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With 3,3′-(2,2-bis(hydroxymethyl)propane-1,3-diyl)bis(1-methyl-1H-imidazol-3-ium) hydrogen sulfate for 2h; Dean-Stark; Reflux;
2.4. Synthesis of dibutyl phthalate as a typical procedure for esterificationreaction of phthalic anhydride with butanol
General procedure: The typical procedure for esterification of phthalic anhydride withbutanol is as follows: phthalic anhydride (1 mmol, 0.15 g), butanol(5 mmol, 0.46 mL, 0.37 g) and HFDAIL as catalyst (10 mol% to phthalicanhydride, 0.05 g) were charged into a 50 mL round bottom flask witha dean-stark apparatus, reflux condenser and a magnetic stirrer. Thenthe mixture was stirred at 125 °C for 7 h. The completion of reactionwas monitored by TLC using (EtOAC/Hexane 2:8) as eluent. After completionof the reaction as indicated by TLC, the product (dibutyl phthalate)was separated simply by extraction with ethyl acetate (3 × 5 mL)and ethyl acetatewas evaporated under vacuum to afford desired productas yellowoil liquid at 95% yield (0/26 g, boiling point=340 °C). Theobtained product dried under vacuumat 70 °C for 5 h. Viscous ionic liquidcould be reused after removal ofwater under vacuumat 80 °C for 5 hwithout any disposal.
Bei an einer mit einem Trockenmittel gefuellten Kolonne;
With [(O3/2)SiCH2CH2SO3X]a[Si(O4/2)]b at 130℃; for 18h;
1; 11 EXAMPLE 11
A mixture of vinyltrimethoxysilane (42.9 mL, 240 mmol) and di-tert-butyl peroxide (2 mL) was added dropwise over 20 min to a stirred solution of thioacetic acid (26.6 mL, 312 mmol) at reflux (86° C.). Reflux was maintained for a total of 3 h and the solution cooled and then added dropwise to a stirred solution of concentrated nitric acid (68%, 210 mL) at room temperature. After addition was complete, the mixture was heated at reflux for a further 90 min and then diluted to a volume of 510 mL with deionised water. Silica (171 g) was added and the mixture stirred at reflux for 6 h and then cooled. The filtered solid was washed with water (3×500 mL) and then methanol (3×500 mL) and dried to give a compound of Formula I where c=0.; A mixture of maleic acid (23.2 g, 0.2 mol), 2-ethylhexanol (78.10 g, 0.6 mol), and the compound from Example 1 (0.38 g, 0.4 wt %) was heated on an oil bath at 130° C. with stirring under reduced pressure (200 mbar). After 18 h, the mixture was cooled, filtered to recover catalyst, and analysed to show 97% diester present.
With 3-mercapto-1-propane sulfonate fuctionalized vinyl silica gel at 120℃; for 12h;
21 Example 21
Maleic acid (116.0 g, 1 mol), 2-ethylhexanol (390.0 g, 3 mol) and the compound (3.0 g) obtained in Example 2 were mixed under reduced pressure and stirred under a 120 ° C oil bath Heat with stirring. 12h the mixture was cooled and the catalyst recovered by filtration. After removal of excess alcohol, the analysis showed a 98% purity of the diester. The compounds obtained in Examples 3, 4-6, 10-12 and 16-18 also have the same effect.
9
EXAMPLE 9; To 2-(butylamino)ethanol (53.50 g, 0.46 moles) and Di-2-ethylhexyl maleate (155.45 g, 0.46 moles) was added carbon disulfide (36.00 g, 0.47 moles) dropwise with stirring. The mixture was then heated at 500C for 2 hours, then 700C for 2 hours. The reaction was then cooled to give 240.80 g of product following distillation of the excess carbon disulfide.
11
EXAMPLE 11; To diethanolamine (35.51 g, 0.34 moles), di-2-ethylhexyl maleate (115.00 g, 0.46 moles), and 70 g of isopropanol was added carbon disulfide (40.00 g, 0.53 moles) dropwise with stirring. The mixture was then heated at 500C for 2 hours, then 75-800C for 2 hours. The reaction was then cooled to give 174.17 g of product following distillation of the excess carbon disulfide and isopropanol.
7
EXAMPLE 7; To 2-ethylaminoethanol (24.00 g, 0.27 moles) and Di-2-ethylhexyl maleate (95.19 g, 0.27 moles) was added carbon disulfide (50 g, 0.65 moles) dropwise with stirring. The mixture was then heated at 500C for 2 hours, then 700C for 3 hours. The reaction was then cooled to give 135.84 g of product following distillation of the excess carbon disulfide.
EXAMPLE II Di-2-ethylhexyl-2-(N,N-dibenzylaminoxy)succinate A solution of 13.67 g of <strong>[621-07-8]N,N-dibenzylhydroxylamine</strong> and 21.82 g of di-(2-ethylhexyl)maleate in 50 ml of tetrahydrofuran is heated under reflux for 48 hours. The solvent is removed under reduced pressure and the residue is chromatographed to afford the title compound as a clear colorless liquid. Anal. Calcd. for C34 H51 NO5: C, 73.7; H, 9.3; N, 2.5. Found: C, 72.6; H, 9.3; N, 2.2.
III Di-2-ethylhexyl-2-(N,N-diethylaminoxy)succinate
EXAMPLE III Di-2-ethylhexyl-2-(N,N-diethylaminoxy)succinate A solution of 10.7 g of diethylhydroxylamine and 34.1 g of di(2-ethylhexyl)maleate in 100 ml of diglyme is heated under reflux for 32 hours. The solvent is removed under pressure and the residue is purified by liquid chromatography to afford the title compound as a clear colorless liquid. Anal. Calcd. for C24 H47 NO5: C, 67.1; H, 11.0; N, 3.3. Found: C, 67.9; H, 11.3; N, 2.9.
With potassium <i>tert</i>-butylate In toluene at 0 - 20℃; for 1h;
14
Example 14; Preparation of compound 183; To a suspension of 100 mg (0.87 mmol) of potassium tert-butanolate in 60 ml of dry toluene is added dropwise under nitrogen at 0°C 21.7 g (86.7 mmol) of 3-mercapto-propyltriethoxy- silane, followed by the dropwise addition of 29.5 g (86.7 mmol) of bis(2-ethylhexyl)maleate. The reaction mixture is stirred for one hour at room temperature. Water was then added and the product is extracted by ethyl acetate. The organic phase is washed with H2O, NaCI, dried over sodium sulfate, filtered and evaporated to dryness using a rotary evaporator to afford 54.0 g of compound 183 as yellow liquid.
With sodium disulfite; In water; at 104℃; for 3.16667h;Inert atmosphere;
Example 1 (Comparison)Production of Sodium di-(2-ethylhexyl)-sulfosuccinate (Solution in Water/Ethanol)556 g (1.63 mol) di-(2-ethylhexyl)-maleate, 40 g Hydropalat 875, 160 g (0.84 mol) sodium disulfite and 194 g deionized water were introduced into a 1-liter four-necked flask equipped with a mechanical stirrer, heating system, reflux condenser and nitrogen inlet and were heated under reflux at 104 C. in a gentle stream of nitrogen until a clear solution was obtained (ca. 3 hours). After stirring for 10 minutes, no more sulfite could be detected in the product. On cooling, the product gelled/solidified which could be avoided by addition of a co-solvent: to this end, 50 g ethanol was added at ca. 80 C. The solution thus obtained contained 75% by weight sulfosuccinate and had the following characteristic data: Epton: 16.39%; dry residue: 74.29%.
bis(2-ethylhexyl) 3,4-cis-2-acetyl-5-(trifluoromethyl)pyrazolidine-3,4-dicarboxylate[ No CAS ]
bis(2-ethylhexyl) 3,4-trans-2-acetyl-5-(trifluoromethyl)pyrazolidine-3,4-dicarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74 % de
With potassium carbonate In toluene for 30h; Reflux; Overall yield = 47 %; Overall yield = 46 mg;
Pyrazoldines 3 and 7; General Procedure
General procedure: A mixture of trifluoromethylated N-acylhydrazone 1 or 6 (0.20 mmol), dimethyl maleate (2; 58 mg, 0.40 mmol) and K2CO3 (1. 4 mg, 0.01 mmol) in toluene (5 mL) was stirred at reflux for 30-40 h and monitored by TLC until the starting material could not be detected. Toluene was removed under vacuum and sat. aq NH4Cl (10 mL) was added to the reaction mixture and stirred for 10 min, and then the mixture was extracted with EtOAc (3 × 10 mL). The combined organic extracts were dried (MgSO4) and concentrated. Purification of the residue by silica gel column chromatography using PE/EtOAc (2:1) as eluent furnished the product 3 or 7, respectively. The isomers could not be fully separated by silica gel chromatography. One of the isomers could be isolated by recrystallization, except for 3pa and 3pa′, 3xa and 3xa′, 3ya and 3ya′, 7e and 7e′.
bis(2-ethylhexyl) 3,4-cis-2-(2-methylbenzoyl)-5-(trifluoromethyl)-pyrazolidine-3,4-dicarboxylate[ No CAS ]
bis(2-ethylhexyl) 3,4-trans-2-(2-methylbenzoyl)-5-(trifluoromethyl)-pyrazolidine-3,4-dicarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72 % de
With potassium carbonate In toluene for 30h; Reflux; Overall yield = 80 %; Overall yield = 102 mg;
Pyrazoldines 3 and 7; General Procedure
General procedure: A mixture of trifluoromethylated N-acylhydrazone 1 or 6 (0.20 mmol), dimethyl maleate (2; 58 mg, 0.40 mmol) and K2CO3 (1. 4 mg, 0.01 mmol) in toluene (5 mL) was stirred at reflux for 30-40 h and monitored by TLC until the starting material could not be detected. Toluene was removed under vacuum and sat. aq NH4Cl (10 mL) was added to the reaction mixture and stirred for 10 min, and then the mixture was extracted with EtOAc (3 × 10 mL). The combined organic extracts were dried (MgSO4) and concentrated. Purification of the residue by silica gel column chromatography using PE/EtOAc (2:1) as eluent furnished the product 3 or 7, respectively. The isomers could not be fully separated by silica gel chromatography. One of the isomers could be isolated by recrystallization, except for 3pa and 3pa′, 3xa and 3xa′, 3ya and 3ya′, 7e and 7e′.
[0049] In another experiment, AREA and DEHM were reacted together, and after 24 hours, 1 equivalent of butyl acrylate (BA) was added and either a stoichiometric amount of acetic acid or a catalytic amount (1 to 5 mol%) of a Lewis acid such as SnCl2 or FeCl3. The mixture was heated to 100 °C for another 24 hours and monitored by GCMS, HPLC, and NMR. The crude product can be purified by standard techniques such as flash chromatography over silicagel or recrystallization in ethyl acetate. After isolation, the DEHM:APEA:BA adduct was formed:
2-(tetrahydro-2-furanyl) butanedioic acid 1,4-bis(2-ethylhexyl) ester[ No CAS ]
2-(tetrahydro-2-furanyl) butanedioic acid 1,4-bis(2-ethylhexyl) ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1: 59%
2: 29%
With di-tert-butyl peroxide at 20℃; for 4h; UV-irradiation; Inert atmosphere; Overall yield = 96 percent; diastereoselective reaction;
General procedure for the photolysis
General procedure: A THF (2) (10 mL) solution of olefin (1a-f) (0.2 mmol) and DTBP (0.1 mmol) was introduced into a quartz cylindrical cell (diameter: 3 cm) equipped with a three-way stopcock. The three-way stopcock was connected to the cell, a nitrogen source, and small vacuum pump. The solution was evacuated to about 50 mmHg under sonication for 5 s and nitrogen was then introduced into the cell; this cycle was repeated 10 times to remove oxygen efficiently from the solution. The photolysis was conducted using a 500-W xenon lamp (USHIO Optical Modulex SX-UI500XQ) fitted with an 18-cm water filter and a cut-off filter (Toshiba UV-29) under a nitrogen atmosphere. The irradiated light intensity was 2.0 mW/cm2, which was measured by an Ushio UIT-150-A Ultraviolet Radiometer equipped with a UVD-S365 photo detector. After photolysis, THF was removed in vacuo at 40-50 C / < 70 Torr (most of the products were volatile under reduced pressure) and the consumption of the olefin and the products yield were determined by NMR spectroscopy using a precise amount of naphthalene as an internal standard. The isolation of the products was conducted using silica gel column chromatography.