Structure of 432025-97-3
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CAS No. : | 432025-97-3 |
Formula : | C10H6O4 |
M.W : | 190.15 |
SMILES Code : | O=C(O)C1=CC(C#C)=CC(C(O)=O)=C1 |
MDL No. : | MFCD14635840 |
InChI Key : | XKEUZQRIANAGPB-UHFFFAOYSA-N |
Pubchem ID : | 12080905 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
99.5% | With hydrogenchloride; In water; | [Preparation of 5-ethynylisophthalic acid from dipotassium 5-ethynylisophthalate] Dipotassium 5-ethynylisophthalate in an amount of 5 g (0.019 moles) was dissolved into 20 ml of ion-exchanged water and insoluble substances were removed by filtration with a 5C filter paper. To the obtained filtrate, a 5 moles/liter hydrochloric acid was added under stirring until the pH became 1. The formed solid substance was separated by filtration, washed with ion-exchanged water and filtered. The filtration and the washing were repeated twice. The obtained solid substance was dried at 50ØC under a reduced pressure and 3.6 g of 5-ethynylisophthalic acid was obtained (the yield: 99.5%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.2% | In a 200 ml three-neck flask, 34.5 g of dimethyl 5-(3-hydroxy-3-methylbutyl-1-yl)isophthalate (the compound represented by the formula (2)), 60 g of water, and 2.2 g of ascorbic acid (a reducing agent) were added in a nitrogen stream, and stirred. Added thereto was 60 g of a 25% aqueous solution of sodium hydroxide, and thereafter, the mixture was heated and the temperature thereof was elevated to 80 C. The mixture was reacted at 80 C. for 4 hours, and thereafter, cooled down to 50 C. Added thereto was activated carbon, and stirred for 30 minutes. Subsequently, the activated carbon was removed by suction filtration using celite, and water used for washing a filter element was also added thereto. 50.7 g of 35.5% concentrated hydrochloric acid was added to the aforementioned aqueous solution, and the inner temperature was once elevated to 80 C., and thereafter, gradually cooled down to room temperature over 4 hours. A precipitated product was taken out by suction filtration, and washed with 50 g of running distilled water and dried by air at 50 C. for 2 days, whereby 22.6 g of white powder of 5-ethynylisophthalic acid was obtained (yield percent: 95.2%).The white powder thus obtained was analyzed based on HPLC. The area ratio of light absorbance at 254 nm was 97.8%, and 1,4-bis(3,5-dicarboxylphenyl)-1,3-butadiyne that is an oxidation by-product was almost not detected. | |
93.5% | 5-ethylnylisophthalic acid was synthesized without using ascorbic acid in Example 2, and was taken out by distillation under reduced pressure (yield: 22.2 g, percent yield: 93.5%).This product was analyzed based on HPLC, and the area ratio of the light absorbance at 254 nm was 81.1%, and 1,4-bis(3,5-dicarboxylphenyl)-1,3-butadiyne that is an oxidation by-product was detected at the area ratio of 16. 9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With triethylamine; triphenylphosphine;tris-(dibenzylideneacetone)dipalladium(0); copper(l) iodide; In N,N-dimethyl-formamide; at 40℃; for 4h; | The dibrominated porphyrin dimer 16 (29.0 mg, 15.2 μmol), tris(dibenzylideneacetone)dipalladium (1.44 mg, 1.58 μmol), triphenylphosphine (0.83 mg, 3.15 μmol) and copper(i) iodide (0.30 mg, 1.58 μmol) were dried under vacuum in a two necked pear-shaped flask with a vacuum adaptor and septum fitted for 2 hrs at 40 0C. The system was flushed with nitrogen, and 5- ethynylisophthalic acid, (30.0 mg, 158 μmol) was added under a flow of nitrogen. Dry dimethylformamide (900 μL) and distilled triethylamine (100 μL) were added by syringe. The solution was degassed by three freeze-thaw cycles before purging with nitrogen and the reaction stirred at 40 0C. The reaction was monitored by TLC (95:5 CH2CI2 : MeOH) until no starting material was present (4 hr), the mixture was diluted with dichloromethane (1 ml_) and passed through a <n="36"/>celite plug with 9:1 dichloromethane:methanol as the eluent. Purification of the mixture by semi-prep HPLC gave isophthalic acid Sonogashira dimer F as a green glass, yield 9.7 mg, (30 %). mp > 250 C. λmax (DMF / 1 % pyridine) / nm (log ε) = 463 (5.57), 496 (5.19), 589 (4.23), 683 (4.89), 746 (5.04); 1H NMR (500 MHz, DMSO- d6 / 5 % pyridine-d5) J3.14 (s, 12 H, CH3) 3.34 - 3.40 (m, 8 H, CH2) 3.48 - 3.53 (m, 8 H, CH2) 3.55 - 3.60 (m, 8 H, CH2) 3.63 - 3.70 (m, 8 H, CH2) 3.86 - 3.93 (m, 8 H, CH2) 4.32 - 4.41 (m, 8 H, CH2) 7.46 - 7.52 (m, 4 H, Ar-H) 7.72 - 7.77 (m, 4 H, Ar-H) 7.83 - 7.88 (m, 4 H, Ar-H) 7.92 (s, 4 H, Ar-H) 8.95 (s, 2 H, Ar- H) 8.97 - 9.02 (m, 8 H) 9.07 (d, J = 4.5 Hz, 4 H, β-H) 9.91 (d, J = 4.5 Hz1 4 H, β- H) 9.99 (d, J = 4.5 Hz, 4 H, /3-H). m/z MALDI-TOF 2122.6 (C116H102N8O24Zn2, M+, requires 2122.6, 100%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | 5-Ethynylisophthalic acid (4). 5-Ethynylisophthalic acid was prepared in one step by reacting dimethyl-5-(trimethylsilylethynyl)isophthaloate (3) (0.7 g, 3.2 mmol) with NaOH (1.412 g, 35.3 mmol) in THF (20 ml) at r. t. for 4 h. The precipitate formed was centrifuged down, dissolved in aq. NaOH (0.1 M, 50 ml) and stirred for 2 h at room temperature. The reaction mixture was cooled to 0 C. on an ice bath, acidified with 10% HCl to pH1-2. The precipitate formed was isolated by centrifugation, washed twice with water and dried, giving the target compound as a powder. Yield: 0.47 g, 77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Diethyl 4,4′-[(5-ethynyl-1,3-phenylene)bis(carbonylimino)]dibutanoate (5). To a solution of <strong>[432025-97-3]5-ethynylisophthalic acid</strong> (4) (0.37 g, 1.95 mmol) in dry DMF (20 ml), HBTU (2 g, 5.28 mmol) was added in one portion. After stirring for 10 min at r. t., the mixture of ethyl 4-aminobutyrate hydrochloride (1 g, 5.97 mmol) and DIPEA (2 ml, 11.5 mmol) in dry DMF (10 ml) was added, and the reaction mixture was stirred overnight at r. t. The reaction mixture was poured into ice-cold water (200 ml), and a few drops of conc. HCl were added. The formed precipitate was centrifuged, washed 3 times with water and dried in vacuum. The product was purified by column chromatography (SiO2, eluent CH2Cl2/THF, gradient from 100:0 to 80:20) to yield the target compound as a yellowish solid. Yield: 0.6 g, 74%. NMR 1H (DMSO-d6), ε, ppm: 1.16 (6H, t, 3J=7.0 Hz, -OCH2CH3), 1.77 (4H, dddd, 3J1=3J2=7.0, 3J3=3J4=7.3 Hz, -CH2-), 2.35 (4H, t, 3 J=7.3 Hz, -CH2C(O)-), 3.24-3.31 (4H, m, broad, -NHCH2-), 4.03 (4H, q, 3J=7.0 Hz, -OCH2CH3), 4.37 (1H, s, -C≡H), 8.05 (2H, d, 4J=1.7 Hz, to Ar), 8.30 (1H, t, 4J=1.7 Hz, Ar), 8.60 (2H, t, 3J=5.5 Hz, -NH-). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In water; at 100℃; for 50h; | [Co (EPA)(TPT)]·1.5DMF·1.5H2O (2): Co(NO3)2·4H2O (3.4 mg, 0.012 mmol), H4EPA (6 mg, 0.0429 mmol) and TPT (5.5 mg, 0.0170mmol) were dissolved in 5 mL mixed solvents of DMF and H2O (v/v = 1:1) in a sealed tube, then heated at 100 oC for 50 h gaving rise topale yellow crystals of 2 (80% based on H4EPA). Elemental Anal. Calcd. for 2: C, 55.80%; H, 4.43%; N, 15.02%; Found: C, 55.69%; H,4.46%; N, 14.92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Synthesis of F: C (2.94 g, 30 mmol,) were dissolved in methanol (50 mL), K2CO3 (3 g, excess) was added and the mixture stirred at RTfor 3 h. After removal of the solvents, water (60 mL) was added and the mixtyre was extracted with dichoromethane and dired withMgSO4. The solution was filtered through silica plug, and rinsed with dichloromethane. 1H NMR (400 MHz, CD3Cl): δ 3.19(s, 1 H)3.97 (s, 6 H), 8.34(d, 2 H), 8.66 (t, 1 H).Synthesis of G (H2EPA): F (7.649 g, 19 mmol) was suspended in 150 mL of THF/methanol (1:1) mixed solvent, to which 100 mL of 1mol/L NaOH aqueous solution was added. The mixture was stirred at room temperature for 1 h, organic solvent was removed undervacuum and diluted hydrochloric acid was added to the remaining aqueous solution until it because acidic (pH 2). The precipitate wascollected by filtration,washed with water and dried under vacuum at 80 oC to give H2EPA. 1H NMR (DMSO-d6): δ 4.43 (s, 1 H), 8.18 (s,2 H), 8.47 (s, 1 H), 13.49 (s, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Add 2.3g to 50mL DMF solvent5-ethynyl isophthalic acid (0.012 mol) and 4.8 g potassium bicarbonate(0.048 mol), stirred at room temperature to form a potassium salt.4.80 g of n-bromohexane (0.03 mol) was added to the mixed solution,The reaction was stirred at 90 C for 12 hours. Stop the reaction,After the solution was cooled to room temperature, it was poured into 300 mL of water.It was extracted with ethyl acetate. Dry over anhydrous sodium sulfate, filter and then dry the solvent.Column chromatography using petroleum ether/ethyl acetate (20/1) as eluentLeave to give a white solid. |
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