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CAS No. : | 117-21-5 | MDL No. : | MFCD00023107 |
Formula : | C8H3ClO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UERPUZBSSSAZJE-UHFFFAOYSA-N |
M.W : | 182.56 | Pubchem ID : | 67014 |
Synonyms : |
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 41.2 |
TPSA : | 43.37 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.05 cm/s |
Log Po/w (iLOGP) : | 1.19 |
Log Po/w (XLOGP3) : | 1.92 |
Log Po/w (WLOGP) : | 1.65 |
Log Po/w (MLOGP) : | 2.24 |
Log Po/w (SILICOS-IT) : | 2.47 |
Consensus Log Po/w : | 1.89 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.55 |
Solubility : | 0.513 mg/ml ; 0.00281 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.45 |
Solubility : | 0.641 mg/ml ; 0.00351 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.08 |
Solubility : | 0.151 mg/ml ; 0.000828 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.89 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | 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 |
---|---|---|
87.7% | at 30℃; for 8 h; Inert atmosphere | In a 1000 ml three-necked flask, 18.3 g (0.1 mol) of 4-chlorophthalic anhydride and 18.3 g (0.1 mol) were added 3-chlorophthalic anhydride, 300 g of anisole as solvent, 0.13 g (0.001 mol) of nickel chloride as a catalyst, 0.198 g (0.001 mol) of C-1 as a catalyst ligand, and 0.03 g (0.0003 mol) of sodium bromide as a catalyst Auxiliary, 13 g (0.2 mol) of zinc powder was used as a reducing agent, and the reaction was stirred at 30 ° C for 8 hours under a nitrogen atmosphere. The reaction solution was filtered to remove insoluble solids in the reaction liquid. 300 g of methanol was added to the filtration mother liquor, and the product was precipitated, filtered, and dried to obtain 25.8 g of the product 2,3,3',4'-biphenyltetracarboxylic dianhydride, yield 87.7percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetic acid; for 3h;Reflux; | SYNTHESIS EXAMPLE 105-1 An acetic acid (200 mL) solution of <strong>[117-21-5]3-chlorophthalic anhydride</strong> (36.5 g) and aniline (18.6 g) was heated to reflux for 3 hours. After cooling to room temperature, the reaction mixture was poured into iced water, and the precipitated crystal was collected by filtration, washed with water and 5% isopropanol aqueous solution, and then dried. The resulting crude crystal was washed with a t-butylmethylether/petroleum ether mixed solvent to obtain 3-chloro-N-phenylphthalimide (50.1 g). 1H-NMR (CDCl3, δ ppm): 7.38-7.55 (5H, m), 7.69-7.74 (2H, m), 7.85-7.91 (1H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With aluminum (III) chloride; at 90℃; for 2h; | General procedure: A mixture of the corresponding phthalic anhydride (1 mol. equiv.), the appropriate halobenzene (8 mol. equiv.), and aluminium chloride (2.4 mol. equiv.) was heated at 90 oC for 2h, then cooled to room temperature. Ice was added followed by conc. HCl (5 mL) and the mixture was extracted into DCM (3 x 50 mL) and washed with 10% Na2CO3 solution (2 x 50 mL). The Na2CO3 washings were combined and acidified to pH3 with conc. HCl acid. The resulting precipitate was collected by filtration and dried in a vacuum oven. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrazine hydrate; acetic acid; at 0 - 125℃; for 2h;Inert atmosphere; | 3-Chloro-phthalic anhydride (5a, purchased from TCI) (10 g, 54.95 mmol) was dissolved in glacial acetic acid (100 mL), and hydrazine hydrate (20 mL) was added dropwise at 0C, and then refluxed for two hours at 125C. When the reaction was completed, the solution was cooled down to room temperature, filtrated, and washed with water until the filtrate pH=6.0, and then dried to give 5-chloro-2,3-dihydrophthalazin-1,4-dione (5b), 10.08 g white solid (yield 93%). |
93% | With hydrazine hydrate; acetic acid; In acetic acid; at 0 - 125℃; for 2h; | 3-Chloro-phthalic anhydride (5a, purchased from TCI) (10 g, 54.95 mmol) was dissolved in glacial acetic acid (100 mL), and hydrazine hydrate (20 mL) was added dropwise at 0 C., and then refluxed for two hours at 125 C. When the reaction was completed, the solution was cooled down to room temperature, filtrated, and washed with water until the filtrate pH 6.0, and then dried to give 5-chloro-2,3-dihydrophthalazin-1,4-dione (5b), 10.08 g white solid (yield 93%). |
With hydrogenchloride; hydrazine hydrate; In quinoline; for 24h;Reflux; | General procedure: A stirred solution of phthalic anhydride (S1, 1.0 equiv), HCl (10 wt% aq), and N2H4*H2O (1.5 equiv) was refluxed in an oil bath for 24 hours under air. Then, the reaction mixture was cooled to room temperature and filtered through filter paper.The filter cake was washed with H2O and dried under reduced pressure to give 2,3-dihydrophthalazine-1,4-dione (S2). The crude material was used for the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With acetic acid; at 100℃; for 3h; | Add <strong>[117-21-5]3-chlorophthalic anhydride</strong> (365 mg, 2.0 mmol) and aminopropionic acid (190 mg, 2.1 mmol) to glacial acetic acid(10 mL), heated to 100 C for 3 h. The reaction was quenched with water (10 mL), and the pH of the solution was adjusted to NaOH solution (0.1 mol/L).6-8. Filtered and dried to give a yellow solid 425mg, LC-MS and 1H-NMR confirmed the expected intermediate compound, yield 96.0%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A 45.85 g sample of an oxidation mixture in acetic acid from the oxidation of 3- and 4-chloroxylene in the presence of a catalyst composition comprising cobalt and manganese was treated with 0.143 g. of oxalic acid dihydrate and brought to reflux for 30 minutes (this process removed about 90% of the cobalt and >50% of the manganese by precipitation as the oxalate salts). The solution was then passed through a glass frit under vacuum. The remainder of the solvent was removed by evaporation (down to 16.2 g.) and distillation (down to 14.0 g. residue). The remaining light yellow solid was combined with 60 ml. of water and 40 ml. of toluene, and mixed. There was some emulsion layer which was treated in a second wash with an additional 15 ml. each of water and toluene. The solvent was removed by evaporation of each fraction to leave 10.6 g. in the water fraction and 2.7 g. in the toluene fraction. The fractions were analyzed by GC. The analytical results are shown in Table 7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; at 60℃; for 2h; | A 35 wt. % solution of crude chlorophthalic acid in water was prepared by adding appropriate amounts of 4- and 3-chlorophthalic anhydride (70/30 isomer ratio) along with a mixture of about 3 wt. % (based on crude chlorophthalic anhydride) of synthetic 4- and 7-chlorophthalide (produced by reduction of 3-chlorophthalic anhydride). This mixture was stirred at approximately 60 C. for 2 hours after which all of the chlorophthalic anhydride had hydrolyzed to chlorophthalic acid as shown by gas chromatographic (GC) analysis which showed no anhydride in the extracted organic phase. A number of vials were prepared each containing 5 milliliters (ml.) of an aqueous phase comprising a certain concentration of crude chlorophthalic acid (5 wt. % to 35 wt. %, based on the weight of the entire aqueous phase and, optionally, acetic acid (0 wt. % to 36 wt. %, based on the weight of the entire aqueous phase). Each vial was then treated with 5 ml. of either toluene, o-dichlorobenzene (ODCB), or ortho-xylene. The vials were then shaken vigorously in a mechanical shaker for 50 minutes at a specified temperature (22 C., 42 C., or 60 C.). The phases were allowed to separate over several hours (actual phase separation occurred much quicker than this) and then each phase was sampled using a pipette. No stable emulsions were observed under the conditions which were examined. The organic phase was analyzed directly by GC (using biphenyl internal standard, following silylation of the product mixture), while for the aqueous phase, water was evaporated and solid residue was redissolved in organic solvent before GC analysis. The analytical data were used to calculate an equilibrium constant, K, which represented the ratio of chlorophthalides mass fraction in the organic phase to that in the aqueous phase. The analytical data were also used to calculate a selectivity constant, beta, which represented the quotient of [(wt. fraction of chlorophthalides in xylene)/(wt fraction of chlorophthalic acids in xylene)] divided by the quotient of [(wt fraction of chlorophthalides in water)/(wt fraction of chlorophthalic acids in water)]. The data in Table 1 show results of extractions performed at 22 C. with no acetic acid present. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic anhydride; at 122 - 136℃; for 2h;Product distribution / selectivity; | Example 2a (Cyclization Procedure Using Acetic Anhydride) The crude reaction product of Example 2 was divided into two identical fractions each weighing 1355 grams. One of the two fractions was subjected to distillation at atmospheric pressure (pot temperature 150 C.) until a total of about 952.9 grams of a mixture of water and acetic acid had been collected in the receiving vessel. The maximum head temperature was 122 C. When the head temperature reached 122 C. acetic anhydride (196.5 g, 1.93 mole) was added dropwise to the distillation flask and the resultant blue solution (no precipitate was observed) was heated at reflux (136 C.) for a two hour period. A mixture of acetic acid and acetic anhydride (198.6 grams) was then distilled off at atmospheric pressure (pot temperature 160 C.). Thereafter, vacuum was carefully applied to remove any remaining acetic anhydride, and the product chlorophthalic anhydride was distilled under vacuum. Two fractions were collected, the first distilled at 70-98 C. at a pressure in a range between 18 and 645 mbar. The first fraction (81.2 grams) contained residual acetic acid, acetic anhydride and product chlorophthalic anhydride. The second fraction distilled at between 136 and 144 C. at a pressure in a range between 3 and 5 mbar. The second fraction distilled at between 136 and 144 C. at a pressure in a range between 3 and 5 mbar. The second fraction consisted essentially of a mixture of 3- and 4-chlorophthalic anhydride (276.6 g, 1.52 mole, 86.6% of theory). Examples 3a-14a were carried out as described for Example 2. Data are gathered in Table 2. | |
at 175℃; under 60.006 Torr; for 3h;Product distribution / selectivity; | The crude reaction product of Example 14 was sampled for analysis and then divided into two identical fractions (fractions ?a? and ?b?) each weighing 1351 grams. Fraction ?b? was charged to a 2-liter flask. Distillation was carried out at atmospheric pressure (maximum pot temperature 175 C.) until a total of about 1012.8 grams of distillate had been removed. Vacuum was then carefully applied until a pressure of about 80 mbar was achieved and the mixture was heated under vacuum for about 3 hours at 175 C. to effect ring closure and water removal. The crude anhydride was vacuum distilled to afford purified chlorophthalic anhydride (282.6 g, 88.5%) as a colorless solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | 1,1,2,2,3,3-Hexaethylguanidiniumchlorid; In 1,2-dichloro-benzene; at 180℃; for 2.0h; | A dry 100 mL flask was charged with 2.0 g (7.3 mmol) of the <strong>[2444-90-8]disodium bisphenol</strong> A, 2.67 g (14.6 mmol) of 3-chlorophthalic anhydride, 4 mL (14 mmol) of hexaethylguanidinium chloride as a 15 weight % solution in o-dichlorobenzene, 48 g of dry o-dichlorobenzene, and 100 mg of o-terphenyl (internal standard). The flask was immersed in an oil bath maintained at 180 C. and the mixture was stirred magnetically. The reaction was followed as in Example 1. The yield of bisphenol A dianhydride had reached 40 % after 2 hour. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In acetic acid; | (1-1) Production of 3-chloro-N-[4-(1,1,2,2-tetrafluoroethoxy)-2-methylphenyl]phthalimide In 10 ml of acetic acid were dissolved 0.55 g of <strong>[117-21-5]3-chlorophthalic anhydride</strong> and 0.67 g of 4-(1,1,2,2-tetrafluoroethoxy)-2-methylaniline, and the reaction was carried out with heating under reflux for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the resulting residue was washed with an ether-hexane mixed solvent to obtain 1.1 g of the desired compound. Physical property: m.p. 121-122 C. Yield: 95%. |
95% | In acetic acid; | (1-1) Production of 3-chloro-N-[4-(1,1,2,2-tetrafluoroethoxy) -2 -methylphenyl]phthalimide In 10 ml of acetic acid were dissolved 0.55 g of <strong>[117-21-5]3-chlorophthalic anhydride</strong> and 0.67 g of 4-(1,1,2,2-tetrafluoroethoxy)-2-methylaniline, and the reaction was carried out with heating under reflux for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the resulting residue was washed with an ether-hexane mixed solvent to obtain 1.1 g of the desired compound. Physical property: m.p. 121-122 C. Yield: 95%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With sodium acetate; In acetic acid; | EXAMPLE 9 2-(2,6-Dioxo(3-piperidyl))-4-chloroisoindoline-1,3-dione 2-(2,6-Dioxo(3-piperidyl))-4-chloroisoindoline-1,3-dione was prepared by the procedure of Example 1 from <strong>[117-21-5]3-chlorophthalic anhydride</strong> (0.40 g, 2.2 mmol), 3-aminopiperidine-2,6-dione hydrogen chloride (0.36 g, 2.2 mmol) and sodium acetate (0.19 g, 2.4 mmol) in acetic acid (10 mL). The product was a white solid (0.44 g, 69% yield); mp, 290.0-291.5 C.; 1H NMR (DMSO-d6) δ2.05-2.11 (m, 1H, CHH), 2.49-2.64 (m, 2H, CH2), 2.64-2.92 (m, 1H, CHH), 5.17 (dd, J=5.2, 12.7 Hz, 1H, NCH), 7.86-7.94 (m, 3H, Ar), 11.17 (br s, 1H, NH); 13C NMR (DMSO-d6) δ21.83, 30.91, 49.12, 122.41, 126.94, 129.84, 133.52, 136.11, 136.39, 164.77, 165.76, 169.73, 172.77; Anal Calcd for C13H9N2O4Cl: C, 53.35; H, 3.10; N, 9.57; Cl, 12.11. Found: C, 53.37; H, 2.94; N, 9.30, Cl, 11.97. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminum (III) chloride; In 1,2-dichloro-ethane; for 0.5h;Heating / reflux; | To a solution of <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3.7 g, 20 mmol) ((J. Org. Chem., 1987, 52,129-134) in 60 mL ofanhydrous 1,2-dichloroethane was added 6.6 g (50 mmol) of AlCls followed by 4.6 g (20mmol) of methyl 3-(3-chloro-2,4-dihydroxyphenyl)propanoate (WO 03/023357). Thereaction was heated at reflux for 30 min, cooled and concentrated. The resultant gelatinousmaterial was partitioned between cold 2 N HC1 (100 mL) and ethyl acetate (100 mL). Theorganic layer was washed with 1 N HC1, brine, dried over Na2SO4 and concentrated to affordan oily material (mixture of 6- and 2-chloroisomers). The oil was dissolved indichloromethane (~40 mL) and briefly sonicated (ultrasound bath) to initiate crystallization.The mixture was cooled (ice/water bath) and allowed to crystallize for 30 min (extendedcrystallization time will result in co-crystallization of undesired 2-chloro isomer). Thecrystals were collected by filtration washed with cold dichloromethane. Drying undervacuum afforded 4.01 g of desired 6-chloro isomer (32). *H NMR (DMSO-d6) 8 12.47 (br s,1H), 10.78 (br s, 1H), 8.06 (d, J=7.7 Hz ,1H), 7.89 (d, J-7.9 Hz, 1H), 7.71 (t, J=7.9 Hz, 1H),6.76 (s, 1H), 3.46 (s, 3H), 2.27 (m, 2H), 2.41 (t, J=6.6 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With thionyl chloride; potassium fluoride; urea; In sulfolane; water; acetone; | EXAMPLE 2 500 parts (2.739 moles) of <strong>[117-21-5]3-chlorophthalic anhydride</strong> and 49.9 parts of thionyl chloride are added to 820 parts of sulfolane, while stirring. The mixture is stirred for 30 minutes at 100 C., after which the evolution of gas is complete. Excess thionyl chloride is stripped off under reduced pressure from a water pump, after which 175 parts of potassium fluoride are added and stirring is continued for 6 hours at 210 C. The mixture is cooled to 60 C., and 82 parts (1.37 moles) of urea are then added. The mixture is stirred for 1 hour 30 minutes at 130 C., when evolution of gas is complete, after which stirring is continued for a further 15 minutes at 170 C. The mixture is then cooled to room temperature, 300 parts of acetone are added, while stirring, and the predominantly inorganic precipitate is filtered off under suction. The filtrate is freed from acetone in a rotary evaporator, and the residue is then distilled over a 10 cm packed column at a bath temperature of 140-170 C. under 0.4 mbar. The distillation residue is stirred with water, and the product is filtered off under suction, washed with methyl tert.-butyl ether and dried, 382 parts (84.5% of theory) of 3-fluorophthalimide of melting point 176-179 C. being obtained. By treating the inorganic residue with 300 parts of acetone, separating off the extract and evaporating it down under reduced pressure, a further 29 parts (6.8% of theory) of 3-fluorophthalimide of melting point 166-178 C. are isolated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; formamide; | EXAMPLE 2 (b 1) 300 parts of 3-chlorophthalic anhydride in 1,200 parts by volume of formamide are stirred for 2 hours at 140 C. The mixture is then allowed to cool to 100 C. after which the solution is poured into 5,000 parts by volume of water. The precipitate which forms is filtered off, washed with water and dried under reduced pressure. 275 parts (92.2% of theory) of 3-chlorophthalimide, of melting point 236-238 C., are obtained. (b 2) one part of sulfamic acid and 3 parts by volume of <strong>[126-71-6]triisobutyl phosphate</strong> are added to a 3-chlorophthalimide solution (consisting of 182 parts of 3-chlorophthalimide, 2,500 parts by volume of water and 82 parts of 50 percent strength by weight sodium hydroxide solution). A solution of 550 parts of 13.4 percent strength by weight sodium hypochlorite solution in 800 parts by volume of water is added in one shot at 5 C., with vigorous stirring. 10 seconds after the start of the addition of the hypochlorite, the mixture is brought to pH 7 by adding 25 percent strength by weight sulfuric acid, and is then kept at pH 7 by further addition of acid. 1.5 hours after the first addition of acid, the precipitate which has formed is filtered off, washed with water and dried under reduced pressure at 60 C. 174 parts by weight (88% of theory) of a mixture of 8-chloroisatoic anhydride and 5-chloroisatoic anhydride in the ratio of 1:3 are obtained; the mixture melts, with decomposition, at 244-246 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium fluoride; | (A) A mixture of 20 parts of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, and 20 parts of anhydrous potassium fluoride was heated and maintained at about 235 C. for about 9 hours. The reaction mixture was then cooled and the crude product removed by vaccum distillation and recrystallized from chloroform to yield 12.65 parts of purified 3-fluorophthalic anhydride (69% yield). |
99 g | In a 1L three-necked flask, add 500ml of sulfolane, and then add 180g of <strong>[117-21-5]3-chlorophthalic anhydride</strong> to it,The ice bath is cooled to below 10C, and 280g of thionyl chloride is added dropwise to it. After the dropping is completed, the temperature is raised to about 100C to react for 3 hours, the temperature is lowered to room temperature, and the thionyl chloride is removed by rotary evaporation.Then 180g of anhydrous potassium fluoride was added to it. After adding potassium fluoride, the system was heated to 100C for 6 hours, and then cooled to room temperature. The inorganic salt was filtered off with suction. The filtrate was slowly poured into 900ml of ice water to precipitate a large amount of solids. Continue to stir for 2 hours and filter with suction to obtain the filter cake,Dry under vacuum to obtain crude 3-fluorophthalic anhydride.Dissolve the crude 3-fluorophthalic anhydride with 800ml of dichloromethane, dry with anhydrous magnesium sulfate, and filter with suction.Rotate the filter cake until solids are precipitated, add 2L of petroleum ether to it, continue to stir for 1 hour, and filter with suction.The filter cake is vacuum dried,99g of pure 3-fluorophthalic anhydride was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81 wt.% | With sodium hydroxide; | B. 3-Nitrophthalic Anhydride Phenyltrichlorophosphonium hexachlorophosphide (4 g, 8.8 mM) was added to phenylphosphonic dichloride (10 ml). To this solutoin, 3 nitrophthalic anhydride (1.7 g, 8.8 mM) was added. The reaction mixture was heated to 170 C. for 12 hours, then cooled to room temperature and poured onto ice. After neutralizing with 50% aqueous sodium hydroxide, the reaction was extracted with ethyl acetate. The combined ethyl acetate extracts were washed with brine, dried over magnesium sulfate, and concentrated in vacuo to give 3-chlorophthalic anhydride (1.3 g, 81 wt. % yield) as a tan solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52%. | In ethanol; | EXAMPLE 1 Preparation of 1,2-Dihydrazinocarbonyl-3-Chlorobenzene (Compound No. 1) A mixture of 3-chlorphthalic anhydride (0.01 mol) and a stoichrometric excess of hydrazine hydrate was dissolved in 25 ml of absolute ethanol. The solution was refluxed for 24 hours. The solvent was then evaporated and the product was recrystallized from ethanol. The product, 1,2-dihydrozinocarbonyl-3-chlorobenzene, was obtained in a yield of 52 percent. The pure compound was tested, using a Thomas-Hoover melting point apparatus, to determine its melting temperture at atmospheric pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In tetrahydrofuran; diethyl ether; water; | EXAMPLE X2 1,2-Bishydroxymethyl-3-chlorobenzene To a suspension of 5 g of lithium aluminium hydride in 50 ml of dry diethyl ether was added dropwise with stirring a solution of 10 g (54.8 mmole) of <strong>[117-21-5]3-chlorophthalic anhydride</strong> in 120 ml of dry tetrahydrofuran. After heating under reflux for 6 hours, the mixture was cooled and treated carefully with 5 ml of water, 5 ml of 10% sodium hydroxide solution and 10 ml of water. The solution was filtered, the filtrate was dried over magnesium sulphate, filtered and evaporated to yield the title compound as a colourless waxy solid. 1 H nmr δ(CDCl3) 7.5-7.0 (3H,m); 4.79 (2H,s); 4.60 (2H,s); 4.4-3.9 (2H, broad m, exchanges with D2 O). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 5,5-dimethyl-1,3-cyclohexadiene; chloroform; | The starting material is prepared as follows: The mixture of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, 2.5 g of 4-nitro-o-toluidine and 200 ml of xylene is refluxed for 2 days on a water-trap and evaporated. The residue is taken up in chloroform, the mixture filtered, the filtrate chromatographed on silica gel and the column eluted with chloroform-ethyl acetate (9:1), to yield the N-(4-nitro-o-tolyl)-3-chlorophthalimide melting at 229-232. | |
In 5,5-dimethyl-1,3-cyclohexadiene; chloroform; | The starting material is prepared as follows: The mixture of 3.0 g of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, 2.5 g of 4-nitro-o-toluidine and 200 ml of xylene is refluxed for 2 days on a water-trap and evaporated. The residue is taken up in chloroform, the mixture filtered, the filtrate chromatographed on silica gel and the column eluted with chloroform-ethyl acetate (9:1), to yield the N-(4-nitro-o-tolyl)-3-chlorophthalimide melting at 229.232. | |
In 5,5-dimethyl-1,3-cyclohexadiene; chloroform; | The starting material is prepared as follows: The mixture of 3.0 g of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, 2.5 g of 4-nitro-o-toluidine and 200 ml of xylene is refluxed for 2 days on a water-trap and evaporated. The residue is taken up in chloroform, the mixture filtered, the filtrate chromatographed on silica gel and the column eluted with chloroform-ethyl acetate (9:1), to yield the N-(4-nitro-o-tolyl)-3-chlorophthalimide melting at 229-232. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With formamide; at 125℃; for 3h; | A mixture of 3-chlorophthalic acid anhydride (9 g, 49.2 mmol) and formamide (100 mL) was heated to 125 C. and stirred for 3 h. Water (300 mL) was then added and the mixture was cooled to room temperature. The mixture was filtered and the resulting white solid was washed with water and dried to give 4-chloro-1H-isoindole-1,3(2H)-dione (7.7 g, 86% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Sodium phenylphosphinate; In 1,2-dichloro-benzene; at 180 - 230℃; for 7h;Product distribution / selectivity; | Comparative Example-2; Imidization in Parr Reactor with Up-Front CLPA Addition; A 450 ml Parr pressure-rated reactor equipped as in Comparative Example-1 with two side quartz windows and a partial condenser was charged with solid <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClPA, 21.578 g; 118.2 mmol), phthalic anhydride (0.2664 g; 1.8 mmol), DDS (14.898 g; 60 mmol), sodium phenylphosphinate (50 mg; 0.3 mmol) and o-DCB (85 ml). The reactor was sealed and the temperature was gradually raised. At about 180 C. the reaction mixture was observed to become homogeneous. As water of imidization was removed via the partial condenser the reaction gradually became heterogeneous and eventually the mixture became so thick that mixing of the solid adhering to the quartz window ceased to occur. As the temperature of the reaction mixture was raised further to about 190 C. the heterogeneous reaction mixture began to thin and the viscosity of the heterogeneous mixture was visibly diminished by the time the reaction mixture reached 200 C. Between about 210 C. and about 215 C. most of the solid material present in the reaction mixture dissolved. Thereafter the temperature was raised to 230 C. After about 7 hours imidization was deemed to be complete. Heating was discontinued and as the temperature decreased to about 215 C. the product bisimide began to precipitate from solution. When the temperature had decreased to about 200 C. the product mixture became so thick that efficient stirring could no longer be effected. This Comparative Example illustrates the limitations of “up-front” addition of all of the reactants. Thus, when each of the reactants is added to the reaction vessel at ambient temperature and thereafter the temperature of the reaction mixture is raised. While the reaction mixture is initially homogenous at about 180 C., as water of imidization is removed, the reaction mixture exhibits thick phase behavior which persists until the temperature reaches a higher threshold temperature, in this Comparative Example about 215 C., at which the reaction mixture becomes homogeneous again. The thick phase behavior is undesirable in that it prevents the efficient mixing of the reaction mixture while the thick phase persists and makes accurate measurement of reaction stoichiometry difficult.; Example-1; Imidization in Parr Reactor with Melt CLPA Addition-Procedure:; A 450 ml Parr pressure-rated reactor equipped as in Comparative Example-1 was charged with DDS (14.898 g; 60 mmol), sodium phenylphosphinate (50 mg, 0.3 mmole) and o-DCB (85 mL). The temperature was gradually raised to about 225-230 C. The resultant homogeneous solution was maintained at about 230 C. for 1 hr after which time molten <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClPA, 21.578 g, 118.2 mmole) and phthalic anhydride (0.2664 g; 1.8 mmol) at about 130 C. was added from a stainless steel bomb mounted on top of the reactor. The addition of 3-ClPA was carried out over a period of about 30 to 40 minutes. Water of imidization was azeotropically removed from the reactor via the partial condenser. Throughout the 3-ClPA/PA addition, and thereafter, the reaction mixture was observed to remain a homogeneous solution while at 230 C. No thick phase behavior was observed during the reaction. As the reactor was cooled, the product bisimide was observed to precipitate over a temperature range from about 215 to about 210 C. The reactor was vented when the temperature had decreased to about 170 C. and a sample of the pasty product mixture was withdrawn and analyzed by HPLC. The quality of the product bisimide (“ClPAMI”) was found to be equivalent to the quality of ClPAMI made using known methods.Larger scale imidization reactions using the method of the present invention were conducted in a 5 gallon reactor. The larger reactor was equipped with sampling features which allowed the withdrawal of samples of the reaction mixture as a homogeneous solution without venting the reactor or causing the product bisimide to precipitate during sampling. Examples 2 and 3 are illustrative.A reactor system 10 utilized in various embodiments of the invention is shown in FIG. 1. The reactor system comprised a 5-gallon stainless steel reactor 12 connected directly to monomer and catalyst feed lines 14 and inert gas purge line 15, and indirectly to feed lines 16 for addition of molten reactants. The reactor 12 was connected via distillation line 17 to a partial reflux condenser 18, a total condenser 20 and a back-pressure regulator 22. Feed lines 14 were employed for the batchwise addition of DDS, SSP catalyst, and optionally a portion of the ClPA, whereas, monomer feed lines 16 served for the semi-batch mode introduction of a molten mixture of ClPA and the chain stopper phthalic anhydride (PA). Solvent could be introduced into the reactor via solvent feed line 23.Reactant DDS, ODCB solvent and SPP catalyst were charged to the reactor 12 in batch mode, i.e. prior to starting the reaction. In some reactions a portion of th... | |
Sodium phenylphosphinate; In 1,2-dichloro-benzene; at 184.1 - 230.7℃; for 0.05 - 2.41667h;Product distribution / selectivity; | Example 2; The 5-gallon reactor described above and shown in FIG. 1 was equipped with 2 flights of 4-blade pitched turbines, and was charged according to Table I below. TABLE I Component Mass (g) Moles Source 4,4 Diamino Diphenyl Sulfone 1520.8 6.125 Atul (DDS) Phthalic Anhydride (PA) 27.19 0.184 Aldrich Sodium Phenyl Phosphinate 5.0 0.030 Akzo (SPP) 3-Chloro Phthalic Anhydride 2202.8 12.066 Pressure Chem. (ClPA) 1,2 Dicholoro Benzene (ODCB) 9756 66.37 PPG Grade F The reactor was purged with inert gas at 100 SCCM, and the agitation rate was set to 200 rpm. The partial condenser was heated by means of an oil jacket to a temperature of about 130 C. The reactor was heated by setting the reactor oil jacket temperature to 200 C. After 30-minutes of heating, the reactor oil jacket temperature was increased to 230 C. The reactor internal temperature reached a temperature of about 177 C. Water and ODCB were collected as condensed distillate. The reactor pressure was 26.3 psig. Amounts of distillate collected of the course of the reaction, reactor temperature and pressure are shown-in Table II. TABLE II Reactor P Time (min) Reactor T ( C.) (PSIG)H2O (ml) ODCB (ml) 3 184.1 26.3 36 25 6 190.4 26.3 86 52 8 197.4 26.0 114 76 10 205.9 26.4 132 92 16 219.2 25.0 171 117 22 223.5 26.4 186 128 26 225.6 26.4 191 134 30 226.7 26.3 194 138 35 227.7 26.3 198 140 57 230.7 26.2 207 145 After about 1.4 hrs of distillation, the reaction mixture was sampled via the heated sampling port. HPLC analysis of the homogeneous sample indicated that additional 3-ClPA (6.1 grams) was needed to adjust the stoichiometry to within the specified limits. At 2.5 hours of distillation, the 6.1 grams of 3-ClPA was added as a solution of about 9.8 wt % in ODCB.After a total of 4.5 hours the reaction mixture was again sampled. Sample analysis by HPLC indicated that ratio of anhydride to amine was in the range required, from about 1.00 to about 1.03. Therefore, there was no need for any further stoichiometry correction. Heating was continued for a total 9.5 hours at a reactor oil jacket set temperature of 230 C. The reaction was then cooled and diluted with ODCB to provide a slurry of the product so that approximately 3500 grams of solids was obtained as a slurry in 17.8 Kg of ODCB.; Example 3; Melt 3-CLPA Semi-Batch Reaction Mode; The 5-gallon reactor described above and shown in FIG. 1 was equipped with 2 flights of 4-blade pitched turbines, and was charged according to Table III below. TABLE III Component Mass (g) Moles Source 4,4 Diamino Diphenyl Sulfone 1520.8 6.125 Atul Inc. (DDS) Sodium Phenyl Phosphinate 5.0 0.030 Akzo Inc. (SPP) 1,2-Dicholoro Benzene 9991 68.0 PPG Grade F (ODCB) Heated tank 24 (FIG. 1) was charged with phthalic anhydride (PA) and <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClP) in the amounts shown in Table IV and heated to 140 C. in order to melt the 3-ClPA/PA solids. ODCB (240 grams) was then added to the molten mixture of 3-ClPA and PA which was completely miscible with the ODCB. Thus, the mixture in heated tank 24 comprised 3-ClPA (89.2 wt %), ODCB (9.7 wt %), and PA (1.1 wt %). The small amount of ODCB solvent employed helped to facilitate complete transfer of the anhydride reactants into the reaction mixture. TABLE IV Component Mass (g) Moles Source Phthalic Anhydride 27.20 0.184 Aldrich 3-Chlorophthalic Anhydride 2203.0 12.067 Pressure Chem. 1,2-Dicholorobenzene 240.0 1.63 PPG Grade F The 5-gallon reactor was purged with inert gas at 100 SCCM, and the agitation rate was set to 200 rpm. The partial condenser was heated by means of an oil jacket to a temperature of 130 C. The reactor was heated commenced by setting the reactor oil jacket temperature to 180 C. After 30-minutes, the oil jacket temperature was increased to 225 C. At the 1.0-hour mark, the reactor reached a temperature of 226 C., at which point the melt addition of the 3-ClPA-PA-ODCB melt mixture from heated tank 24 was commenced. The reactor pressure was 25.1 PSIG. The 3-ClPA-PA-ODCB melt mixture was pumped via melt feed pump 26 and melt feed line 27 into reactor 12 at an average rate of about 21.5 grams/minute. Addition of the 3-ClPA at a temperature in excess of 210 C. avoided the thick phase reaction stage observed when the reactants are brought into contact at temperatures below about 190 C.About 15 minutes after the addition of the 3-ClPA-PA-ODCB melt mixture was initiated, water and ODCB distillate were observed in the overheads from the partial reflux condenser 18. Addition of the 3-ClPA-PA-ODCB melt mixture required about 2 hours to complete. During the addition of the 3-ClPA-PA-ODCB melt mixture, the amounts of water and ODCB condensed from the overheads emerging from the partial reflux condenser were recorded as a function of time and are recorded in Table V, along with the reactor temperature and pressure profiles. TABLE V Reactor P Time (min)* Reactor T ( C.) (PSIG)H2O (ml) ODCB (ml) 10 222.4 26.5 23 20 20 223.1 26.4 42 33 25 223.2 26.4 53 39 30 223.3 26.5 63 46... |
Yield | Reaction Conditions | Operation in experiment |
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SYNTHESIS EXAMPLE 6-1; Diethyl amine (4.39 g) was added to a dimethylacetamide solution (116 mL) of 3- chlorophthalic acid anhydride (9.13 g) at -5C, and the mixture was stirred at O0C for 1 hour. Then, 30% sodium hydroxide aqueous solution (6.5 g) was added thereto, and the mixture was stirred at 00C for another 1 hour. After t-butylmethylether (200 mL) was added to the reaction liquor solution and stirred for 10 minutes, the precipitated crystal was collected by filtration, washed with t-butylmethylether and air-dried. The obtained crystal was dissolved in water (50 mL), and the solution was adjusted to pH 4 by addition of 2N hydrochloric acid at 5C. The precipitated crystal was collected by filtration, washed with water and dried under reduced pressure to obtain 3-chloro-2-(diethylcarbamoyl)- benzoic acid (9.24 g).1H-NMR (CDCl3, δ ppm) : 1.09 (3H, t), 1.28 (3H, t), 3.24 (2H, q), 3.61 (2H, q), 7.37 (IH, t), 7.48- 7.58 (IH, m), 8.00 (IH, d). | ||
SYNTHESIS EXAMPLE 6-1 Diethyl amine (4.39 g) was added to a dimethylacetamide solution (116 mL) of 3-chlorophthalic acid anhydride (9.13 g) at -5 C., and the mixture was stirred at 0 C. for 1 hour. Then, 30% sodium hydroxide aqueous solution (6.5 g) was added thereto, and the mixture was stirred at 0 C. for another 1 hour. After t-butylmethylether (200 mL) was added to the reaction liquor solution and stirred for 10 minutes, the precipitated crystal was collected by filtration, washed with t-butylmethylether and air-dried. The obtained crystal was dissolved in water (50 mL), and the solution was adjusted to pH 4 bp addition of 2N hydrochloric acid at 5 C. The precipitated crystal was collected by filtration, washed with water and dried under reduced pressure to obtain 3-chloro-2-(diethylcarbamoyl)-benzoic acid (9.24 g). 1H-NMR (CDCl3, δ ppm): 1.09 (3H, t), 1.28 (3H, t), 3.24 (2H, q), 3.61 (2H, q), 7.37 (1H, t), 7.48-7.58 (1H, m), 8.00 (1H, d). |
Yield | Reaction Conditions | Operation in experiment |
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To 4-chloroisobenzofuran-l,3-dione (1.82 g, 10 mmol) in tetrahydrofuran (20 mL) was added lithium tri-tert-butoxyaluminum hydride (0.5 M, 20 mL, 10 mmol, diglyme) at -20 0C. The mixture was stirred at room temperature overnight.(Triphenylphosphoranylidene)acetonitrile (3.0 g, 10 mmol) was added, and the resultant mixture was heated at 120 0C for 16 hours. 2 N Sodium hydroxide(aq) was added and the mixture was extracted with ethyl acetate (2x). ΗCl(aq) (1 M) was added to the aqueous layer to pH3, and the mixture was extracted with ethyl acetate. The organic extracts was dried and concentrated. The residue was dissolved in 20 mL of 1:1 CH2Cl2: methanol followed by the addition of (trimethylsilyl)diazomethane (4 mL, 2 N in diethyl ether, 8 mmol). The mixture was stirred for 1 hour and quenched with acetic acid. The mixture was concentrated and purified by silica gel column chromatography eluting with 2: 1 hexanes:ethyl acetate to afford the title compound. 1H ΝMR (500 MHz, DMSO-J6) δ ppm 7.85 (dd, J = 1.0, 7.5 Hz, IH), 7.81 (dd, J = 1.0, 8.0 Hz, 1 H), 6.04 (d, J = 17 Hz, 1 H), and 3.84 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
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61%; 95% | zirconium(IV) chloride; at 160℃; for 16h; | {Example 1-6} In a 2L volume 4-necked flask, 365g (2.0 mole) of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, 460g (2.0 moles) of 4-chloro(trichloromethyl)benzene, and 1.83g (0.39% with respect to <strong>[117-21-5]3-chlorophthalic anhydride</strong>) of anhydrous zirconium chloride were placed, and heated at 160C. While keeping this temperature, 230g (1.0 mole) of 4-chloro(trichloromethyl)benzene was added dropwise to the reaction mixture over 3 hours, and then stirring was still continued for 13 hours. Gas chromatographic analysis of a liquid sample 6a that was already reacted confirmed that 0.65% of <strong>[117-21-5]3-chlorophthalic anhydride</strong> remains. The liquid sample 6a that was already reacted was distilled under reduced pressure, thereby obtaining 992g (yield: 94.6%) of colorless liquid 6b. A boiling point (bp) of the colorless liquid 6b was from 153C to 155C/9 torr. The colorless liquid 6b was rectified by a 23-step distillation column, thereby obtaining sample 6 containing 290g (yield of 61 % on the basis of <strong>[117-21-5]3-chlorophthalic anhydride</strong>) of 3-chlorophthaloyl dichloride. A boiling point (b p) of sample 6 was from 134-138C/4-5 torr (value in literature: b p 140C /8mbar: Patent Literature 5). As a result of gas chromatographic analysis, a purity of 3-chlorophthaloyl dichloride in the sample 6 was 99.0%. Further, 332g (yield of 95% on the basis of consumed 4-chloro(trichloromethyl)benzene) of 4-chlorobenzoyl chloride with a purity of 99.7% was obtained by distillation. |
Yield | Reaction Conditions | Operation in experiment |
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82.5% | With glacial acetic acid; In water monomer; toluene; at 50℃; | (1) Add 300.0g of <strong>[117-21-5]3-chlorophthalic anhydride</strong> (1.64mol), 600mL of acetic acid and 600mL of toluene to the reaction bottle, and then heat up to 50±5 C, add 250.0g, 40wt% of the aqueous solution of monomethylamine (3.23mol) to the reaction bottle, drip heating to reflux water separation reaction, HPLC monitoring reaction completely.After the end of the reaction, the solvent was concentrated and recovered, and then 200mL of toluene was added to dissolve, cooled and crystallized, filtered, dried to give N-methyl-3-chlorophthalimide 265.0g, purity of 99.2%, yield of 82.5%. |
(1) <strong>[117-21-5]3-chlorophthalic anhydride</strong> was placed in a reaction vessel, and <strong>[117-21-5]3-chlorophthalic anhydride</strong> and acetic anhydrideAdd 13ml: 45ml ratio, add acetic anhydride, stirring at 50 for 30min, to 3-chlorinated phthalic anhydride completely dissolved, will<strong>[117-21-5]3-chlorophthalic anhydride</strong> and methylamine aqueous solution in accordance with the 13g: 9ml ratio, then add the mass fraction of 30% methylamine water solubleLiquid, heated to reflux, toluene with water reaction 3.5-5h, then cooled to room temperature and cooled to below 10 with ice water,Filter, dry, that product A |
Yield | Reaction Conditions | Operation in experiment |
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0.36 g; 0.20 g | With montmorillonite KSF; for 0.25h;Microwave irradiation; | General procedure: Phthalic anhydride (A, 1.50g, 10.13mmol), methylhydrazine (0.53ml, 0.46g, 10.13mmol) and montmorillonite KSF (10.0g, previously activated at 120C for 8h), were mixed and ground in a mortar and placed in a clean and dry beaker. The reaction mixture was irradiated in a microwave oven for 15min in 1-min period (320W), the reaction was monitored by TLC. After completion of the reaction, it was cooled to room temperature and the resulting product was extracted into CH2Cl2 (4×50ml). The KSF Montmorillonite was filtered out and the solvent was evaporated under vacuum. The residue was purified by FC (CH2Cl2/CH3OH 95:05, 90:10) affording 1a[39] (1.46g, 82% yield) as a white solid, m.p. 231-232C |
Yield | Reaction Conditions | Operation in experiment |
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74% | With sulfuric acid; nitric acid; at 0 - 20℃; for 12h; | Synthesis of XXIV:To a stirred solution of nitric acid and sulphuric acid (172 ml: 439 ml) at 0C was addedportion wise compound XCII (250.0 g, 1.37 mol) and the reaction mixture was stirred at room temperature for 12 h. The reaction mixture was cooled to 0C followed by addition of crushed ice. The solid which precipitated out was filtered to afford 3-chloro-6-nitrophthalic acid as a white solid (XXIV; 250.0 g; 74% yield). ‘H NMR (400MHz, DMSO-d6): 14.34 (bs, 2H),8.16-8.13 (d,J= 8.8 Hz, 1H), 7.93-7.91 (d,J= 8.8 Hz, 1H). MS (M-1): 243.97. |
63% | With sulfuric acid; nitric acid; at 0 - 25℃; for 12h; | To a mixture of HNO3 and H2SO4 (20 mL:50 mL) was added compound 111-A (3-chloro phthalic anhydride,CAS number 117-21-5, 25.0 g, 137 mmol) in small portions at 0 C. The mixture was stirred at 25 C for 12 hours, thencooled to 0 C, followed by the addition of crushed ice. The solid was filtered and dried to afford compound 111-B (3-chloro-6-nitro phthalic acid, 21.0 g, 63% yield) as a white solid.1H NMR (400 MHz, DMSO-d6): δ 14.34 (br s, 2H), 8.17 (d, J = 8.8 Hz, 1H), 7.93 (d, J = 8.8 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
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In 1,2-dichloro-benzene; at 145 - 185℃; for 6h;Inert atmosphere; Dean-Stark; | Example 1 - Synthesis of C1PAMI in O-DCB and isolationA 500 mL 3-neck round bottomed flask (24/40) was equipped with an overhead stirrer. The flask was also connected to a nitrogen sweep and a nitrogen blanket. The nitrogen blanket was connected to a bubbler via a Dean-Stark trap. Chlorophthalic anhydride (CIPA) (35.028 g, 0.1919 moles, 2.008 equiv) and meta-phenylene diamine (mPD) (10.333 g, 0.0955 moles, 1.0 equiv, APHA=35) were charged under nitrogen. o-DCB (288 mL) was degassed at 130C in a separate 3-neck flask for at least 30 min. The degassed o- DCB was cannulated into the flask (to make a 10% solid mixture). The reaction flask was then immersed into the oil bath and heated to 145C. The reaction generated a gel when the temperature reached 125C. Slow and continuous heating/stirring (100-150 rpm) broke the gel into a slurry. The temperature of the oil bath was increased to 185C; and the reaction mixture was stirred for a total of 6 hr. Stripping off 77 mL o-DCB (and water) provided a C1PAMI slurry in o-DCB with a 13 % solids content. The slurry was free from residual monoamines and CIPAs. Karl-Fisher analysis was used to test the moisture content (<80 ppm). The C1PAMI slurry in o-DCB was filtered through a 2.7 micron filter paper in a Buchner Funnel. The solid cake was then dried in a vacuum oven at 160C for 14 hr. The dry solid was crushed into powder. |
Yield | Reaction Conditions | Operation in experiment |
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63% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
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With ammonium molybdate; urea; copper dichloride; under 0.00262526 Torr; for 4h; | 37.31 parts of 3-chloro-phthalic anhydride, 88.86 parts, the first copper 20.00 parts chloride, 0.45 part of ammonium molybdate, 154 parts of urea, Hisol P (Japan was charged with oil manufactured by alkyl benzene) 4000 parts of 1L pressure cooker, 0.35Pa, it was reacted for 4 hours.Thereafter, vacuum solvent removal, 1% hydrochloric acid heated, washed with 1% sodium hydroxide heated to give 3-chloro-monochloro phthalocyanine dry weight 115 parts. |
Yield | Reaction Conditions | Operation in experiment |
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98% | In toluene; for 6h;Reflux; | 57 g (0.1 mol) of <strong>[117-21-5]3-chlorophthalic anhydride</strong> and 45 g (0.1 mol) of phenethylamine were added to a 1 L three-hole round bottom 500 ml of toluene was added and the mixture was refluxed for 6 hours. The mixture was decanted while being cooled, precipitated and filtered by suction to give Compound 1 (white flake crystal) in a yield of about 98%. 1HNMR (CDCl3, 500MHz) : δ 3.00-3.04 (m, 2H), 3.94-3.97 (m, 2H), 7.23-7.34 (m, 5H), 7.65 (d, J= 1.7,1H), 7.66 (s, 1H), 7.78 (dd, J1= 5.0andJ2= 3.2,1H); ESI-MS(m/z): 287 [M+H]+. |
98% | In toluene; for 6h;Reflux; | 57 g (0.1 mol)<strong>[117-21-5]3-chlorophthalic anhydride</strong> and 45 g(0.10 mol) of phenethylamine was added to a 1 L three-hole round bottom flask,Then, 500 ml of toluene was added,Refluxed for 6 hours, poured out, cooled, precipitated and filtered by suction to give Compound 1 (white flake crystal), A yield of about 98% |
98% | In toluene; for 6h;Reflux; | A solution of 57 g (0. lmol) of <strong>[117-21-5]3-chlorophthalic anhydride</strong> and 45 g (0.1 mol) of phenethylamine was added to a 1 L three-necked round bottom flask, 500 ml of toluene was added, refluxed for 6 hours, Cooling, crystallization, and filtration to give Compound 1 (white) Color-like crystals) in a yield of about 98%. |
71% | In ethanol; for 6h;Reflux; | A mixture of <strong>[117-21-5]4-chloroisobenzofuran-1,3-dione</strong> (36 g, 0.2 mol) and β-phenylethylamine (26 g, 0.2 mol) in anhydrous ethanol was refluxed for 6 h. After cooling to room temperature, crystals of 4-chloro-2-phenethylisoindoline-1,3-dione (7, 40.5 g, 71 %) separated. These were filtered off, washed with ethanol. The product is pure enough for the next reaction. 1H NMR (CDCl3, 500MHz): δH: 7.78 (dd, J1=5.0Hz, J2=3.2Hz, 1H), 7.64-7.68 (2H, m), 7.23-7.34 (m, 5H), 3.94-3.97 (m, 2H), 3.00-3.04 (m, 2H); ESI-MS (m/z): 286 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
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28 mg | A mixture of (5)-i -(((5)-2,3 -dihydrobenzo[b] [1,4] dioxin-2-yl)methyl)piperidin-3 -amine (0.10 g, 0.40 mmol) and 4-chloroisobenzofuran-i,3-dione (74 mg, 0.40 mmol) in AcOH (1 ml) was refluxed for 4 h. The solvent was evaporated off and the residue was dissolved inDCM. The solution was washed with 1 M NaOH, water and brine, dried and evaporated. The residue was purified by flash chromatography yielding 28 mg 4-Chloro-2-((S)-i-(((S)- 2,3 -dihydrobenzo[b] [1,4] dioxin-2-yl)methyl)piperidin-3 -yl)isoindoline- 1,3 -dione hydrochloride after conversion of free base to HC1 salt in Et20-dioxane.‘H NMR (400 MHz, CDC13) ö ppm 1.91-2.07 (2H, m), 2.19-2.60 (2H, m), 2.70-2.93 (1H,m), 3.03-3.21 (1H, m), 3.24-3.54 (2H, m), 3.56-3.95 (2H, m), 4.08-4.21 (1H, m), 4.24-4.34(1H, m), 4.85-5.31 (2H, m), 6.80-6.94 (4H, m), 7.65-7.73 (2H, m), 7.76-7.84 (1H, m), 13.59 (1H, br s). |
Yield | Reaction Conditions | Operation in experiment |
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87.7% | With N-phenylpicolinamide; sodium bromide; nickel dichloride; zinc; at 30℃; for 8h;Inert atmosphere;Catalytic behavior; | In a 1000 ml three-necked flask, 18.3 g (0.1 mol) of <strong>[118-45-6]4-chlorophthalic anhydride</strong> and 18.3 g (0.1 mol) were added 3-chlorophthalic anhydride, 300 g of anisole as solvent, 0.13 g (0.001 mol) of nickel chloride as a catalyst, 0.198 g (0.001 mol) of C-1 as a catalyst ligand, and 0.03 g (0.0003 mol) of sodium bromide as a catalyst Auxiliary, 13 g (0.2 mol) of zinc powder was used as a reducing agent, and the reaction was stirred at 30 ° C for 8 hours under a nitrogen atmosphere. The reaction solution was filtered to remove insoluble solids in the reaction liquid. 300 g of methanol was added to the filtration mother liquor, and the product was precipitated, filtered, and dried to obtain 25.8 g of the product 2,3,3',4'-biphenyltetracarboxylic dianhydride, yield 87.7percent. |
Yield | Reaction Conditions | Operation in experiment |
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General procedure: To a solution of compounds 2a-2h (5 mmol) in acetic anhydride (5 mL) and triethylamine (2.5 mL) was added ethyl acetoacetate (0.71 mL, 5.5 mmol) under argon. The reaction mixture was stirred at rt for 12 h and then poured into the mixture of concentrated HCl (6 g) and ice-water (6 g). After that, the reaction mixture was stirred at rt for 30 min, additional HCl (8.8 mL, 5M) was added into the mixture, and then the reaction mixture was refluxed for 2 h. After the crude product was cooled to rt, water (100 mL) was added and the reaction mixture was extracted with DCM (2 100 mL). The combined organic layers were washed with brine and then dried (Na2SO4). After removing the solvent, the residue was purified by flash column chromatography. | ||
With acetic anhydride; triethylamine; at 200℃; for 22h; | General procedure: Phthalic anhydride (4.41 mmol) was added to a solution of Ac2O (2.4 mL) and NEt3 (1.3 mL). To the resulting orange suspension, ethyl acetoacetate (630 μL, 4.84 mmol) was quickly added. The red solution was stirred at room temperature for 22 h. Ice (1.7 g) and concentrate HCl (1.6 mL) were added followed by the addition of 5 M HCl (7 mL). The resulting mixture was stirred at 80 C for 15 min. After cooling to room temperature, the mixture was extracted with CH2Cl2. The combined organic extract was washed with brine (25 mL), dried over Na2SO4 and the solvent was removed under reduced pressure. Then, to the solution of 1H-indene-1,3(2H)-dione in 5 ml CH3CN, TsN3 (6.6 mmol) and Et3N (8 mmol) was added at 0 . The reaction mixture was allowed to warm to room temperature and stirred for 10 h. Afterwards, the reaction mixture was purified by flash column chromatography to afford the pure product 18b-18i. |
Yield | Reaction Conditions | Operation in experiment |
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86% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
75% | In acetic acid;Reflux; | General procedure: A 10 mL round bottomed flask was charged with 1 (1.00 mmol), 2 (1.00 mmol), acetic acid (5 mL) and provided with a reflux condenser. The reaction mixture was heated to reflux and stirred for an appropriate period. TLC was used to monitor the progress of the reaction. After completion of the reaction, the mixture was diluted with water (20 mL) and extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with water (2 x 20 mL), brine (20 mL), dried over anhydrous Na2SO4, filtered and evaporated in a rotary evaporator under reduced pressure. The crude mixture was purified by column chromatography to afford the pure products (3a-3g’). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In ethyl acetate; at 20℃; | 4-Chloro-isobenzofuran-1,3-dione (274 mg, 1.5 mmol) was dissolved in 10 mL of ethyl acetate, and stirred and stirred at room temperature, and ethyl 2-aminoacetate (155 mg, 1.5 mmol) was added dropwise. Will produce a lot of white solids immediately, TLC monitoring,After the reaction is completed, the filter is allowed to stand still.Drying gave the intermediate 2-chloro-6-((2-ethoxy-2-oxoethyl)carbamoyl)benzoic acid in 90% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.3% | In ethyl acetate; at 20℃; | 4-Chloroisobenzofuran-1,3-dione (230 mg, 1.25 mmol) dissolved in 5 mL of ethyl acetate and stirred at room temperatureSolution, drop into piperine (188mg, 1.25mmol), will immediately produce a large amount of white solids, TLC monitoring, after the reaction is completed, staticThe mixture was filtered and dried to give Compound 4 in a yield: 80.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.1% | With sodium hydrogencarbonate; In dimethyl sulfoxide; toluene; for 16h;Reflux; | (4) by step (3)The molar ratio of compound C to <strong>[117-21-5]3-chlorophthalic anhydride</strong> prepared in the mixture is 1:2.3.The molar ratio of sodium bicarbonate to compound C is 2:1 under the catalysis of sodium bicarbonate.After refluxing with toluene for 7 h, toluene was added to 20% of DMSO.The reaction was continued in DMSO for 9 h. After the reaction was completed, the reaction solution was filtered, washed with water, concentrated, and purified by crystallization to obtain perfluorinated. The dianhydride was obtained in a yield of 89.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.4% | With potassium carbonate; In dimethyl sulfoxide; toluene; for 16h;Reflux; | (4) The molar ratio of the compound C and the <strong>[117-21-5]3-chlorophthalic anhydride</strong> obtained in the step (3) is 1:2.4.The molar ratio of potassium carbonate to compound C is 1.5:1 under the catalyst of potassium carbonate.After refluxing with toluene for 7 h, toluene was added as DMSO.20%, continue to react in DMSO for 9 h. After the reaction is completed, the reaction solution is filtered.After washing with water, concentration and purification by crystallization, a perfluorosubstituted dianhydride was obtained in a yield of 85.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.9% | With potassium carbonate; In dimethyl sulfoxide; toluene; for 16h;Reflux; | (4)Compound C prepared in step (3) andThe molar ratio of <strong>[117-21-5]3-chlorophthalic anhydride</strong> is 1:2.4, which is catalyzed by potassium carbonate.The molar ratio of potassium carbonate to compound C is 1.5:1, and the water is refluxed with toluene for 7 hours.Toluene was added to 20% of DMSO, and the reaction was continued in DMSO for 9 h.After the reaction is completed, the reaction solution is filtered, washed with water, and concentrated.After purification by crystallization, perfluorosubstituted dianhydride was obtained in a yield of 86.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38 g | With sulfolane; hexaammonium heptamolybdate tetrahydrate; urea; at 90℃; for 5h; | In a 1 L flask, 111 g of <strong>[117-21-5]3-chlorophthalic anhydride</strong>, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 600 g of sulfolane were charged and stirred at 190 C. for 5 hours. Then stop heating, allow to cool and filter,It was washed with 80 g of 2-propanol 7, 1000 g of a 1% aqueous solution of sodium hydroxide and 1000 g of 1% hydrochloric acid.After washing with water, the obtained wet cake is dried at 90 C. for 12 hours,Blue solid α-tetrachlorozinc phthalocyanine (38 g) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.4% | With acetic acid; at 100℃; for 3h; | Add 3 - chlorophthalic anhydride (365 mg, 2.0 mmol) and alanine (190 mg, 2.1 mmol) to glacial acetic acid(10 mL), heated to 100 C for 3 h. The reaction was quenched with water (10 mL) and the NaOH solution (0.1 mol/L) was adjusted to pH 6-8. filter,After drying, 430 mg of a yellow solid was obtained.LC-MS and 1H-NMR confirmed the expected intermediate compound to yield 96.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.1% | With acetic acid; at 100℃; for 3h; | 3-Chlorophthalic anhydride (365 mg, 2.0 mmol) and glycine (155 mg, 2.1 mmol) were added to glacial acetic acid (10 mL) and heated to 100 C for 3 h.The reaction was quenched with water (10 mL).The pH of the solution was adjusted to 6-8 by a NaOH solution (0.1 mol/L).filter, after drying, a yellow solid 400mg,LC-MS and 1 H-NMR confirmed the expected intermediate compound, yield 96.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.5% | With acetic acid; at 100℃; for 3h; | 3-Chlorophthalic anhydride (365 mg, 2.0 mmol) and 4-aminobutyric acid (190 mg, 2.1 mmol) were added to glacial acetic acid (10 mL) and heated to 100 C for 3 h.The reaction was quenched with water (10 mL), NaOH solution (0.1 mol/L)The pH of the solution was adjusted to 6-8. filter,After drying, it was 444 mg of a yellow solid.LC-MS and 1 H-NMR confirmed the expected intermediate compound, yield 95.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With potassium acetate; acetic acid; at 100℃; for 18h; | A solution of amine salt 1-127 (23 mg, 0.075 mmol), 4-chloroisobenzofuran-l,3- dione (16 mg, 1.2 equiv.) and potassium acetate (22 mg, 3.0 equiv.) in AcOH was heated to 100 C for 18 hours, cooled to ambient temperature, and concentrated in vacuo. The residue was dissolved in EtOAc and washed with 1 M HC1 then brine, and the combined aqueous washes were back-extracted with EtOAc. The combined organic extracts were dried over sodium sulfate and concentrated in vacuo. The resulting residue was purified by flash chromatography using 15% MeOH in DCM with 1% AcOH to afford 21 mg of intermediate acid 1-134 (79% yield). This material was dissolved in DCM along with pentafluorophenol (16 mg, 0.089 mmol) and EDC (23 mg, 0.118 mmol). The resulting reaction mixture was stirred for 2 hours and concentrated in vacuo. The residue was dissolved in EtOAc. The resulting solution was washed with 1 M HC1 and brine, then dried over sodium sulfate and concentrated in vacuo. Purification of the residue by flash chromatography using EtOAc in hexanes afforded 20 mg of 1-135 (0.038 mmol, 65% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.7% | With sodium sulfide; In tetrahydrofuran; at 20℃; for 4h; | General procedure: I. Phthalic anhydride (2.96 g, 20 mmol) was dissolved in 4ml tetrahydrofuran (THF);4ml Na2S9H2O (2.40 g, 10 mmol) water solution was added one drop at a time.During the process, the reaction solution turned light yellow, and a small amount ofwhite solids were precipitated. At room temperature, stirring was continued for4 hours. 20 ml H2O was added to the reaction solution to quench, and a large amountof white solids were precipitated out. 5ml 2 mol/L HCl was adjusted to pH 6, and1.27 g white crystals were extracted, with a yield of 85%.II. Using 4-chloro-phthalic anhydride (3.65 g, 20 mmol) as raw material, 1.60 g ofwhite powder was obtained with the yield of 87.6%, following the above method.III. Using 3-chloro-phthalic anhydride (3.65 g, 20 mmol) as raw material, 1.40 ggrey powder was obtained with a yield of 76.7%, following the above method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With acetic acid; at 110℃; for 4h; | General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3. |
Tags: 117-21-5 synthesis path| 117-21-5 SDS| 117-21-5 COA| 117-21-5 purity| 117-21-5 application| 117-21-5 NMR| 117-21-5 COA| 117-21-5 structure
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