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CAS No. : | 1116-76-3 | MDL No. : | MFCD00009560 |
Formula : | C24H51N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | XTAZYLNFDRKIHJ-UHFFFAOYSA-N |
M.W : | 353.67 | Pubchem ID : | 14227 |
Synonyms : |
|
Num. heavy atoms : | 25 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 21 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 120.38 |
TPSA : | 3.24 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -0.99 cm/s |
Log Po/w (iLOGP) : | 6.46 |
Log Po/w (XLOGP3) : | 10.52 |
Log Po/w (WLOGP) : | 8.37 |
Log Po/w (MLOGP) : | 6.26 |
Log Po/w (SILICOS-IT) : | 8.57 |
Consensus Log Po/w : | 8.04 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 1.0 |
Egan : | 1.0 |
Muegge : | 3.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -7.27 |
Solubility : | 0.0000188 mg/ml ; 0.0000000532 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -10.54 |
Solubility : | 0.0000000103 mg/ml ; 0.0 mol/l |
Class : | Insoluble |
Log S (SILICOS-IT) : | -8.84 |
Solubility : | 0.000000516 mg/ml ; 0.0000000015 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 3.0 |
Synthetic accessibility : | 2.97 |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P261-P264-P270-P272-P273-P280-P301+P312+P330-P302+P352-P305+P351+P338+P310-P333+P313-P391-P501 | UN#: | 3082 |
Hazard Statements: | H302-H317-H318-H410 | Packing Group: | Ⅲ |
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 |
---|---|---|
95% | With manganese(IV) oxide; oxygen; In chlorobenzene; at 100℃; under 4500.45 Torr; for 4h;Autoclave; Green chemistry; | Add 0.01 g of MnO2 catalyst, 1 mmol of tributylamine and 2 g of chlorobenzene to a stainless steel autoclave with a polytetrafluoroethylene liner. Using automatic temperature control program temperature to the reaction temperature of 100 C, adding 0.6MPa oxygen, reaction 4h, the reaction process to maintain the same pressure. The reaction product was analyzed by GC-MS with a tertiary amine conversion of 90% and a formamide product selectivity of 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With 5-methyl-1,3,4-thiadiazol-2-amine; potassium hydroxide; In ethanol; water; at 25℃; for 1h; | General procedure: A mixture of alkyl halide (1.0 mmol) and 5-methyl-1,3,4-thiadiazole-2-amine (1) (0.3 mmol) were added to a flask containing 3 mmol KOH and 2 cm3 EtOH/H2O (10:1). The reaction continued at room temperature under atmospheric conditions until 1 h. The reaction progress was controlled by thin-layer chromatography. The solvent was evaporated under vacuum. Then, crude reaction mixture was purifiedby column chromatography (petroleum ether/ethyl acetate8:1) to give the tertiary amines in good yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | at 50℃; for 120h; | In einen 1 I Autoklaven werden 282,9 g (0,80 mol) Trioctylamin und 216,2 g (1,20 mol) Natriumbenzolsulfonat gegeben. Dazu werden dann 80,8 g (1,60 mol) Methylchlorid aus einer Gaskartusche in den Autoklav geleitet und das Reaktionsgemisch bei 50C ca. 5 Tage geruehrt. Der entstandene weisse Feststoff wird ueber eine Schutzgasfritte abfiltriert und die sich gebildeten zwei Phasen voneinander mit Hilfe eines Scheidetrichters getrennt. Die untere gelbliche Phase wird ueber Nacht bei 60C im HV getrocknet. Man erhaelt Methyltrioctylammonium benzolsulfonat in 63 %iger Ausbeute. Zum qualitativen Nachweis auf Chloridreste, werden ca. 1 g des Produktes in ca. 5 ml Wasser geloest und mit 2 Tropfen konzentrierter Salpetersaeure angesaeuert. Zu dieser Loesung werden dann ca. 3-4 Tropfen Silbernitrat gegeben um etwaig vorhandenes Chlorid als Silberchlorid auszufaellen. Das Ausbleiben eines Niederschlags spricht fuer die komplette Abwesenheit von Chloridresten. 1H-NMR (300 MHz, CDCl3):delta=7.4 ppm (d,2H,Hl); delta=7.0 ppm (d,2H,Hm); delta=2.8 ppm (m,6H,Hb), delta=2.7 ppm (s,3H,Ha); delta=1.2 ppm (m,6H,Hh); delta=1.0 ppm (m,24H,Hc,d,e,f); delta=0.8 ppm (t,9H,Hj). 13C-NMR (75 MHz, CDCl3):delta=144-126 ppm (C10-C13); delta= 47 ppm (C2); delta= 34-22 ppm (C3-C7); delta= 21 ppm (C1); delta= 13 ppm (C8). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7% | 1,12 Dibromododecane (0.52 g, 1.52 mmol) was dissolved in methyl isobutyl ketone (5 ml). Trioctylamine (1.12 g, 3.17 mmol) was added and the resulting mixture was deoxygenated by freeze/thaw. The mixture was stirred at reflux for 7 days and the solvent was removed under reduced pressure. The crude mixture was purified by flash chromatography (90: 30: 1 CH2C12/MeOH/NH3 (aq)). The combined fractions were then passed a down a column of Lewatit MP-64 anion resin (Cl-). The resulting fractions were combined and the solvent removed under reduced pressure to give the above compound as a yellow oil (0.11 g, 7 %).'H NMR (200 MHz, CDC13): 8 3. 37-3. 29 (12H, m), 3.02- 2.94 (4H, m), 1.78-1. 65 (16H, m), 1.32-1. 23 (76H, m), 0.89-0. 82 (18H, m, 6 x CH3). 13C (300 MHz, CDC13): 59.6, 31.6, 26.5, 22.8, 22.7, 14.3, 8 signals obscured or overlapping ; filz ESI (positive ion) 909 [M-C1-] + (100 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetone; at -20 - 20℃; | 5.0g syn-2-(2-aminothiazol-4-yl)-2-(methylcarbonyloxyimino)-acetic acid dihydrate aresuspended in 100 ml of acetone at ambient temperature and 9.7ml of tri-(n-octyl)amine isadded. The material dissolves and the mixture is cooled to -20C for crystallisation andstirred at this temperature. The crystalline material is filtered, washed with a small portion ofcold acetone and dried in vacuum.Weighed product: 8.2gH20: 0.2%1H-nmr(CDCI3) 8 0.82(t,9H,J=6.8Hz), 1.22(m,30H), 1.61(m,6H), 2.09(s,3H), 2.89(m,6H),6.79(s,1H), 7.55(brs,2H)IR(goiden gate): 3427, 3100, 2924, 2855, 1757, 1612, 1365, 1216 cm"1mp: 90 C (decomposition) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In water; toluene; | Example 17 Production of (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]benzimidazole Under a nitrogen atmosphere, 2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]thio]benzimidazole (5.00 g, 0.014 mol), toluene (35 mL), water (28 mg, 0.0016 mol, total water content 0.0017 mol) and diethyl (+)-tartrate (1.33 mL, 0.0078 mol) were mixed, and the mixture was stirred at 50 to 55 C. for 30 min. Under a nitrogen atmosphere, titanium(IV) isopropoxide (1.04 mL, 0.0035 mol) was added to the mixture, and the mixture was stirred at 50 to 55 C. for 1 hr. Under a nitrogen atmosphere and under cooling, to the obtained mixture was added <strong>[1116-76-3]trioctylamine</strong> (2.04 mL, 0.0047 mol) and then cumene hydroperoxide (3.78 mL, 0.021 mol) was added at 15 to 20 C. The mixture was reacted by stirring at 15 to 20 C. for 1.5 hr. The reaction mixture was analyzed by high performance liquid chromatography (conditions (A)). As a result, it was found that 5.4% of a sulfide form and 5.4% of a sulfone form were present as analogous substances in the reaction mixture, and other analogous substances were not present. The enantiomer excess of the title compound in the reaction mixture was 98.1% ee. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium hydroxide; In water; | EXAMPLE 1 Preparation of dimethylbenzyl cyanide A reactor was charged with 1416 g of sodium hydroxide solution, 33% strength, and 425 g of caustic soda. 6 g of <strong>[1116-76-3]trioctylamine</strong> was then added to this solution, and then 400 g of benzyl cyanide and 380 g of chloromethane were reacted in this mixture at from 20 C. to 40 C. with stirring at superatmospheric pressure. After the internal pressure had dropped to below 0.5 bar, the residual pressure was released. 2000 ml of water were then added, and the mixture was briefly stirred and allowed to settle, and then the phases were separated. The organic phase was distilled under reduced pressure to give 485.5 g of pure dimethylbenzyl cyanide having a content of more than 99%, as determined by gas chromatography "GC". |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.3% | In methanol; | EXAMPLE 18 Into a 100 ml glass reactor equipped with a reflux condenser and a stirrer, 20 g (0.091 mol) of the tetrafluorophthalic anhydride prepared in Example 3 and 32.2 g (0.091 mol) of tri-n-octylamine were charged and 3.5 g (0.109 mol) of methanol was dropwise added thereto. Then, the mixture was reacted at 140 C. for 4 hours. After completion of the reaction, the reaction mixture was separated by distillation to obtain 17.5 g of 3,4,5,6-tetrafluorobenzoic acid methyl ester. The yield was 92.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87.0% | With sodium hydroxide; | EXAMPLE 23 Into a 100 ml three necked flask, 10 g (0.04 mol) of the 4-methoxy-3,5,6-trifluorophthalic acid prepared in Example 22 and 14.2 g (0.04 mol) of trioctylamine were charged, and the mixture was reacted at 140 C. for 4 hours with stirring. After completion of the reaction, 30 ml of a 20% sodium hydroxide aqueous solution was added thereto and stirred. The aqueous phase was separated and neutralized with a 10% hydrochloric acid aqueous solution and extracted with ethyl acetate. Then, the solvent was distilled off to obtain 7.17 g of 3-methoxy-2,4,5-triflourobenzoic acid. The yield was 87.0% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In cyclohexane; | Example 5 In 50 ml of cyclohexane, 2.37 g of 2-tert-butyl-5-bromo-5-methyl-1,3-dioxolan-4-one was dissolved. To this solution, 0.50 g of n-decane (an internal standard substance for gas chromatographic analysis) and 3.89 g of <strong>[1116-76-3]trioctylamine</strong> were added, and the solution was refluxed for 2 hours to carry out dehydrohalogenation. The reaction solution was analyzed by gas chromatography to ascertain that 2-tert-butyl-5-methylene-1,3-dioxolan-4-one was formed in a conversion of 100% and a yield of 93%. The reaction solution was left to have cooled and thereafter successively washed with water, a saturated aqueous sodium hydrogencarbonate solution and a saturated brine. The solvent cyclohexane was evaporated under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 1.33 9 of the intended 2-tert-butyl-5-methylene-1,3-dioxolan-4-one (isolation yield: 85%). Data of physical properties of this compound are shown below. Boiling point: 59.0-61.5 C./6 Torr 1 H-NMR (300 MHz, CDCl3, delta): 0.97 (9H, s), 4.85 (1H, d, J=2.7 Hz), 5.12 (1H, d, J =2.7 Hz, 5.43 (1H, s) 13 C-NMR (75.5 MHz, CDCl3, delta): 24.4, 37.5, 92.6, 111.1, 146.0, 162.6 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.2% | EXAMPLE 15 Into a 100 ml three necked flask, 20 g (0.079 mol) of the 3,4,5,6-tetrafluorophthalic acid-monomethyl ester prepared in Example 14, and 27.9 g (0.079 mol) of tri-n-octylamine were charged, and the mixture was heated and stirred at 140 C. for 4 hours. After completion of the reaction, the reaction mixture was separated by distillation to obtain 15.5 g of 2,3,4,5-tetrafluorobenzoic acid methyl ester. The yield was 94.2%. | |
86.3% | EXAMPLE 16 Into a 100 ml three necked flask, 20 g (0.079 mol) of the 3,4,5,6-tetrafluorophthalic acid-monomethyl ester prepared in Example 14, and 2.8 g (0.0079 mol) of tri-n-octylamine were charged, and the mixture was heated and stirred at 140 C. for 24 hours. After completion of the reaction, the reaction mixture was separated by distillation to obtain 14.2 g of 2,3,4,5tetrafluorobenzoic acid methyl ester. The yield was 86.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With trifluoroacetic acid; In dichloromethane; chloroform; water; | Part F: (2S,4R)-4-Methyl Glutamic Acid The Boc-protected diacid, (2S,4R)-N-t-butoxycarbonyl- 4-methyl glutamic acid, was subjected to a mixture of trifluoroacetic acid:methylene chloride (40:60, 100 mL) for 3 hr at room temperature. The volatiles were removed in vacuo and the residue was azeotroped with toluene (50 mL). Water (150 mL) was added and the aqueous phase extracted with a 5% solution of <strong>[1116-76-3]trioctylamine</strong> in chloroform (3 x 200 mL). The combined organic phases were washed with water (50 mL) and the combined aqueous phases evaporated by being placed on a lyophilizer for 48 hr to give the product (4.6 g, 66% in two steps) as a white foam which was recrystallized in acetone and water. mp=169-170 C., 1 H NMR (200 MHz, D2 O): delta 3.80 (dd, J=7.3, 7.3 Hz, 1H), 2.55 (m, 1H), 2.15 (ddd, J=14.7, 8.7, 6.6 Hz, 1H), 1.75 (ddd, J=14.6, 7.4, 5.4 Hz, 1H), 1.05 (d, J=7.0 Hz, 3H). Anal. Calculated for C6 H11 NO4: C, 44.71; H, 6.88; N, 8.69. Found: C, 44.59; H, 6.85; N, 8.61. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; at 20℃; for 2h; | To orthophosphoric acid (0.37 g, 3.81 mmol, 3 eq) dissolved in 20 ml of methanol, n-<strong>[1116-76-3]trioctylamine</strong> (1.34 g, 3.81 mmol, 3 eq) is added. The mixture is stirred magnetically at ambient temperature for two hours. The methanol is then evaporated and water traces co-evaporated three times with 10 ml of anhydrous pyridine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; at 20℃; for 0.5h; | To 2-methyl-5-phosphonopent-4-enal (0.3 g, 1.27 mmol, 1 eq) dissolved in 20 ml of methanol, n-<strong>[1116-76-3]trioctylamine</strong> (0.45 g, 1.27 mmol, 1 eq) is added. The reaction mixture is stirred magnetically at ambient temperature for 30 min, the solvent is then evaporated and the water traces co-evaporated three times with 10 ml of anhydrous pyridine. To the phosphonic tributylammonium salt obtained in this way dissolved in 18 ml of anhydrous THF, diphenylphosphate chloride (0.34 g, 1.27 mmol, 1 eq) and n-<strong>[1116-76-3]trioctylamine</strong> (1.34 g, 3.81 mmol, 3 eq) are then added respectively. The mixture is kept under magnetic stirring, at ambient temperature and in a nitrogen atmosphere for two hours |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tin(IV) chloride; paraformaldehyde; In ice-water; toluene; | Stage 1: 3-Cyclopentyl-2-hydroxybenzaldehyde 1 mol (162 g) of 2-cyclopentylphenol is dissolved in 200 ml of dry toluene. While stirring vigorously and with exclusion of moisture, 0.1 mol (26 g) of tin tetrachloride and 0.45 mol (159.3 g) of <strong>[1116-76-3]trioctylamine</strong> are successively added dropwise and, after being left to stir at room temperature for 20 min., 2.2 mol (66 g) of paraformaldehyde are added to the resulting suspension. It is subsequently heated at 100 C. for 6-8 h, then poured into 4 liters of ice-water, and the pH is adjusted to 1-2 with 2N hydrochloric acid. The mixture is extracted several times with ethyl acetate, and the combined extracts are washed with saturated NaCl solution, dried over Na2 SO4 and concentrated in vacuo. The crude product is purified by column chromatography on silica gel (70-200 mum, eluent cyclohexane). An oil is obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;palladium 10% on activated carbon; In methanol; under 760.051 Torr; for 20h; | A solution of dibenzyl phosphate 3 (80 mg, 0.13 mrnol) and tri-n-octylamine (35 iLL) in methanol (10 mL) was hydrogenolyzed in the presence of 10% PdJC (100 rng) under 1 atm H2 for 20 h. The mixture was filtered, concentrated, dried anddirectly used in the next step. UMP-morpholidate 4-morpholine- N, N' dicyclohexylcarboxamidine salt (36 rng, 0.198 mmol) was added and the mixture was evaporated three times from anhydrous pyridine (1.5 mL). The mixture was dissolved in pyridine (1.0 mL), 1H-tetrazole (28 mg, 0.40 mmol) was added, and the solution was stirred for three days at rt. After evaporation of the solvent, thereaction product was dissolved in a mixture of MeOHlwater/TEA (2 rnL/0. 8 mL/0.4 mL) and stirred for 24 h. The residue was then dissolved in water and dichioromethane, and the organic phase was extracted twice with water. The aqueous phases were combined and lyophilized. The residue was purified on a Bio-Gel P2 (extra fine) colunm (1.5 x 80 cm), and eluted with 0.1 M NH4HCO3at a flow rate of 0.6 rnL/min. Lyophilization of the desired fractions (determined by HPLC Varian Microsorb C18, 100 mM NEI4HCO3, 4.1 mm) gave 1 (38.7 mg, 0.060 mmol, 45%) as a colorless powder. H NMR (300 MHz, D20): (57.96 (d, J=8.1 Hz, 1H, 6-H), 5.97-5.94 (m, 2H, 5-H, l-H), 5.55 (dd, J=7.8, 3.3 Hz, 1H, 1-H), 4.36-4.33 (m, 2H, 2'-H, 3-H), 4.26- 4.24 (rn, 1H, 4'-H), 4.21- 4.17 (m, 2H,5'-112), 4.13 (t, J=5.1 Hz, 1H, 5-H), 3.88 (rn, 1H, 4-H), 3.79-3.69 (m, 3H, 3-H, 6-H2), 2.79- 2.75 (rn, J=4.2 Hz, 2H, 1-H2), 2.53 (rn, 1H, 2-H), 2.24 (s, 3H, 3-H3). 31P NMR (121 MHz, CDC13): (5-10.74 (d, J=19.5 Hz), -12.06 (d, J=20.1Hz). 13C NMR (75 MHz, D20): (5214.3, 166.3, 151.9, 141.8, 102.9, 96.5, 88.6,83.6, 74.0, 72.1, 69.9, 68.2, 65.1, 63.9, 61.6, 43.5, 41.6, 30.3. HRMS(E1) calcd.for C,8H270,7N2P2 EM-Hr 605.0785, found 605.0803. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In methanol; water; | To a solution of hydroxygallium(III) naphthalocyaninetetrasulfonic acid (1.47 g, 1.31 mmol) in water (20 mL) and methanol (100 mL) was added <strong>[1116-76-3]trioctylamine</strong> (2.3 mL, 1.85 g, 5.24 mmol). The product immediately precipitated and was filtered off, washed with hot water (2×300 mL) and hot methanol/water (70:30, 200 mL) and dried. The solid was then washed with boiling hexane (200 mL) and dried to give the product as a green powder (1.74 g, 52%).1H NMR (CDCl3): delta 0.86 (36H, t, J=7.2 Hz); 1.26 (120H, m); 1.57 (24H, m); 3.02 (24H, m); 7.9-11.2 (20H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With 1,1'-bis-(diphenylphosphino)ferrocene; ruthenium(III) chloride trihydrate; In chlorobenzene; at 145℃; for 15h;Inert atmosphere; | An oven-dried 10 mL reaction vessel was charged with RuCl3·3H2O (2.6 mg, 0.01 mmol), dppf (5.6 mg, 0.01 mmol), 2 (0.6 mmol), and purged with argon three times. 1 (0.2 mmol) and chlorobenzene (0.8 mL) were added to the sealed reaction vessel by a syringe. The resulting solution was stirred at 145 C for 15 h. After cooling to room temperature, the volatiles were removed under vacuum and the residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate) to give 3. All new compounds were characterized by means of 1H NMR, 13C NMR, MS (EI) and HR-MS. Compound 3a: 1H NMR (400 MHz, CDCl3, ppm) delta 7.22 (d, J = 7.7 Hz, 2H), 7.12 (d, J = 7.7 Hz, 2H), 3.53 (s, 2H), 2.41 (t, J = 7.3 Hz, 4H), 2.35 (s, 3H), 1.46 (quintet, J = 7.3 Hz, 4H), 1.31 (sextet, J = 7.3 Hz, 4H), 0.90 (t, J = 7.3 Hz, 6H); 13C NMR (100 MHz, CDCl3, ppm) delta 137.1, 136.0, 128.8, 128.7, 58.4, 53.6, 29.3, 21.1, 20.6, 14.0; MS (EI) m/z (%) 233, 190, 105 (100), 77; HR-MS calcd for: C16H28N [M+H]+ 234.2216, found 234.2212. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With copper diacetate; palladium diacetate; at 70℃; for 12h;Neat (no solvent); | General procedure: A mixture of substituted indoles (2 mmol), Cu(OAc)2 (1.2 mmol), Pd(OAc)2 (0.1 mmol) and tertiary amines (1.3 mmol) was stirred at 70 C for 12 h under neat condition. The reaction mixture was dissolved in ethyl acetate and filtered through a plug of Celite. The residue was washed with ethyl acetate (2 × 20 mL). The filtrate was washed with 100 mL of water and 10 mL of 0.5 N HCl and the organic layer was collected. The aqueous phase was extracted with ethyl acetate (3 × 20 mL). The combined organic phase was washed with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by column chromatography with ethyl acetate (EA) and petroleum ether (Pet) as eluent to afford the corresponding products and appropriate yield is shown in [Table 2] and [Table 3]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 0 - 50℃; for 24h; | Example 8aPreparation of N-methyl-N,N-dioctyloctan-l-ammonium trifluoromethane sulfonateTri-n-octyl amine (10.0 g, 28.3 mmol) was dissolved in dichloromethane and cooled to 0 C. Methyl trifluoromethane sulfonate (5.6 g, 120 mol-%) was added dropwise at 0 C. The mixture was then heated to 50 C and refluxed at 50 C for 24 h. Evaporation ofdichloromethane and of unreacted methyl trifluoromethane sulfonate yields N-methyl-N,N- dioctyloctan-1 -ammonium trifluoromethane sulfonate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 11aPreparation of N,N-dioctyl-N-(4-sulfobutyl)octan-l-ammonium nitrate; Tri-n-octyl amine (19.1 g, 54.0 mmol) and 1,4-butane sultone (5.5 mL, 100 mol-%) were mixed. The mixture was heated to 170 C, refluxed at 170 C for 5 days and cooled to room temperature. 65 % (w/w) aqueous HN03 (5.2 g, 100 mol-%) was added. Extraction with dichloromethane (once with 20 ml) and evaporation of dichloromethane yields N,N-dioctyl- N-(4-sulfobutyl)octan- 1 -ammonium nitrate . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With 5%-palladium/activated carbon; In water; toluene; at 110℃; for 40h;Inert atmosphere; | General procedure: A mixture of o-phenylenediamine (1) (0.108 g, 1 mmol), tributylamine (2a) (0.185g, 1 mmol), 5% Pd/C (0.106 g, 0.05 mmol) and toluene/H2O (10 mL/0.5 mL) was placed in 25 mL round bottom flask. After the system was flushed with Ar from an Ar balloon connected to the flask via a reflux condenser, the reaction mixture was allowed to react at 110 oC for 20 h. The reaction mixture was filtered through a short silica gel column (ethylacetate-hexane mixture) to eliminate catalyst residue. Removal of the solvent left a crude mixture, which was separated by thin layer chromatography (silica gel, ethyl acetate-hexanemixture = 1/1) to give 2-propylbenzimidazole (3a) (0.115 g,72%). All products are known and several selected spectroscopic data are shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
< 0.33% | With water; at 160℃; under 7500.75 - 18751.9 Torr; for 24h;Cooling with ice; Inert atmosphere; Glovebox; Autoclave; | 123.6 g (0.35 mol) of tri-n-octylamine, 16.3 g (0.35 mol) of formic acid (98-100% by weight) and 6.3 g of water were mixed in an ice bath in the laboratory. The solution obtained was subsequently warmed to room temperature (about 20 C.) and degassed by evacuation (2 hPa abs) and admission of pure nitrogen, carried out a total of three times. A two-phase solution was obtained. This was then transferred under an N2 atmosphere in a glove box into a 270 ml autoclave (material: HC) and the autoclave was closed. The autoclave was subsequently pressurized with nitrogen to 1.0 MPa and heated to 160 C. while stirring vigorously. After the temperature had been reached, a total pressure of 2.5 MPa abs was set by injection of further N2. The reaction mixture was then stirred at 160 C. for 24 hours. The autoclave was subsequently cooled to room temperature, depressurized to atmospheric pressure and the contents were transferred to a glass vessel. The output separated into two phases. 138.2 g of organic upper phase and an aqueous lower phase of 1.3 g were obtained. Both phases were analyzed by gas chromatography to determine their di-n-octylformamide content. The upper phase comprised 0.32% by weight, and the lower phase comprised <0.1% by weight. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50%Chromat.; 48%Chromat. | With 2 wtpercent ruthenium immobilized in calcium hydroxyapatite; In octanol; at 130℃; for 3h;Inert atmosphere; | General procedure: All reactions were performed in glass batch reactors under inertargon atmosphere and were stirred magnetically. Ru/HAP is usedwithout further activation. Unless stated otherwise, a Ru/HAP with2 wt% Ru was used. For a standard reaction 1 mL of mesitylenesolvent, 0.5 mmol of amine and 2 mmol of alcohol were added tothe vial containing 3 mol% of Ru/HAP (15 mol Ru, 75 mg of the2 wt% catalyst). As an internal standard tetradecane (0.25 mmol)was added and appropriate response factors were determined. Thebatch reactor was then thoroughly flushed with argon to minimizeoxidation of substrates with residual oxygen, before the reactionwas started at 130C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99%Chromat. | With 2 wtpercent ruthenium immobilized in calcium hydroxyapatite; In octanol; at 130℃; for 24h;Inert atmosphere; | General procedure: All reactions were performed in glass batch reactors under inertargon atmosphere and were stirred magnetically. Ru/HAP is usedwithout further activation. Unless stated otherwise, a Ru/HAP with2 wt% Ru was used. For a standard reaction 1 mL of mesitylenesolvent, 0.5 mmol of amine and 2 mmol of alcohol were added tothe vial containing 3 mol% of Ru/HAP (15 mol Ru, 75 mg of the2 wt% catalyst). As an internal standard tetradecane (0.25 mmol)was added and appropriate response factors were determined. Thebatch reactor was then thoroughly flushed with argon to minimizeoxidation of substrates with residual oxygen, before the reactionwas started at 130C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | at 0 - 20℃; | 10273] Propargyl bis(pentafluoroethyl)phosphinate (4.131 g; 12.1 mmol) is slowly added dropwise to cooled (0 C.) <strong>[1116-76-3]trioctylamine</strong> (4.333 g; 12.3 mmol) in a 100 ml glass flask. An orange, more highly viscous solution forms spontaneously, which is warmed to room temperature. The readily volatile constituents are removed in vacuo (10-s mbar) at room temperature to 120 C. Trioctylpropargylammonium bis(pentafluoroethyl)phosphinate, [(C8H,7)3-NCH2CCH] [(C2F5)2P(0)0], (7.646 g; 11.0 mmol) is isolated as pale- orange liquid in a yield of 91% and a purity of 97%.10274] The isolated product is characterised by means of ?H, ?9F and 31P NMR spectra in CD3CN.10275] ?HNMR: oe in ppm: 4.11 m(2H); 3.25 m(6H); 2.92 m (1H); 1.67 m (6H); 1.34 m (30H); 0.92 M (9H).10276] ?9F NMR: oe in ppm: -81.4 m (6F), -126.1 d(4F),2JF?=66.0 Hz.10277] 3?P NMR: oe in ppm: -1.7 quin,m, 2JFF=66.0 Hz.10278] Elemental Analysis10279] Experimental, %: N 2.03, C 54.79 and H 8.08;10280] calculated for C3,H54F,QNO2P, %: N 2.02, C 53.67 and H 7.85 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | General procedure: To a solution oftri-n-pentylamine (25 mL, 0.09 mol) in ethyl acetate (250 mL) was added 2-bromoacetic acid ethyl ester (8.64 mL, 0.08 mol) and the mixture was stirred at rt for 4 days. The reaction mixture was concentrated to dryness under the reduced pressure and the residue was purified with column chromatography (silicagel CHCl3/methanol20:1). Thus obtained light yellow oil was dissolved in H2O/methanol mixture and was passed through ion-exchange chromatography (Amberite IR-402CL). The eluting solution was evaporate to dryness and was dried in vacuo using P2O5 to give 10 (18.5 g, 83%) as a light yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100 g (249.8 mmol in terms of sulfur trioxide) of fuming sulfuric acid containing 20% by mass of sulfur trioxide was placed in a 4-neck flask having an internal capacity of 200 ml, equipped with a thermometer, a stirring device, a dropping funnel, and a nitrogen gas line, and 15.2 g (49.9 mmol) of TOTP was introduced thereinto for 0.5 hours. Further, the liquid temperature was controlled to a range of 20 C. to 30 C. After completion of the addition, the reaction was carried out at the same temperature for 5 hours. (0199) While controlling the liquid temperature to a range of 20 C. to 30 C., the sulfonated reaction solution was diluted with 500 g of ion exchange water. The aqueous phase was adjusted to pH 8 to pH 9 by adding 400 g of an aqueous 20%-by-mass sodium hydroxide solution. This neutralizing liquid was concentrated to dryness in the range of 38 C. to 70 C. and 4 kPa to 56 kPa. 1100 g of methanol was added to the obtained concentrated solution, followed by naturally filtering, thereby obtaining a filtrate. This filtrate was concentrated to dryness in the range of 15 C. to 50 C. and 4 kPa to 56 kPa, thereby acquiring 17.7 g of a white solid. (0200) A glass-made column (31 mm in diameter and 340 mm in height) filled with 160 g of a strongly acidic cation exchange resin ?Dowex G-26? was prepared. 177 g (17.70 g in terms of white solids, 30.65 mmol in terms of phosphorous atoms) of an aqueous solution including 10% by mass of the white solid was allowed to pass through from the upper part of a column to a linear velocity of 9.3 m/hr to 12.5 m/hr. (0201) 30.50 g (86.24 mmol) of tri-n-octylamine was added to the acquired aqueous solution, followed by stirring in the range of 20 C. to 30 C. for 1 hour, to carry out a reaction. Thereafter, the reaction solution was concentrated in the range of 35 C. to 70 C. and 4 kPa to 56 kPa, thereby acquiring 41.46 g of a highly viscous pale orange liquid. (0202) The acquisition was a mixture including 10.75 g (9.17 mmol, 32.40% by mole) of a bis(6-methyl-3-sulfonatophenyl)(2-methylphenyl)phosphine 2 tri-n-octylammonium salt as a di-form, and 30.72 g (19.13 mmol, 67.60% by mole) of a tris(6-methyl-3-sulfonatophenyl)phosphine 3 tri-n-octylammonium salt as a tri-form. From the viewpoint that 41.46 g (28.30 mmol in terms of phosphorous atoms) of a desired product could be acquired using 15.20 g (49.94 mmol in terms of phosphorous atoms) of TOTP, the yield based on phosphorous atoms was 56.7%. This phosphorous compound was referred to as a ligand F. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.5 g; 94% | Production of Bis(6-methyl-3-sulphonatophenyl)phenylphosphine di(tri-n-octylammonium) Salt An aqueous solution including the acquisition 2 was acquired in the same manner as in Example 1, and 26.28 g (74.3 mmol) of tri-n-octylamine was added thereto, followed by stirring the mixture in the range of 20 C. to 30 C. over 1 hour, to carry out a reaction. Thereafter, the reaction liquid was concentrated to dryness in the range of 35 C. to 70 C. and 4 kPa to 56 kPa, thereby acquiring 37.18 g of a pale yellow solid. 31P-NMR (400 MHz, 305 K, DMSO-d6, phosphoric acid, ppm) delta: a (6-methyl-3-sulphonatophenyl)(2-methylphenyl)phenylphosphine tri-n-octyl ammonium ammonium salt showed a peak at -20.39 (s), and a bis(6-methyl-3-sulphonatophenyl)phenylphosphine di(tri-n-octylammonium) salt showed a peak at -17.20 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46.2% | In chloroform; for 10h;Reflux; | Compound 3 (100mg, 0.260mmol) and 0.1mL <strong>[1116-76-3]trioctylamine</strong> (excessive) in 20mL CHCl3 were stirred and refluxed for 10h. After removal of the solvent, the crude product was chromatographed on a silica gel column by using dichloromethane/ethanol (v/v from 20:1 to 25:1) as eluent to give 6a (74mg) as product. Yield: 46.2%; Yellow solid; m.p.146-148C; 1H NMR (400MHz, CDCl3) delta: 8.43 (s, 1H, Ar-H), 7.60 (s, 1H, Ar-H), 7.29 (s, 1H, Ar-H), 6.73 (s, 1H, Ar-H), 5.23 (s, 2H, ArCH2N+), 4.16 (s, 3H,-OCH3), 3.97 (s, 3H,-OCH3), 3.95 (s, 3H,-OCH3), 3.35 (t, J=8.0Hz, 6H, 3×-N+CH2-), 1.84 (m, 6H, 3×-N+CH2CH2-), 1.32 (m, 30H, 15×-CH2-), 0.87 (t, J=6.8Hz, 9H, 3×-CH3); 13C-NMR (400MHz, CDCl3) delta: 183.0, 180.7, 164.0, 161.8, 160.3, 135.8, 134.5, 133.3, 124.6, 124.2, 120.8, 118.0, 105.4, 102.1, 62.3, 59.6, 58.9, 58.2, 56.4, 55.9, 53.4, 31.6, 29.0, 26.5, 22.9, 22.6, 14.0; Anal. Calcd for C42H66BrNO5 ·0.6H2O: C 66.75, H 8.96, N 1.85; Found: C 66.60, H 8.75, N 1.88; ESI-MS, m/z: 664.47[M-Br]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(I) oxide; tricyclohexylphosphine; In chloroform; at 100℃; for 24h;Schlenk technique; Sealed tube; | General procedure: A reaction tube was charged under air with 2-aminobenzanilide(1a, 0.2 mmol), Et3N (2a, 0.6 mmol), Cu2O (10 mol%), PCy3(10 mol%), and CHCl3 (2 mL). The vessel was sealed, heated at100 C (oil-bath temperature) for 24 h, and then cooled to r.t.DDQ (1 equiv) was added, and the mixture was kept at r.t. for 1h. After filtration of the mixture and evaporation of the solventunder reduced pressure, the crude product was purified by column chromatography [silica gel, hexane-EtOAc (3:1)] to givea light-yellow solid; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With iodine; sodium carbonate; In dimethyl sulfoxide; at 100℃; for 24h;Green chemistry; | A mixture of 55.7 mg (0.2 mmol) of di-p-methoxyphenyl disulfide, 141.5 mg (0.4 mmol) of <strong>[1116-76-3]trioctylamine</strong>, 42.4 mg (0.4 mmol) of Na2CO3, 101.6 mg (0.4 mmol) of iodine was added in the reaction tube, , 2 ml of DMSO was added , heated at 100OC for 24 hours. After completion of the reaction was cooled, filtered, and the filtrate was rotary evaporated to remove the solvent, the residue was purified by silica gel column chromatography, petroleum ether The mixture was evaporated and the solvent removed by evaporation on a rotary evaporator and dried in vacuo to give a yellow liquid 33.1 mg of 2,2-di-p-methoxyphenylsulfenyl octanal in 41% yield. |
41% | With iodine; sodium carbonate; In dimethyl sulfoxide; at 100℃; for 24h;Schlenk technique; | General procedure: Under air atmosphere, a reaction tube was charged with disulfide (0.2 mmol), Tertiary amine (0.4 mmol), I2 (0.4 mmol) Na2CO3 (0.4 mmol) and DMSO (2 mL). The vessel was sealed and heated at 100 C (oil bath temperature) for 24 h and then cooled to room temperature. The reaction mixture was washed with saturated Na2S2O3(2 x 15 mL) and then brine (1 x 15 mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum. The residue was purified by flash column chromatography (hexane/ethyl acetate) to afford the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
After a 2-ethoxy -4- (beta- sulfatoethyl sulfonyl) 32.5 parts of aniline were added to 350 parts of water, added to 12 parts of sodium hydroxide then, the mixture was stirred for 5 hours at 80 .After cooling to room temperature, it was added concentrated hydrochloric acid 80 parts, were added dropwise 18 parts of a 40% aqueous sodium nitrite solution over 30 minutes at 5 to 10 C..After the dropwise addition, the mixture was stirred for 40 minutes at 5~10 , to destroy the excess of nitrous acid at sulfamic acid to obtain a diazotized. 21.9 parts of 3-sulfo-4-methyl-6-hydroxy -N- methyl-2-pyridone the diazo compound, 300 parts of water, 10% sodium hydroxide aqueous solution of 10 parts of soda ash pH = 7 .08.0 was added dropwise over 1 hour at 5 to 10 C. while maintaining the.After the dropwise addition, the mixture was stirred for 2 hours at 5 to 10 C. After stirring, 36 parts of tri -n- octyl amine, was added 62.5% 30 parts of sulfuric acid, 70and stirred for 2 hours at 80 C..The reaction solution was filtered by filtration, washed with water, then drying the obtained wet cake to obtain a dry cake 77.2 parts. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
After the 2-methoxy-5-methyl -4- (beta- sulfatoethyl sulfonyl) 32.5 parts of aniline were added to 350 parts of water, N- methyl was added to 7.8 parts and 12 parts of sodium hydroxide ethylenediamine, the mixture was stirred for 3 hours at 80 .After cooling to room temperature, it was added concentrated hydrochloric acid 80 parts, were added dropwise 18 parts of a 40% aqueous sodium nitrite solution over 30 minutes at 5 to 10 C..After the dropwise addition, the mixture was stirred for 40 minutes at 5~10 , to destroy the excess of nitrous acid at sulfamic acid to obtain a diazotized. The diazotized 3-cyano-4-methyl-6-hydroxy-N- (2-sulfoethyl) -2-pyridone 25.8 parts, 300 parts of water, 10% sodium hydroxide aqueous solution of 10 parts of soda ash in was added dropwise over 1 hour at 5 to 10 C. while maintaining the pH = 7.0~8.0.After the dropwise addition, the mixture was stirred for 2 hours at 5 to 10 C. After stirring, 36 parts of tri -n- octyl amine, was added 62.5% 30 parts of sulfuric acid and stirred for 2 hours at 70 to 80 C. The reaction solution was filtered by filtration, washed with water, then drying the obtained wet cake to obtain a dry cake 85.5 parts. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
After the (beta- sulfatoethyl sulfonyl) 28.1 parts of aniline were added to 350 parts of water, ethylenediamine 6.3 parts and 12 parts of sodium hydroxide And the mixture was stirred at 80 C. for 3 hours.After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of 40% aqueous solution of sodium nitrite was added dropwise at 5 to 10 C. over 30 minutes.After the dropwise addition, the mixture was stirred at 5 to 10 C. for 40 minutes, and excess nitrous acid was decomposed with sulfamic acid to obtain a diazotized product. This diazotized product was added dropwise to a solution of 14.6 parts of diethylaniline, 300 parts of water and 11 parts of concentrated hydrochloric acid at 5 to 10 C. over 30 minutes.After the dropwise addition, the mixture was stirred at 5 to 10 C. for 2 hours while maintaining pH = 7.0 to 8.0 with 10% aqueous sodium hydroxide solution.The reaction solution was filtered by filtration, washed with water, and the resultant wet cake was dried to obtain 37.4 parts of a dry cake. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
After 2-methoxy-5-methyl-4-(beta-sulfatoethylsulfonyl sulfonyl) 32.5 parts of aniline were added 350 parts of water, sodium hydroxide It was added to 12 parts, and the mixture was stirred for 6 hours at 80 .After cooling to room temperature, it was added concentrated hydrochloric acid 80 parts, 18 parts of 40% aqueous sodium nitritewas added dropwise over 30 minutes at 5 to 10 C..After the dropwise addition, the mixture was stirred for 40 minutes at 5~10 , to destroy the excess of nitrous acid at sulfamic acid to obtain a diazotized. 30.7 parts of the disazo compound 1-naphthol-3,6-disulfonic acid, 500 parts of water was added dropwise over 30 minutes at 5 to 10 C. in solution of 4.2 part of sodium hydroxide.After the addition, the mixture was stirred for 3 hours at 5 to 10 C. while maintaining the pH = 7.0 to 8.0 with 10% sodium hydroxide solution.After stirring, 71 parts of tri -n- octyl amine, was added 62.5% 30 parts of sulfuric acid and stirred for 2 hours at 70 to 80 C..The reaction solution was filtered by filtration, washed with water, then drying the obtained wet cake to obtain a dry cake 113.9 parts. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 60℃; for 24h; | General procedure: The new PILs group was synthesized through neutralization reaction between <strong>[1116-76-3]trioctylamine</strong> (TOA) and selected carboxylic acids. The corresponding PILs were synthesized by mixing equimolar amounts of (TOA) with 3,4-dimethylbezoic acid and salicylic acid, whilst (2:1) molar ratio was used for the TOA and nonanedioic acid [13]. The two necked flask equipped with a reflux condenser and a dropping funnel was used to conduct the neutralization reaction. The reaction flask was placed in an oil bath. The TOA was placed first in the reaction flask before carboxylic acid was added gradually under continuous stirring. After completing the acid addition, the temperature of the mixture was slowly increased and maintained at 60C using oil bath. The reactions of 3,4-dimethylbezoic acid with salicylic acid were left for 24h and with the nonanedioic acid for 96h, under continuous stirring. All obtained PILs were found to be liquid at room temperature and showed a slight yellowish color. Each synthesized PIL was dissolved in methanol, stirred with activated carbon for 15min prior to subjecting them to filtration to remove the activated carbon. The methanol was then removed using rotary evaporator, and the PILs were dried using vacuum line at 50mbar with temperature kept at 60C for 24h. | |
4.92 g | at 20℃; for 1h; | 3.54 g (10mmol) of <strong>[1116-76-3]trioctylamine</strong> and the salicylic acid 1.38g (10mmol) were measured, respectively, and it taught the reaction container. Contents were stirred and mixed at the room temperature for 1 hour, and 4.92 g of trioctyl ammonium salicylate (the chemical formula 1, colorlessness - light yellow liquid) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16%; 61%; 22% | With hydrogen; at 180℃; under 760.051 Torr;Flow reactor; | The reactions were performed in a flow-through reactor at atmospheric pressure and temperature 160-230. The reduced humid catalyst was loaded in the reactor between the glass layers of the nozzle and dried in a hydrogen stream at 120 prior to the reaction. The laboratory-grade reaction was a 12Kh18N10T steel tube (inner diameter 9 mm) put in an electric oven (heating zone height 50 mm). Temperature in the reactor was measured using a thermocouple. Hydrogen feed was adjusted using a GV-7 hydrogen generator. The feeding rate of the starting amines was 0.9 and 3.6 L kgcat-1 h-1 and that of hydrogen was 0.5 L h-1 gcat-1 at atmospheric pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | at 180℃; under 760.051 Torr; | 285 g of trioctylamine ([CH3(CH2)713N; 0.8 mol, 98%; Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany; catalog T81000) were mixed with 123.4 g of solid 3-<strong>[590-92-1]bromopropionic acid</strong> (3-BrPA; 0.8 mol, 97%; Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany; catalog 101281) in a three-necked glass reactor in a molar ratio of 1:1 at room temperature and atmospheric conditions. The reaction mixture was heated to 180C under continuous stirring with a magnetic stirring bar at a speed of 500 rpm. After the reaction mixture reached a constant temperature of 180C, the reaction products were semi-batchwise removed under reduced pressure (90-100 mbar).The liquid products were condensed and collected in an ice-cooled flask, and the gaseous byproducts were routed to the off-gas. After an overall process time of 30 mm the collected distillate was analyzed via off-line ?H NMR (JEOL ECX 400 MHz). ?H qNMR analysis of the product mixture gave an acrylic acid yield of about 90 mol% and selectivity of more than about 90 mol%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tert.-butylhydroperoxide; In water; 1,2-dichloro-ethane; at 80℃; for 12h; | General procedure: To a 5-mL screw-cap vial containing sulfonyl azide (2.0 mmol) and tertiary amine or secondary amine (1.0 mmol) in 2.0 mL of DCE, was added T-HYDRO (70 wt% in H2O, 1.0 equiv.) in a single delivery via syringe. The vial was tightly capped and the reaction mixture was stirred at 80 C for the indicated time (monitored by TLC). After the reaction was completed, the solvent was removed under reduced pressure. The crude residue was purified via silica gel column chromatography with an appropriate eluting solvent system (ethyl acetate-petroleum ether). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tert.-butylhydroperoxide; In water; acetonitrile; at 80℃; for 24h;Inert atmosphere; | General procedure: Tributylamine (1; 1.5 mmol, 3 equiv), diethyl H-phosphonate (2; 0.5 mmol, 1 equiv), TBHP (1 or 2 equiv, 70% in water) and MeCN (2.5 mL) were sequentially placed in a round-bottom flask at room temperature. The reaction mixture was heated at 80 C with stirring under an argon atmosphere for 24 hours. Upon completion, the reaction mixture was concentrated under vacuum. The residue was purified by silica gel column chromatography using petroleum ether/EtOAc (20:1 to 2:1, v/v) as eluent to give the corresponding product 3 (CAS no: 875228-32-3) (ref. 9) as a light-yellow oil (144.5 mg, 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.17 g | 7 mL of acetonitrile and 14.2 g of <strong>[1116-76-3]trioctylamine</strong> were added to epichlorohydrin (3.70g), and stirring was performed at 80 degrees C for 3 hours. Then, it condensed under decompression and obtained the rough product 15.2g. It added to what added DMF7mL, 5 mL of water, ascorbic acid (5.0g), and sodium hydroxide (1.21g), and agitated the obtained rough organism for 10 minutes at the room temperature, and performed stirring at 80 degrees C for 3 hours. 28.8 g of residue obtained by condensing under decompression was given to silica gel column chromatography. Then, it eluted with chloroform / methanol / water =7/3/0.5 mixture, condensed under decompression, and acquired output (0.17g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile; at 50℃; for 24h; | 10 parts by mass of commercially available trioctylamine, 4.29 parts by mass of methyl chloride and 30 parts by mass of acetonitrile are charged and reacted at 50 C. for 24 hours. After completion of the reaction, the reaction solution is washed with 10 parts by mass of hexane, and the solvent is distilled off to obtain 10.99 parts by mass of methyltrioctylammonium chloride. The resultant methyltrioctylammonium chloride is brought into contact with 16.8 parts by mass of a 25% NaOH aqueous solution five times, and a salt exchange reaction is carried out to methyltrioctylammonium hydroxide. Subsequently, the separated upper phase (liquid organic salt-containing phase) was taken out and dehydrated by using an evaporator to obtain a water content of 30 parts by mass based on 100 parts by mass of the total amount of the solid organic salt and the liquid organic salt To obtain 12.7 parts by mass of methyltrioctylammonium hydroxide. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate; oxygen; potassium iodide; In acetonitrile; at 90℃; under 6080.41 Torr; for 12h;Sealed tube; | General procedure: Aryl propiolic acid (1.0mmol), tertiary amine (1.5mmol), Pd(PPh3)2Cl2 (25mg, 0.05mmol), KI (25mg, 0.3mmol), and K3PO4 (100mg, 2.0mmol) were added to CH3CN (5.0mL) in a 20-mL sealed tube reactor, which was purged with carbon monoxide and oxygen. The solution was stirred at 90C for 12h. The resulting mixture was placed in a separating funnel, followed by the addition of water and NH4Cl, and the mixture was extracted with EtOAc. The separated organic layer was washed with water and dried over anhydrous MgSO4. After removal of the organic layer under vacuum, the crude product was purified by silica gel column chromatography with n-hexane/ethyl acetate as the eluent to obtain the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In toluene; for 72h;Reflux; | In a 250 mL flame-dried flask the following were loaded: 1,3-propane sultone 2 (0.20 mol, 24.4 g),<strong>[1116-76-3]trioctylamine</strong> 1 (0.15 mol, 53.1 g), dry toluene (100 mL), and a stirring bar. The reaction mixture washeated under reflux under an inert Ar-atmosphere. After 72 h, the solvent was evaporated in vacuo,and the residual brown waxy residue was thoroughly washed with Et2O until white and dried under ahigh vacuum. The zwitterion 3 (Scheme 1) was obtained as a powder in quantitative yield, its puritywas confirmed by 1H-NMR. 50% HClO4 in H2O was added (22.5 mol, 45.2 g), and the mixture washeated to 50 C for 5 h, after which two phases had formed. A 50 mL amount of deionized water wasadded, and the mixture was extracted with 3 50 mL Et2O. Every piece of glassware that came intocontact with the ionic liquid was rinsed with Et2O to minimize the losses and maximize the yield ofthe viscous ionic liquid. The combined organic phases were evaporated in vacuo and dried under ahigh vacuum until 81.32 g (94.1% overall yield). Pure trioctyl-(3-sulfopropyl)ammonium perchlorate 4(Figure 2) was obtained as a very viscous brown liquid, and its purity was confirmed by 1H-NMR and13C-NMR. These spectra can be found in the Supporting Information. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.5% | In chloroform; for 6h;Reflux; | Add about 2.6 mL (6 mmol) of <strong>[1116-76-3]trioctylamine</strong> to 15 mL of chloroform in a 100 mL three-necked flask.Further, 0.5 g (about 1.9 mmol) of p-benzyl bromide (trade name alpha,alpha -dibromo-p-xylene) was dissolved in 5 mL of chloroform and transferred to a constant pressure dropping funnel.Slowly drip the liquid in the constant pressure dropping funnel into the three-neck bottle.After refluxing for 6 h, a colorless clear liquid was obtained, and the solvent was removed under reduced pressure;A colorless viscous liquid is obtained, which is then purified using a silica gel column.Using CH2Cl2/C2H5OH (v/v=50:1?10:1) as the eluent,A colorless viscous liquid was obtained, and the structural characterization results showed the desired product.The product characterization data is as follows:Yield 80.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.1% | In chloroform; for 6h; | 1.0g (4mmol) was added to a 100mL three-necked bottle p-dibenzyl bromide (trade name alpha,alpha -dibromo-p-xylene) was dissolved in 30 ml of chloroform. At the same time, 435 ul (1 mmol) of tri-n-octylamine was dissolved in 5 ml of chloroform, transferred to a constant pressure funnel, and slowly added dropwise to a three-necked flask. After 6 h of reaction, a colorless clear liquid was obtained, and the solvent was evaporated under reduced pressure to give a colorless viscous liquid. The colorless viscous liquid was dissolved in an appropriate amount of CH2Cl2 , and the product was purified using a silica gel column, using CH2 Cl2 and ethanol as an eluent (v/v=50:1?10:1), and eluting with a gradient to obtain a colorless 438.5 mg of the viscous liquid, Compound 1, the characterization data is as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With Wilkinson?s catalyst; 1,3-bis-(diphenylphosphino)propane; water; In tetrahydrofuran; at 140℃; for 12h;Inert atmosphere; Sealed tube; | General procedure: Rh(PPh3)3Cl (2.5 mol%) and DPPP (0.04 mmol) were transferred into an oven-dried tube(15 mL), which was evacuated and backfilled with N2 (5x). THF(2 mL), H2O (1 mmol), aryl iodides (1.2 mmol), furfural (1 mmol)and amine (1.8 mmol) were added into the tube via syringe and sealed with Teflon plug. The reaction mixture was stirred at 140 C for 12 h. After the reaction was complete, the mixture was concentrated by rotary evaporation. The crude product was purified by column chromatography (EA/PE = 1/20) on a silica gel to afford the desired product. |
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