 40% (20 mL) and tert-butyl ammonium iodide (TBAI) (0.66 g, 1.8 mmol) in 20 mL toluenewas heated with stirring at 80 C for 1 h. The mixture was then cooled and mixed with 100 mL ofwater, followed by ethyl acetate extraction (4 60 mL). The organic layer was washed with a saturatedaqueous solution of ammonium chloride and then water. After drying the organic layer with sodiumsulfate anhydrous and evaporation under reduced pressure, a brown oil of the product was obtained.The product was puried by column chromatography (eluent: petroleum ether: ethyl acetate 98:2) onsilica gel to aord the pure oily product in 59% yield. 1H-NMR (850 M Hz, DMSO-d6) (ppm): 0.84 (t,3H, J = 7.65 Hz, CH3), 1.20-1.27 (m, 16H, 8CH2), 1.37 (quintet, 2H, J = 7.65 Hz, CH2), 1.67 (quintet, 2H,J = 7.65 Hz, CH2), 2.55 (s, 3H, COCH3), 3.91 (t, 2H, J = 6.8 Hz, N-CH2), 6.96 (td, 1H, J = 6.8, 0.85 H,Ar-H), 7.03 (dd, 1H, J = 7.65, 0.85 Hz, Ar-H), 7.14 (dd, 1H, J = 7.65, 1.7 Hz, Ar-H), 7.22 (td, 1H, J = 6.8,1.7 Hz, Ar-H), 7.27 (d, 1H, J = 8.5, Ar-H), 7.40 (sd, 1H, J = 1.7 Hz, Ar-H), 7.53 (dd, 1H, J = 7.65, 1.7 Hz,Ar-H). 13C-NMR (213 M Hz, DMSO-d6) (ppm): 14.43, 22.55, 26.22, 26.36, 26.44, 28.86, 29.13, 29.20,29.27, 29.40, 29.42, 31.73, 46.84, 113.91, 115.72, 122.70, 122.95, 123.61, 126.96, 127.41, 127.62, 132.04,136.24, 144.57, 145.57, 197.45. IR cm1: 2922, 2852 (aliphatic C-H), 1681 (C=O), 1591, 1558(C=C). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 3-sulfanylpropanol With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 20℃; for 0.333333h; Stage #2: 1-Iodododecane In N,N-dimethyl-formamide at 65℃; for 3h; | 18.A A. Synthesis of 3-(dodecylthio)propan-1-ol (MD-1-192) To an Ar degassed solution of 3-mercaptopropanol (1.46 mL, 16.9 mmol, 2.00 eq) in anhydrous DMF (42 mL) was added 1,8-diazabicyclo(5.4.0)undec-7-ene (2.52 mL, 16.9 mmol, 2.00 eq), and the solution was stirred for 20 min at room temperature.1-Iodododecane (2.08 mL, 8.44 mmol, 1.00 eq) was added dropwise, and the reaction mixture was heated to 65 °C for 3 hr. After confirming complete conversion by TLC, the reaction mixture was diluted with EtOAc (10 × DMF volume). The organic layer was washed with water (2 ×) and sat. aq. NH4Cl (2 ×), dried with Na2SO4, and concentrated, producing an off-white solid. The solid was purified by column chromatography (0-15% EtOAc in hexanes), yielding MD-1-192 as a white powder (1.92 g, 87% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77.3% | Stage #1: dibenzofuran With n-butyllithium In tetrahydrofuran; hexane at -78℃; Schlenk technique; Stage #2: 1-Iodododecane In tetrahydrofuran; hexane at 20℃; Schlenk technique; | Synthesis of 4-dodecyldibenzo[b,d]furan (4) A 150 mL Schlenk flask was charged with dibenzofuran (3 g, 17.85 mmol), a stir bar, and THF (75 mL; anhydrous and degassed). The flask was cooled to -78° C. on a dry ice-acetone bath. To the flask, n-BuLi (12.25 mL of n-BuLi in hexane; 1.6 M) was added via syringe over 2 min. The flask was carefully removed from the dry-ice-acetone bath and allowed to stir for 30 mins. The flask was then resubmerged in the dry-ice-acetone bath. To the flask, dodecyl iodide (5.54 g, 17.85 mmol) was added over 1 min via syringe. The reaction was allowed to stir and warm to room temperature. The reaction was quenched with water (150 mL) and the mixture was extracted with CH2Cl2 (250 mL). The organic fraction was dried (Na2SO4), filtered, and the solvent was removed on a rotory evaporator. The product was purified by column chromatography on a 100 g silica Biotage column using hexane as the eluent. Mass of product as a colorless liquid=4.64 g; yield=77.3%. 1H NMR (400 MHz, Chloroform-d) δ 7.88 (dd, J=7.7, 1.2 Hz, 1H), 7.78-7.70 (m, 1H), 7.60-7.52 (m, 1H), 7.45-7.35 (m, 1H), 7.32-7.18 (m, 3H), 3.00-2.88 (m, 2H), 1.77 (tt, J=7.8, 6.2 Hz, 2H), 1.50-1.14 (m, 18H), 0.87 (t, J=6.9 Hz, 3H). 13C NMR (101 MHz, Chloroform-d) δ 156.18, 154.94, 127.32, 127.04, 126.95, 124.83, 123.91, 122.79, 122.60, 120.75, 118.13, 111.77, 32.12, 30.08, 30.06, 29.88, 29.84, 29.81, 29.69, 29.56, 22.88, 22.84, 14.29. |
Tags: 4292-19-7 synthesis path| 4292-19-7 SDS| 4292-19-7 COA| 4292-19-7 purity| 4292-19-7 application| 4292-19-7 NMR| 4292-19-7 COA| 4292-19-7 structure
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