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[ CAS No. 610-92-4 ] {[proInfo.proName]}

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Chemical Structure| 610-92-4
Chemical Structure| 610-92-4
Structure of 610-92-4 * Storage: {[proInfo.prStorage]}
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Product Details of [ 610-92-4 ]

CAS No. :610-92-4 MDL No. :MFCD00132933
Formula : C8H6O6 Boiling Point : -
Linear Structure Formula :- InChI Key :OYFRNYNHAZOYNF-UHFFFAOYSA-N
M.W : 198.13 Pubchem ID :69131
Synonyms :

Calculated chemistry of [ 610-92-4 ]

Physicochemical Properties

Num. heavy atoms : 14
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 6.0
Num. H-bond donors : 4.0
Molar Refractivity : 44.41
TPSA : 115.06 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.54 cm/s

Lipophilicity

Log Po/w (iLOGP) : 0.33
Log Po/w (XLOGP3) : 1.37
Log Po/w (WLOGP) : 0.49
Log Po/w (MLOGP) : 0.09
Log Po/w (SILICOS-IT) : -0.3
Consensus Log Po/w : 0.4

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.56

Water Solubility

Log S (ESOL) : -2.12
Solubility : 1.51 mg/ml ; 0.00764 mol/l
Class : Soluble
Log S (Ali) : -3.39
Solubility : 0.0809 mg/ml ; 0.000408 mol/l
Class : Soluble
Log S (SILICOS-IT) : 0.0
Solubility : 198.0 mg/ml ; 1.0 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.29

Safety of [ 610-92-4 ]

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:

Application In Synthesis of [ 610-92-4 ]

* 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.

  • Downstream synthetic route of [ 610-92-4 ]

[ 610-92-4 ] Synthesis Path-Downstream   1~72

  • 2
  • [ 13731-82-3 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
> 98% In a round bottom flask with reflux condenser, 1.00 g (3.1 mmol) of 2,5-dibromoterephthalic acid was combined with 10 mL of H2O. 0.85 g of Na2CO3 (7.8 mmol) was added to this mixture. Subsequently, 0.12 mL (0.031 mmol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile was added, followed by addition of 0.12 mL (0.062 mmol, 2 mol %) of 0.5 M rac-trans-N,N'-Dimethylcyclohexane-1,2-diamine (Ligand F). The reaction mixture was heated to 90 C. with stirring, then stirred for 18 h at 90 C. A sample was taken after 6 h and analyzed by 1H NMR. No starting material was detected. After 18 h, the conversion of 2-bromo-5-hydroxyterephthalic acid was larger than 99%, and the product selectivity to 2,5-dihydroxyterephthalic acid was above 98%. After cooling to 25 C., the reaction mixture was acidified with 15% HCl, producing a light green precipitate. The precipitate was filtered and washed with water and dried. The water phase did not show any detectable organic products by 1H NMR analysis. The purity of the solid product was determined to >98%.
97% Under nitrogen, 5.00 g (15.4 mmol) of 2,5-dibromoterephthalic acid was combined with 20 g of H2O. 1.71 g (16.1 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 2.38 g (22.5 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 28 mg of CuBr and 50 mg of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved to give a blue-purple solution. This solution was added to the stirred reaction mixture at 90 C. under nitrogen and stirred for 2 h at 90 C. After cooling to 25 C., the reaction mixture was acidified with 15% HCl, producing a yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 2.96 g (15 mmol, 97% yield) 2,5-dihydroxyterphtalic acid was collected. The purity was determined by 1H NMR to be >98%.
92% Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid was combined with 15 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.940 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.06 mmol) (0.01 mol equiv) of CuBr and 25 mg (0.14 mmol) (0.02 mol equiv) of 2,2',6,6'-tetramethylheptanedione-3,5 were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.26 g of crude 2,5-dihydroxyterephthalic acid and 2-hydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 89%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 92%.
72% Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromooterephthalic acid were combined with 10 g of H2O, 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.950 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.01 mol equiv) of CuBr and 40 mg (0.02 mol equiv) of N,N'-dimesityl-2,3-diiminobutane were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.09 g of crude 2,5-dihydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 81%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 72%.
97 - 99%Spectr. Eight 2 mL reaction vials were each charged with 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid, followed by various amounts of 0.5 M aqueous sodium carbonate solution as shown in Table 3. Each of the mixtures was then treated with 0.003 mL of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL of 0.5 M rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). The reaction vials were closed and loaded into an 8-well reactor. The reactor was then sealed. About 12 psi (83 kPa) of N2 pressure was applied. The reactor was heated to 90 C. and held at that temperature for 5 hours, then allowed to cool to room temperature. The reaction mixture was then acidified with 15% aqueous HCl, producing a light green precipitate. The precipitate was filtered, washed with water, dried, and analyzed by 1H NMR in DMSO-d6. Results are presented in Table 3.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.

  • 3
  • [ 5870-38-2 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide; In water; at 80℃; for 5h;Inert atmosphere; The mixture of compound 3 (2.00 g, 7.87 mmol) and sodium hydroxide (1.61 g, 40.3 mmol) in water (40 mL) was heated at 80C under argon protection for 5 h. The reaction solution was cooled to room temperature, and the pH was adjusted to approximately 1.0 with concentrated hydrochloric acid. A large amount of bright yellow solids were precipitated, and the mixture was stirred at room temperature for 1 h. The mixture was filtered, and the filter cake was washed with water until neutral and dried at room temperature to obtain crude product 4 (1.50g, 96.2%) as a bright yellow solid which was used without further purification. 1H NMR (400MHz, DMSO-d6) delta 10.59 (brs, 2H), 7.29 (s, 2H), 3.96 (brs, 2H).
  • 5
  • [ 124-38-9 ]
  • [ 123-31-9 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
70% With potassium carbonate; Potassium bicarbonate; potassium hydroxide at 220℃; for 12h; Autoclave; 1; 7-8 After mixing 0.91mol of 1,4-benzenediol with 0.091mol of potassium hydroxide, 0.118mol of potassium carbonate and 0.33mol of potassium bicarbonate, it was added to the 1L autoclave, and after replacing the air in the autoclave with carbon dioxide gas, The reaction was carried out for 12 h under the conditions of a temperature of 220 ° C and a pressure of 2.2 MPa, the crude product obtained from the reaction was dissolved in hot water at 80 ° C, the pH of the obtained solution was adjusted to 1-2 with hydrochloric acid with a mass concentration of 36%, and the crude product was obtained by filtration, The obtained crude product was placed in an acetone solution, slurried at room temperature of 25°C, and the system was stirred evenly and filtered to obtain a purified product of 2,5-dihydroxyterephthalic acid with a product purity of 99.8% and a yield of 70%.
With potassium carbonate at 220℃;
With Potassium bicarbonate; propane-1,2,3-triol at 160 - 170℃;
  • 6
  • [ 610-92-4 ]
  • [ 137-09-7 ]
  • 2,5-bis(5-amino-2-benzoxazolyl)-1,4-benzenediol [ No CAS ]
  • 7
  • 2,5-dihydroxy-1,6-benzenedicarboxylic acid disodium salt [ No CAS ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; In water; at 20℃; Under nitrogen 10 mmol of 2,5-dibromoterephthalic acid was stirred with a solution of 25 mmol Na2CO3 in 10 mL H2O at 50-75 C. until all of the 2,5-dibromoterephthalic acid was dissolved. Separately, 0.01 mmol of the copper compound [Example 1 and Examples 2 and 3 (Comparative)] or 0.05 mmol of Cu powder [Example 4 (Comparative)], respectively, was mixed with 1 mL of deionized water and 0.02 mmol of the ligand (Examples 1-3) or no ligand [Examples 2-4 (Comparative)], respectively, and the resulting copper containing mixture was added to the reaction mixture containing 2,5-dibromoterephthalic acid and Na2CO3 in H2O. The resulting reaction mixture was heated at the given temperature and for the given time (Table 1). After cooling to ambient temperature, the reaction mixtures were carefully acidified with 35% aqueous HCl. The products were isolated by filtration, washed with water and dried under vacuum. The crude reaction product was analyzed by 1H NMR (d6-dmso). The results are summarized in Table 1. TABLE 1 CONV SEL T Cu Ligand Example Ligand (% mol) (% mol) ( C.) t (h) source Structure 1 Proline 100 91 80 3CuBr2
With hydrogenchloride; In water; at 25℃;Acidic aqueous solution; Example 1. This example demonstrates the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using CuBr and N,N'-dimesityl-2,3-diiminobutane Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid were combined with 10 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.950 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.01 mol equiv) of CuBr and 40 mg (0.02 mol equiv) of N,N'-dimesityl-2,3-diiminobutane were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.09 g of crude 2,5-dihydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 81%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 72%. Example 2. Under nitrogen, 3.24 g (10 mmol) of 2,4-dibromoterephthalic acid was combined with 10 g of H2O; 1.10 g (10.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 1.54 g (14.5 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 minutes. Separately, 22 mg (0.01 mol equiv) of CuBr2 and 69 mg (0.02 mol equiv) of N,N'-di(trifluoromethylbenzene)-2,3-diiminoethane were combined under nitrogen, followed by addition of 2 mL H2O under air. This solution was added to the stirred reaction mixture via syringe at with 80 C. under nitrogen and stirred for 26 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The precipitate was filtered and washed with water and dried. The conversion and selectivity of 2,4-hydroxyterephthalic acid were determined to be 100% and 72%, respectively, by 1H NMR. The net yield was determined to be 72%.
  • 8
  • [ 13731-82-3 ]
  • [ 610-92-4 ]
  • 2-bromo-5-hydroxy-terephthalic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 48 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water at 20℃; 41 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 37 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 45 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 44 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 35 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 46 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 43 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 36 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water at 20℃; 40 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 33 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 39 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 47 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 38 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 34 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 42 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 49 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 3 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 19 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 11 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 7 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 18 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 14 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 5 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 16 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 13 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 6 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 10 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 9 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water at 20℃; 8 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 15 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 4 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 12 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; A Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; 17 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃; B Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.

Reference: [1]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[3]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[4]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[5]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[6]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[7]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[8]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[9]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[10]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[11]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[12]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[13]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[14]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[15]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[16]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[17]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[18]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[19]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[20]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[21]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[22]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[23]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[24]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[25]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[26]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[27]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[28]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[29]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[30]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[31]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[32]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[33]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[34]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[35]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[36]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
  • 9
  • [ 13799-90-1 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
94% Under nitrogen, 2.00 g (8.51 mmol) of <strong>[13799-90-1]2,5-dichloroterephthalic acid</strong> was combined with 10 g of H2O. 0.938 g (8.85 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 1.31 g (12.34 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 12 mg of CuBr and 24 mg of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved to give a deep purple solution. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 20 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.59 g (8.03 mmol, 94% yield) 2,5-dihydroxyterephthalic acid was collected. The purity was determined by 1H NMR to be 95%.
94% This example demonstrates the formation of 2,5-dihydroxyterephthalic acid from <strong>[13799-90-1]2,5-dichloroterephthalic acid</strong> using CuBr and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, 2.00 g (8.51 mmol) of <strong>[13799-90-1]2,5-dichloroterephthalic acid</strong> was combined with 10 g of H2O. 0.938 g (8.85 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 1.31 g (12.34 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 12 mg of CuBr and 24 mg of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved to give a deep purple solution. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 20 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.59 g (8.03 mmol, 94% yield) 2,5-dihydroxyterephthalic acid was collected. The purity was determined by 1H NMR to be >95%.
  • 11
  • [ 10196-18-6 ]
  • [ 610-92-4 ]
  • zinc(II) 2,5-dihydroxy-1,4-benzenedicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% In propan-1-ol; DMF (N,N-dimethyl-formamide); water; at 105℃; for 21.4167h; 2,5-Dihydroxyterephthalic acid (19 mg, 0,10 mmol) and Zn [(N03)] [2. 4H20] (53 mg, 0.20 mmol) were dissolved in a mixed solution of DMF (2.0 mL), PrOH [(0.] 10 mL) and water (0.10 mL), which was placed in a pyrex tube (10 mm x 70 mm). The tube was frozen and evacuated, and flame sealed under vacuum. The tube was heated to [105C] at [2C/MIN,] held for 20 hours, then cooled to room temperature at [2C/MIN.] Yellow needle crystals were col- lected and washed with DMF (3 x 5 mL). Yield: 26 mg, 81 % based on the 2,5- dihydroxyterephthalic acid.
  • 12
  • [ 610-92-4 ]
  • [ 77-78-1 ]
  • [ 21004-12-6 ]
YieldReaction ConditionsOperation in experiment
73% With potassium carbonate; In acetone; for 24h;Heating / reflux; [00239] A suspension of <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (5 g, 25 mmol), K2CO3 (10 g, 72 mmol) and dimethyl sulphate (11 ml, 116 mmol) in acetone (100 ml) was stirred and refluxed for 24 h. The mixture was filtered while still hot and the solvent was evaporated to about half of the original volume. On cooling white needles precipitated and were filtered and dried obtaining 4.6 g of the title compound (yield 73%), mp=141-143 C.
  • 13
  • [ 610-92-4 ]
  • [ 121-90-4 ]
  • [ 338447-36-2 ]
YieldReaction ConditionsOperation in experiment
90.6% Example 4 (1)Synthesis of 2,5-bis(m-nitrobenzoate)terephthalic acid 19.61 g (0.1 mol) of 2,5-dihydroxy terephthalic acid, 17 g of pyridine and 200 mL of acetone were placed in a reaction vessel. Then 74.22 g (0.4 mol) of m-nitrobenzoyl chloride was dissolved in 400 mL of acetone. The obtained solution was slowly added dropwise in the aforementioned reaction vessel at 50 C. After completion of dropping, the solution was refluxed with stirring for 2 hours. Then the 4 ml of water was added and refluxed with stirring for another 2 hours. After the reaction, the reaction solution was cooled to room temperature to precipitate a solid. The solid was filtered off and then washed with water to remove pyridine hydrochloride. Thus 45 g (90.6% yield) of 2,5-bis(m-nitrobenzoate)terephthalic acid was obtained.
  • 14
  • [ 13731-82-3 ]
  • [ 636-94-2 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
92% Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid was combined with 15 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.940 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.06 mmol)(0.01 mol equiv) of CuBr and 25 mg (0.14 mmol)(0.02 mol equiv) of 2,2',6,6'-tetramethylheptanedione-3,5 were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.26 g of crude 2,5-dihydroxyterephthalic acid and 2-hydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 89%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 92%.
  • 15
  • [ 610-92-4 ]
  • Mg2(2,5-dioxido-1,4-benzenedicarboxylate) [ No CAS ]
YieldReaction ConditionsOperation in experiment
1 g With magnesium(II) nitrate hexahydrate; In ethanol; water; N,N-dimethyl-formamide; at 20 - 120℃; for 24.5h;Inert atmosphere; Comparison Example 1 Synthesis of Mg-MOF: [Mg2(<strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong>)] (IRMOF-74-I; commercial name: Basolite M74) To 300 ml DMF under nitrogen atmosphere 3.20 g Mg(NO3)2×6 H2O (12.5 mmol) and 0.76 g <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (3.8 mmol) were added under stirring. To the obtained slightly yellow solution 20.0 ml Ethanol was added, followed by drop-wise addition of 20.0 ml distilled water. After stirring for 30 min at ambient temperature the reaction mixture was heated to 120 C. for 24 h under gentle reflux and stirring (100 RPM). After cooling down to ambient temperature the mother liquor was separated via filtration on a glass frit under nitrogen atmosphere. The precipitate was washed twice with 20 ml DMF, twice with 20 ml of dry Methanol and then transferred to a Soxhlett extractor and extracted with Methanol for 16 h. The received solid was dried at 50 mbar for 2 h at ambient temperature and 16 h at 130 C. After drying 1.00 g of an off-white solid was obtained (yield based on linker 107.5%). The surface area was 1133 m2/g (BET-method) and 1535 m2/g (Langmuir method). The XRD pattern exhibits reflexes in the area typical for microporous materials.
1 g With magnesium(II) nitrate hexahydrate; In ethanol; water; N,N-dimethyl-formamide; at 20 - 120℃; for 24.5h;Inert atmosphere; Comparison Example 1 Synthesis of Mg-MOF: [Mg2(<strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong>)] (IRMOF-74-I; commercial name: Basolite M74) To 300 ml DMF under nitrogen atmosphere 3.20 g Mg(NO3)2×6 H2O (12.5 mmol) and 0.76 g <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (3.8 mmol) were added under stirring. To the obtained slightly yellow solution 20.0 ml Ethanol was added, followed by drop-wise addition of 20.0 ml distilled water. After stirring for 30 min at ambient temperature the reaction mixture was heated to 120 C. for 24 h under gentle reflux and stirring (100 RPM). After cooling down to ambient temperature the mother liquor was separated via filtration on a glass frit under nitrogen atmosphere. The precipitate was washed twice with 20 ml DMF, twice with 20 ml of dry Methanol and then transferred to a Soxhlett extractor and extracted with Methanol for 16 h. The received solid was dried at 50 mbar for 2 h at ambient temperature and 16 h at 130 C. After drying 1.00 g of an off-white solid was obtained (yield based on linker 107.5%). The surface area was 1133 m2/g (BET-method) and 1535 m2/g (Langmuir method). The XRD pattern exhibits reflexes in the area typical for microporous materials.
With magnesium nitrate 9-hydrate; In ethanol; water; N,N-dimethyl-formamide; at 120℃; 0.59 g of 2,5-dihydroxybenzene-1,4-dicarboxylic acid (organic ligand L4) and 0.24 g Mg(NO3)2.9H2O (metal ion M1) were dissolved in the dimethylformamide, ethanol and water mixed solution and heated under 120 C. The obtained product Mg2(dobpdc) was immersed in the dimethylformamide for 4 days and dried under the vacuum at 180 C. 1.94 g of 4-trifluoromethyl phenol (organic anion X1) was dissolved in the anhydrous triglycol, meanwhile, 8.57 mL tetrahydrofuran with N, N-Diisopropylformamide was dropwise added in anhydrous triglycol. Both the tetrahydrofuran and N,N-Diisopropylformamide were removed after two hours and then the triglycol solution mixed with 125 mg Mg2(dobpdc), reacting for 7 days at 80 C. The obtained product (the third kinds of materials in the appended claim) was further activated. Then, the activated adsorbent was loaded into the column (inner diameter 4.6 mm, length 50 mm), the propylene/propyne (99/1, v/v) mixture was introduced into the column at 2 mL/min under 25 C. During the first 30 min, only propylene with low content of propyne (below 25 ppm) was obtained. The adsorption was stopped. The adsorbed propylene was desorbed under vacuum at 30 C.
  • 17
  • [ CAS Unavailable ]
  • [ 610-92-4 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
53% Stage #1: cobalt(II) nitrate hexahydrate; 2,5-dihydroxy-1,4-benzenedicarboxylic acid In ethanol; water; N,N-dimethyl-formamide Sonication; Stage #2: In ethanol; water; N,N-dimethyl-formamide at 100℃; for 24h; Further stages;
50% In tetrahydrofuran; water High Pressure; the acid and Co-salt were dissolved in THF-H2O (1:1 v/v) with stirring, the mixt. was sealed in Teflon autoclave and heated in an oven at 110°C for 3 days; crystals were filtered, dried under vac.;
46% In ethanol; water; N,N-dimethyl-formamide at 100℃; for 25h;
In ethanol; water; N,N-dimethyl-formamide at 100℃; for 18h;
In ethanol; water; N,N-dimethyl-formamide at 100℃; for 18h;
In water; N,N-dimethyl-formamide at 100℃; for 72h; Autoclave; Sealed tube;
Stage #1: cobalt(II) nitrate hexahydrate; 2,5-dihydroxy-1,4-benzenedicarboxylic acid In ethanol; water; N,N-dimethyl-formamide Sonication; Sealed tube; Stage #2: In ethanol; water; N,N-dimethyl-formamide at 100℃; for 24h; Sealed tube;
In ethanol; water; N,N-dimethyl-formamide at 100℃; for 24h; Sealed tube;
In ethanol; water; N,N-dimethyl-formamide at 100℃; for 24h;
In ethanol; water; N,N-dimethyl-formamide at 100℃; for 48h; Sealed tube;
With N-ethyl-N,N-diisopropylamine at 20℃; for 0.0833333h; Milling;
Stage #1: cobalt(II) nitrate hexahydrate; 2,5-dihydroxy-1,4-benzenedicarboxylic acid In ethanol; water; N,N-dimethyl-formamide at 120℃; for 24h; Autoclave; Stage #2: In methanol for 168h; Preparation of Ni-MOF-74 and Co-MOF-74 General procedure: NiCo-MOF-74 was synthesized by a solvothermal reaction based on a modified reference method [22]. Typically, nickel (II) nitrate hexahydrate (0.36 g, 1.2 mmol) and cobalt (II) nitrate hexahydrate (0.09 g, 0.3 mmol) were dissolved in 7mL mixture solution of deionized water (D.I.) and ethanol (1:1, volume ratio), respectively. The two solutions were mixed until they became clear and transparent. Then, a solution of 3.5 mL of N, N-dimethyl formamide including 2,5-dihydroxyterephthalic acid (H4DOBDC, 0.15 g, 0.75 mmol) was added to the mixed solution slowly and stirred for15 min. The volume ratio of the final mixed solutions was EtOH:DI:DMF = 1:1:1. The solution was continuously stirred 20 min at room temperature until uniform and transferred to the Teflon autoclave and heated at 120 °C for 24 h. When it was cooled to room temperature, the product was filtered and washed three times with DMF and methanol, respectively. And then, the obtaining product was immersed in methanol for a week. Finally, the resulting product was dried 12 h in a vacuum oven at 80 °C and was named 4NiCo-MOF-74. Similarly, 2NiCo-MOF-74 and 1NiCo-MOF-74 were also synthesized as the described above except changing the mole ratio of Ni(NO3)2*6H2O and Co(NO3)2*6H2O were 2:1 and 1:1, respectively. Ni-MOF-74 and Co-MOF-74 were prepared by following a similar process with only one metal source. For acquiring Ni-MOF-74 and Co-MOF-74, nickel (II) nitrate hexahydrate (0.45 g,1.5 mmol) and cobalt(II) nitrate hexahydrate (0.45 g, 1.5 mmol) were used as metal source, respectively and the composition of the final solution were the same as that of Ni/Co-MOF-74.
With salicylic acid In ethanol; water at 75℃; 1-5 The polytopic organic linkers were reacted with a compounds of formula Co(NO3)2·6H2O in a 1:1 H2O/EtOH solution buffered with 0.2 mM MOPS adjusted to pH 7. The concentration of the polytopic organic linkers in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. Present in the solution was a modulator of formula: . [00149] The concentration of the modulator in the solution was 35 mM. The solution was held at a temperature of 75Υ during the reaction thereby affording Co2(dobdc) crystals illustrated in the lower panel of Figure 8A, top panel.
With salicylic acid In ethanol; water at 75℃; 1-5 The polytopic organic linkers were reacted with a compounds of formula Co(NO3)2·6H2O in a 1:1 H2O/EtOH solution buffered with 0.2 mM MOPS adjusted to pH 7. The concentration of the polytopic organic linkers in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. Present in the solution was a modulator of formula: . [00149] The concentration of the modulator in the solution was 35 mM. The solution was held at a temperature of 75Υ during the reaction thereby affording Co2(dobdc) crystals illustrated in the lower panel of Figure 8A, top panel.

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[13]Current Patent Assignee: UNIVERSITY OF CALIFORNIA; EXXON MOBIL CORP - WO2023/14513, 2023, A1 Location in patent: Paragraph 0033; 00148-00157
[14]Current Patent Assignee: UNIVERSITY OF CALIFORNIA; EXXON MOBIL CORP - WO2023/14513, 2023, A1 Location in patent: Paragraph 0033; 00148-00157
  • 18
  • nickel(II) nitrate hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • Ni2(2,5-dihydroxybenzenedicarboxylic acid) [ No CAS ]
YieldReaction ConditionsOperation in experiment
1.91 g In water; N,N-dimethyl-formamide; at 110℃; for 21.5h;Autoclave; Sonication; [Ni2(dhtp)] was prepared in accordance with the following procedure as a PCP for Example 2. 72 mL of N,N-dimethylformamide and 3.6 mL of water were added to 3.63 g of nickel (II) nitrate hexahydrate and 0.72 g of <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> and an ultrasonic wave was applied to this mixture for dissolution. The obtained solution was reacted in an autoclave at 110 C. for 21.5 hours. A solid was collected by suction filtration and was dried in a vacuum to obtain a solid of 2.44 g. This solid was washed with ethanol and a solid collected thereafter by suction filtration is dried in a vacuum to obtain 1.91 g of the PCP for Example 2.
  • 19
  • zinc(II) nitrate hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • Zn<SUB>2</SUB>(2,5-dioxido-1,4-benzenedicarboxylate) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In water; N,N-dimethyl-formamide; at 110℃; for 21.5h;Sonication; To a 400 mL bottle was added <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (2,5-DHTA, 1 g, 5.0 mmol), Zinc nitrate hexahydrate (4.52 g, 15.2 mmol) and dimethylformamide (100 mL) were added and sonicated to dissolve. 5 mL of water was added, sonication was carried out, the lid of the bottle was closed and heated at 110 C. for 21.5 hours to obtain a powder metal complex. The supernatant was removed and washed three times with dimethylformamide and methanol. Thereafter, it was immersed in methanol for 3 days, the supernatant liquid was removed and heated at 265 C. under vacuum, followed by drying to obtain a porous metal complex (4) as a solid powder.
  • 20
  • [ 67-56-1 ]
  • [ 610-92-4 ]
  • [ 5870-37-1 ]
YieldReaction ConditionsOperation in experiment
87% With hydrogenchloride; In water; for 10h;Reflux; A solution of 2,5-dihydroxyterephthalic acid (500 mg, 2.5 mmol) in methanol (10 mL) and 2 drops of HC1 was refluxed for 10 h. The solvent was removed under vacuum and the residue was diluted with water and extracted with CH2Cl2. The organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by SiO2 column chromatography (elution with ethyl acetate:hexane in 1:2 v:v) to give A in 87% yield. A mixture of A (450 mg, 2.0 mmol), allyl bromide (530 mg, 4.4 mmol), potassium carbonate (1098 mg, 8.0 mmol) in acetonitrile (10 mL) was refluxed for 12 h. The solvent was removed under vacuum and the residue was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by SiO2 column chromatography (elution with ethyl acetate:hexane in 1:3 v:v) to give B in 75% yield. Compound B (400 mg, 1.3 mmol) was refluxed with an ethanolic solution of KOH (30%) for 12 h. The solvent was removed under vacuum and the residue was diluted with water and the pH was adjusted to 5.0 by addition of HCl (1.0 M). The white solid precipitated was filtered with a Buchner funnel, washed with water, and recrystallized from ethanol to give linker H2L in 85% yield. 1H NMR (DMSO-d6, 400 MHz): δ=4.57 (d, J=4.5 Hz, 4 H), 5.21 (d, J=10.5 Hz, 2 H), 5.41 (d, J=16.0 Hz, 2 H), 6.02-5.95 (m, 2 H), 7.28 (s, 2 H), and 12.97 ppm (s, 2 H, COOH); 13C NMR (DMSO-d6, 200 MHz) δ=70.6, 115.5, 118.4, 125.4, 133.2, 151.0, and 167.22 ppm; Elemental Analysis: Anal. Calcd for C14H1406: C, 60.43; H, 5.07; Found: C, 60.59; H, 5.10.
  • 21
  • [ 112-16-3 ]
  • [ 610-92-4 ]
  • [ 1374209-17-2 ]
YieldReaction ConditionsOperation in experiment
68% With zinc(II) chloride; at 95℃;Inert atmosphere; Example 1; Preparation of Compound 2; Preparation of Compound 1: 2,5-Dihydroxyterephthalic acid was chosen as the building block as it possesses both two carboxylic acids and two hydroxyl groups for functionalization.; 2,5-Dihydroxyteraphthalic acid (5.0 g, 25 mmol) and zinc chloride (0.81 g, 5.9 mmol) were stirred with lauroyl chloride (87 ml, 378 mmol). The solution was heated to 95 C. in a temperature-controlled oil bath and stirred under argon overnight. Diethylether (100 ml) and water (30 ml) were added and the solution was allowed to stir for 45 minutes. The organic phase was washed with water (5×100 ml) and then concentrated via rotary evaporation. The concentrated solution was precipitated from hexanes (2.5 L) yielding 1. (10.1 g, 68%). 1H NMR (CDCl3): 0.80-0.93 (t, 6H, CH3), 1.20-1.45 (m, 32H, CH2), 1.70-1.81 (m, 4H, CH2), 2.51-2.65 (m, 4H, CH2), 7.70 (s, 2H, Ar-CH); 13C NMR (CDC13): 14.32, 22.87, 29.34, 29.53, 29.67, 29.80, 29.82, 32.10, 34.37, 127.37, 128.74, 147.84, 165.27, 172.42; IR (NaCl cm-1): 2847, 1768, 1690 (CO), 1268, 1177, 935, 897; Tm=71 C.
  • 22
  • [ 590-29-4 ]
  • [ 123-31-9 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
66% Stage #1: potassium formate; hydroquinone With potassium carbonate at 200℃; for 6h; Stage #2: With hydrogenchloride In water
  • 24
  • [ 30652-11-0 ]
  • zinc(II) nitrate hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • [ 7732-18-5 ]
  • 3Zn(2+)*2C8H4O6(2-)*2C7H8NO2(1-)*2C3H7NO*2H2O [ No CAS ]
  • 25
  • [ 610-92-4 ]
  • [ 6018-89-9 ]
  • Ni<SUB>2</SUB>(2,5-dihydroxyterephthalate)(H2O)<SUB>2</SUB> [ No CAS ]
YieldReaction ConditionsOperation in experiment
86.2% In water; ethylene glycol; at 94℃; The MOF known as CPO-27-Ni has the composition Ni2(dhtp)(H20)2, where dhtp is 2,5- dihydroxyterephthalate. CPO-27-Ni was prepared by the following method. Ni(ll) acetate 4H20 (Alfa Aesar, 98%) was dissolved in a volume of distilled water, shown in Table 1. <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (dhtp)(Aldrich, 98%) was dissolved in the same volume of tetrahydrofuran (THF) (Sigma-Aldrich, 99.9%). The two solutions were stirred until a clear solution was obtained and then placed in a round-bottom-flask, which was subsequently attached to a reflux condenser. Each of the two precursors was dissolved in three quarters of the amount of solvent shown in Table 1, the remaining volume of solvent being used to rinse thebeakers to ensure that all of the reactants were washed into the flask. The molar ratio Ni(ll)/2,5 dihydroxyterephthalic acid was 2:1. The mixture was kept under reflux with stirring for 24 hours. The temperature of reaction was 67C. Once the reaction was completed, the final product was washed three times with 500m1 distilled water for 20 minutes each time. The product was filtered by vacuum filtering using ceramic funnels and then dried in air for a day, then under vacuum at80C for 24 h. The dried product consisted of yellow-ochre crystals.
  • 26
  • manganese(II) chloride tetrahydrate [ No CAS ]
  • cobalt(II) chloride hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • C8H2O6(4-)*0.57Co(2+)*0.43Mn(2+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% In ethanol; water; N,N-dimethyl-formamide; at 135℃; for 24h;Autoclave; This compound was prepared accordingto the literature method for CPO-27-Mn. H4dhtp (0.34 mmol,67 mg), MnCl2.4H2O (0.56 mmol, 110 mg), and CoCl2.6H2O(0.56 mmol, 132 mg) were dissolved in a mixture of DMF, ethanoland water (13/1/1, v/v; 15 mL) in a 23 mL Teflon lined stainlesssteel autoclave and heated at 135 C for 24 h. After cooling to roomtemperature, the solid was filtered out, washed with methanolthree times, and dried in air. Yield: 90%. The metal contents in theproduct were determined by EDS analysis
  • 27
  • [ 610-92-4 ]
  • [ 6156-78-1 ]
  • [ 6147-53-1 ]
  • C8H2O6(4-)*0.90Co(2+)*0.10Mn(2+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% In tetrahydrofuran; water; at 110℃; for 72h;Autoclave; This compound was prepared according to the literature method for CPO-27-Co. H4dhtp (0.34 mmol,67 mg) in THF (1.5 mL) and a solution of Co(OAc)2.4H2O (0.56 mmol,138 mg) and Mn(OAc).4H2O (0.56 mmol, 136 mg) in H2O (2 mL)were combined in the Teflon lined steel autoclave. The autoclavewas sealed and heated in a pre-heated oven at 110 C for 3 days.After cooling to room temperature, the solid was filtered out,washed with methanol three times, and dried in air. Yield: 85%. Themetal contents in the product were determined by EDS analysis.
  • 28
  • cobalt(II) nitrate hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • Co2(dihydroxyterephthalate) [ No CAS ]
YieldReaction ConditionsOperation in experiment
With polyvinylpyrrolidone; In ethanol; water; N,N-dimethyl-formamide; at 100℃; for 6h; Synthesis of P-0, P-5, P-7, and P-14. 2,5-Dihydroxyterephthalicacid (DHTA) (0.0362 g, 0.182 mmol), Co(NO3)2·6H2O(0.178 g, 0.613 mmol), PVP (0 g for P-0, 0.608 g for P-5,1.014 g for P-7, 2.028 g for P-14), and 15 mL of DMF:ethanol:water (1:1:1, v:v:v) were combined in a 20 mL vialequipped with a magnetic stir bar. The vial was then cappedwith a Teflon-lined cap and sonicated for 5 min to obtain ahomogeneous solution. The resulting reaction mixture wasplaced in a 100 oC oil bath and vigorously stirred (300 rpm).After 6 h, orange powder was precipitated from the reactionmixture. The resulting suspension was cooled to roomtemperature. Finally, the sample was washed twice withDMF (40 mL) and twice with MeOH (40 mL) to removeexcess PVP and centrifuged at 2500 rpm. The remainingorange powder was then stored in MeOH until further use.
In ethanol; water; N,N-dimethyl-formamide; at 100℃; for 24h; Co-MOF-74 was synthesized using the conventional solvothermal method following a procedure reported in the literature [18]: a solid mixture of H4DHBDC (2,5-dihydroxybenzenedicarboxylic acid, 0.729 mmol) and Co(NO3)2·6H2O (cobalt nitrate hexahydrate, 2.45 mmol) was added to a 1:1:1 mixture of DMF-ethanol-water (60 mL) in a 100 mL Duran bottle, and stirred for 1 h until it became homogeneous. The reaction vial was capped tightly and placed in an oven at 100 C. After 24 h, the bottle was removed from the oven and allowed to cool to room temperature. The MOF crystals were separated by filtration and soaked in methanol for 24 h under stirring, in order to exchange the DMF that remained in the pores of the material. Methanol was replaced three times during the procedure.
  • 29
  • [ 610-92-4 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
90% With sodium hydroxide In water for 1h; Reflux; 2.1 Synthesis of Na2(H2-dhbdc)·0.5H2O To a suspension in water of H4-dhbdc, a stoichiometric amount of sodium hydroxide was added leading to a clear solution that was evaporated to dryness. The obtained solid was then dissolved in ethanol and refluxed for one hour. Addition of ethoxyethane provokes precipitation. The obtained brown precipitate was filtered, washed with ethoxyethane and dry in air. The yield was about 90%. C8H5Na2O6.5 (MW=251g.mol-1) Analysis: (calc.) found: C (38.2%) 38.5%; H (2.0%) 2.2%; O (41.4%) 41.3%; Na (8.3%) 8.0 %. Thermogravimetric analysis confirms that this salt is hemi-hydrated. Its X-ray powder diffraction diagram is reported in Fig. S1.
  • 30
  • [ 610-92-4 ]
  • 6C2H3O2(1-)*Fe2CoO(6+) [ No CAS ]
  • 3C8H4O6(2-)*3H2O*Fe2CoO(6+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With acetic acid; In water; at 150℃; for 24h;Sonication; L3 (10mg), Fe2COO(CH3COO)6 (10 mg) and acetic acid (0.25 ml) in 2 mL of DEF and H2O (v / v = 1 / 1) wereultrasonically dissolved in a Pyrex vial. The mixture was heated in 150 C oven for 24 h. After cooling down to roomtemperature, dark brown crystals were harvested by filtration (Yield. 80%).
  • 31
  • copper(II) nitrate trihydrate [ No CAS ]
  • [ 610-92-4 ]
  • Cu<SUB>2</SUB>(2,5-dioxido-1,4-benzenedicarboxylate) [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% In N,N-dimethyl-formamide; isopropyl alcohol; at 85℃; for 18h; In a typical preparation, a solid mixture of H2dhtp (H2dhtp=<strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong>; 0.495g, 2.5mmol), and Cu(NO3)2·3H2O (1.21g, 5mmol) was dissolved in a mixture of DMF (DMF=N,N?-dimethylformamide; 47mL), and 2-propanol (3mL). The resulting solution was then distributed to seven 10mL vials. The vials were heated at 85C in an isothermal oven for 18h. After cooling the vials to room temperature, the solid product was removed by decanting with mother liquor and washed in DMF (3×20mL). Solvent exchange was carried out with 2-propanol (3×20mL) at room temperature. The material was then evacuated under vacuum at 150C for 5h, yielding 0.50g of Cu-MOF-74, Cu2(DOBDC), in the form of reddish black crystals (62% yield based on H2dhtp).
  • 32
  • [ 30652-11-0 ]
  • bismuth (III) nitrate pentahydrate [ No CAS ]
  • [ 610-92-4 ]
  • [ 7732-18-5 ]
  • [ 68-12-2 ]
  • [Bi2(2,5-dihydroxy-1,4-benzenedicarboxylic acid-2H)(deferiprone-H)4(H2O)2]·2DMF [ No CAS ]
  • 33
  • [ 288-88-0 ]
  • zinc(II) nitrate hexahydrate [ No CAS ]
  • [ 610-92-4 ]
  • 2Zn(2+)*2C2H2N3(1-)*C8H4O6(2-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Ca. 90% In methanol; N,N-dimethyl acetamide; water; at 90℃;High pressure; Sealed tube; In a 25 ml glass vial, 30mg Zn(NO3)26H2O, 7mg HTRZ, and 20mg DOBDC were dissolved in a mixture of 2ml DMA, 1ml CH3OH and 1ml H2O. The vial was sealed and placed in a 90C oven for 5days. Pure block crystals were obtained after cooling to room temperature. The yield was about 90% based on Zn. Elemental analysis for 2, Calcd: H, 1.53; C, 31.19; N, 18.19; Found: H, 1.63; C, 31.61; N, 19.24.
  • 34
  • [ 610-92-4 ]
  • C8H4O6(2-)*Mg(2+)*6H2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With magnesium(II) nitrate hexahydrate; sodium hydroxide; In ethanol; water; for 24.0667h;Reflux; A solution of Mg(NO3)2·6H2O (11.4g, 44.4mmol) in water (49mL) and ethanol (24mL) was added dropwise to a stirred solution of <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (3.83g, 19.3mmol) in aqueous sodium hydroxide (0.5M, 77.4mL, 38.7mmol) over a period of 4min. The resulting solution was heated to reflux for 24h. The solution was cooled to room temperature and an initial yellow solid collected via filtration, washed with hot ethanol and allowed to dry overnight yielding a yellow powder (CPO-27-Mg, 0.846g, 2.0mmol, 10%). The brown mother liquor was allowed to stand at room temperature for a further 3days, over which time brown crystals (4.145g, 12.6mmol, 65% yield) formed as the solvent slowly evaporated. Elemental analysis calcd. for C8H16MgO12 C: 29.24, H: 4.91, found C: 29.30H: 4.95%.
  • 35
  • europium nitrate pentahydrate [ No CAS ]
  • [ 610-92-4 ]
  • [ 171058-17-6 ]
  • [1-hexyl-3-methylimidazolium]Eu(2,5-dihydroxyterephthalate)2 [ No CAS ]
  • 36
  • [ 610-92-4 ]
  • [ 615-47-4 ]
  • 2,5-bis(5-amino-2-benzimidazole)-1,4-dihydroxybenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
75.2% Example 3(1) under the conditions of the protection of nitrogen, in the 1000 ml flask are added respectively in three 78.43g (0.4mol) 1, 2, 4-triaminobenzene hydrochloride, 700gP2O5content is 80% poly phosphoric acid, 1.19g (0.01mol) tin powder, in the 100 C stirring under 6h, to obtain 1, 2, 4-triaminobenzene of the mixed solution of 2nd(2) in the mixed solution to the above-mentioned 2nd 42.57g (0.3mol) P2O5, 39.62g (0.2mol) 2,5-dihydroxy terephthalic acid, in 190 C reaction under 8h, a reaction mixture is obtained(3) lowering the temperature to the above reaction mixture to 100 C, then poured into ice water stirring 2h, through filtering, the distilled water is washed, after the filter cake is taken out, by adding a small amount of water, and of saturation Na2CO3solution to adjust the pH value to 7, through filtering, the distilled water is washed, the last 120 C vacuum drying 24h, obtained crude product containing hydroxy benzimidazole diamine(4) using N-methyl pyrrolidone as a solvent, the crude product containing hydroxy benzimidazole diamine performing recrystallization, to obtain light yellow powder, and then sequentially through filtering, methanol washing, 120 C vacuum drying 24h, containing hydroxy benzimidazole diamine obtained, HPLC purity is 97.8%, the yield is 75.2%.
  • 37
  • [ 610-92-4 ]
  • [ 7786-30-3 ]
  • iron(II) chloride [ No CAS ]
  • Fe<SUB>0.1</SUB>Mg<SUB>1.9</SUB>(2,5-dioxido-1,4-benzenedicarboxylate) [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% In methanol; N,N-dimethyl-formamide; at 120℃; for 16h; In a 500 mL schlenk flask, H4(dobdc) (1.75 g, 8.8 mmol), MgCl2 (1.47 g, 15.4 mmol), and FeCl2 (0.84 g, 6.6 mmol) were dissolved in DMF (310 mL) and MeOH (40 mL). The reaction was stirred vigorously at 120 C. for 16 hours. The precipitate was filtered and stirred in fresh DMF (250 mL) at 120 C. for three hours. Two more DMF washes at 120 C. were performed, after which the precipitate was filtered and soaked in methanol at 60 C. The methanol exchanges were repeated until no DMF stretches were visible by IR. The framework was fully desolvated under dynamic vacuum (<15 mubar) at 210 C. for 2 days to afford Fe0.1Mg1.9 (dobdc) as a bright yellow-green solid (2.02 g, 8.2 mmol, 93% yield). Fe0.44Mg1.56(dobdc) and other analogs with different Fe:Mg ratios can be obtained by simply varying the ratio of MgCl2 and FeCl2 while keeping all other synthetic conditions the same. The iron to magnesium ratio was determined by ICP-OES. Anal. Calc. for C8H2Fe0.1Mg1.9O6: C, 39.08; H, 0.82. Found: C, 39.37; H, 0.43. IR (solid-ATR): 1577 (s), 1484 (m), 1444 (s), 1429 (s), 1372 (s), 1236 (s), 1210 (s), 1123 (m), 911 (m), 892 (s), 828 (s), 820 (s), 631 (s), 584 (s), 492 (s).
  • 38
  • [ 3140-93-0 ]
  • [ 610-92-4 ]
  • 2,5-bis(3-bromothiophen-2-yl)benzene-1,4-diol [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 6h;Schlenk technique; 1) accurate weighing 2, 3 - dibromo thiophene (2.0 mmol), 2, 4 - dihydroxy terephthalic acid (1.0 mmol), and in turn to 25 ml of in shu Lunke bottle, adding potassium carbonate (552 mg, 4.0 mmol), four (triphenylphosphine) palladium (0.05 equivalent), 1, 4 - dioxane/water (volume ratio 4:1), is 90 C reaction in oil bath 6 hours. After the reaction, the solvent is removed under reduced pressure, the use of silica gel column separation, petroleum ether/ethyl acetate as eluant, obtaining the intermediate 3n,
  • 39
  • zinc(II) nitrate hexahydrate [ No CAS ]
  • [ 57654-36-1 ]
  • [ 610-92-4 ]
  • [ 33513-42-7 ]
  • [Zn2(μ-2,5-dihydroxyterephthalate)2(μ-3,6-bis(4-pyridyl)-1,2,4,5-tetrazine)(DMF)4]·2DMF·H2O}n [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% at 95℃; for 72h;
  • 40
  • [ 106-42-3 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
80.6% With dihydrogen peroxide; trifluoroacetic acid In ethanol at 90℃; for 10h; 1-10 Example IV: Pipette 2.5mL (≈20mmol) of p-xylene into a 100mL round-bottomed flask, and add Cu-MCM41 (0.20g, Cu content of 10%), ethanol (17mL), trifluoroacetic acid (3mL), hydrogen peroxide (30%) in sequence , 7mL), after reacting at 90°C for 10h, stop the reaction, cool, filter, and separate to obtain 3.0g (separated yield is about 80.6%) of 2,5-dihydroxyterephthalic acid.
With dihydrogen peroxide In ethanol at 70℃; for 10h; 1 Example 1: Catalytic Preparation of 2,5-Dihydroxyterephthalic AcidInclude the following steps: Step S1,Under the effect of solid catalyst,The paraxylene in the solvent is reacted with the oxidant at 70°C for 10 hours;Step S2,Stop the reaction and filter the catalyst for repeated application to obtain a mixed solution containing 2,5-dihydroxyterephthalic acid;Step S3,The mixed solution is purified by chromatography to obtain the product 2,5-dihydroxybenzeneacid. The solvent is ethanol, which is 7 times the volume of p-xylene. Acetonitrile can also be used. Hydrogen peroxide was used as the oxidant and the ratio of oxidant to paraxylene was 1.8:1.The solid catalyst uses magnesium-aluminum hydrotalcite as a precursor, modified nano-kaolin as a carrier, and the precursor mass is 35% of the carrier mass. The precursor and carrier are ground and uniformly mixed and then calcined at 600° C. for 3 hours. The molar ratio of magnesium to aluminum in the magnesium-aluminum hydrotalcite is 2.5:1. The preparation method is as follows: The magnesium salt and aluminum salt are mixed and dissolved in deionized water.A mixed salt solution is prepared; the precipitant is dissolved in deionized water to obtain an alkaline solution; the mixed salt solution and the alkali solution are added into the reaction vessel in a cocurrent manner, and then reacted at a temperature of 60° C. and a pH of 10. After 45 minutes, it was allowed to stand for 12 hours and the resulting precipitate was washed to neutrality and dried. The modified nano kaolin preparation method comprises: taking 35 parts of nano kaolin dispersed in 55 parts of an aqueous solution of disodium ethylenediaminetetraacetate with a mass fraction of 10%, stirring at 45° C. for 1.5 hours, and then adding 10 parts of zinc sulfate. , Stir for 25min, filter after cooling and dry.
  • 41
  • [ 610-92-4 ]
  • N-(2-methoxybenzyl)-N-methylpropane-1,3-diamine [ No CAS ]
  • 2,5-dihydroxy-N<SUP>1</SUP>,N<SUP>4</SUP>-bis(3-((2-methoxybenzyl)(methyl)amino)propyl)terephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
48.4% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 42
  • [ 616885-82-6 ]
  • [ 610-92-4 ]
  •  N1,N4-bis(3-(ethyl(2-methoxybenzyl)amino)propyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
47.3% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 43
  • [ 610-92-4 ]
  • [ 221196-25-4 ]
  • N<SUP>1</SUP>,N<SUP>4</SUP>-bis(4-(benzyl(methyl)amino)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
45.2% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 44
  • [ 610-92-4 ]
  • [ 131334-11-7 ]
  •  N1,N4-bis(4-(benzyl(ethyl)amino)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
65.7% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 45
  • [ 610-92-4 ]
  • N-(2-methoxybenzyl)-N-methylbutane-1,4-diamine [ No CAS ]
  • 2,5-dihydroxy-N<SUP>1</SUP>,N<SUP>4</SUP>-bis(4-((2-methoxybenzyl)(methyl)amino)butyl)terephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
39.1% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 46
  • N1-ethyl-N1-(2-methoxybenzyl)butane-1,4-diamine [ No CAS ]
  • [ 610-92-4 ]
  •  N1,N4-bis(4-(ethyl(2-methoxybenzyl)amino)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
47.5% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 47
  • [ 610-92-4 ]
  • N-(2-(dimethylamino)benzyl)-N-ethylbutane-1,4-diamine [ No CAS ]
  •  N1,N4-bis(4-((2-(dimethylamino)benzyl)(ethyl)amino)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
31.9% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 48
  • [ 610-92-4 ]
  • N-(4-(dimethylamino)benzyl)-N-ethylbutane-1,4-diamine [ No CAS ]
  •  N1,N4-bis(4-((4-(dimethylamino)benzyl)(ethyl)amino)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
37.7% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 49
  • [ 610-92-4 ]
  • 4-(2,3-dihydrobenzo[f][1,4]oxazepin-4(5H)-yl)butan-1-amine [ No CAS ]
  •  N1,N4-bis(4-(2,3-dihydrobenzo[f][1,4]oxazepin-4(5H)-yl)butyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
55.3% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 50
  • [ 610-92-4 ]
  • [ 101098-52-6 ]
  •  N1,N4-bis(6-(benzyl(methyl)amino)hexyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
47.2% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 51
  • [ 610-92-4 ]
  • [ 131334-14-0 ]
  •  N1,N4-bis(6-(benzyl(ethyl)amino)hexyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 52
  • N1-(2-methoxybenzyl)-N1-methylhexane-1,6-diamine [ No CAS ]
  • [ 610-92-4 ]
  • 2,5-dihydroxy-N<SUP>1</SUP>,N<SUP>4</SUP>-bis(6-((2-methoxybenzyl)(methyl)amino)hexyl)terephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
49.2% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 53
  • [ 616885-86-0 ]
  • [ 610-92-4 ]
  •  N1,N4-bis(6-(ethyl(2-methoxybenzyl)amino)hexyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
46.1% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 54
  • [ 13910-49-1 ]
  • [ 610-92-4 ]
  •  N1,N4-bis(3-(benzyl(methyl)amino)propyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
62.6% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10. 4.1.4.1 N1,N4-bis(3-(benzyl(methyl)amino)propyl)-2,5-dihydroxyterephthalamide (8a) Compound 8a was synthesized from intermediate 4 and 5a according to the general procedure. After purification by chromatography on silica gel using dichloromethane/acetone (1:3) as eluent, the pure product 8a was obtained as yellow oil, yield 62.6%. 1H NMR (400 MHz, CDCl3) delta 11.80 (brs, 2H), 8.76 (brs, 2H), 7.33-7.26 (m, 10H), 6.87 (s, 2H), 3.64 (s, 4H), 3.55-3.45 (m, 4H), 2.65-2.60 (m, 4H), 2.39 (s, 6H), 1.86-1.79 (m, 4H); 13C NMR (100 MHz, CDCl3) delta 168.7, 152.7, 136.9, 129.4, 128.6, 127.6, 119.2, 114.3, 62.9, 56.1, 41.8, 40.0, 24.6. ESI-MS m/z: 519.4 [M+H]+
  • 55
  • [ 610-92-4 ]
  • [ 140134-63-0 ]
  •  N1,N4-bis(3-(benzyl(ethyl)amino)propyl)-2,5-dihydroxyterephthalamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
44.5% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine; In tetrahydrofuran; at 20℃; General procedure: To a stirred solution of compound 4 (50 mg, 0.252 mmol), EDCI (169 mg, 0.882 mmol), HOBt (119 mg, 0.881 mmol) and triethylamine (0.176 mL, 1.26 mmol) in tetrahydrofuran (3 mL), corresponding primary amines 5-7 (0.882mmol) was added. The reaction mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was concentrated. Then dichloromethane (15 mL) was added to the residue and the mixture was washed with saturated aqueous sodium bicarbonate solution (10 mL) and brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude compound. The obtained residue was purified by silica gel column chromatography to afford 8-10.
  • 56
  • [ 110144-22-4 ]
  • zinc nitrate tetrahydrate [ No CAS ]
  • [ 610-92-4 ]
  • [ 33513-42-7 ]
  • [Zn2(trans,trans-1,4-bis[2-(4′-pyridyl)ethenyl]benzene)-(2,5-dihydroxy-benzene-1,4-dicarboxylate)(formate)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
In water at 100℃; High pressure;
  • 57
  • [ 610-92-4 ]
  • [ 149590-60-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: hydrogenchloride / water / 10 h / Reflux 2: potassium carbonate / acetonitrile / 12 h / Reflux 3: potassium hydroxide / ethanol / 12 h / Reflux
Multi-step reaction with 3 steps 1: hydrogenchloride / water / 10 h / Reflux 2: potassium carbonate / acetonitrile / 12 h / Reflux 3: potassium hydroxide / ethanol / 12 h / Reflux
  • 58
  • [ 610-92-4 ]
  • [ 26239-59-8 ]
YieldReaction ConditionsOperation in experiment
90% With [2,2]bipyridinyl; thionyl chloride; at 80℃; for 2h;Sonication; A preparation method of the high-purity 2,5-dihydroxyterephthaloyl chloride of the invention comprises the following steps: (1) 50 g of <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong>, 61.1 g of thionyl chloride and 0.4 g of 2,2'-bipyridine were added to a round bottom flask with a reflux condenser. In the ultrasonic instrument, the ultrasonic power is 250W, and the ultrasonic reflux reaction is 80 C 2h. The hydrogen chloride and sulfur dioxide formed by the reaction were promptly passed into a potassium hydroxide solution having a mass concentration of 20%, and then the reaction was observed after the absence of exhaust gas, and the thionyl chloride and the catalyst 2,2'-bipyridine were distilled off under reduced pressure to obtain a coarse 20.6-dihydroxyterephthaloyl chloride 60.6 g, isolated yield 90%; (2) adding 0.31 g of FeCl3 to the crude 2,5-dihydroxyterephthaloyl chloride obtained after the step (1), heating to 120 C, and maintaining the temperature for 1 h.High purity 2,5-dihydroxyterephthaloyl chloride was distilled off in vaccum.
  • 59
  • gadolinium nitrate hydrate [ No CAS ]
  • [ 610-92-4 ]
  • [Gd2(2,5-dihydroxyterephthalato)3(H2O)6]*2H2O}n [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With sodium hydroxide; In water; at 140℃; for 12h;Autoclave; High pressure; The reaction mixture was obtained combining 6.0 mL of a 0.50 M aqueous solution of hydrated gadolinium nitrate (0.30 mmol Gd), <strong>[610-92-4]2,5-dihydroxyterephthalic acid</strong> (0.091 g, 0.46 mmol) and 9.00 mL of a 0.1 M standard aqueous solution of NaOH (0.900 mmol of NaOH) in a Parr Teflon-lined stainless-steel autoclave (30 mL). The vessel was sealed and transferred in an oven where it was heated to 140 C for 12 h. The brownish crystalline product, mainly single block crystals, was filtered and air dried. (0.127 g; 83 % yield). El. Anal.: Found: C 27.6, H 2.7. Calc. for [Gd2(H2L)3(H2O)6]·2H2O}n, C12H14O13Gd: C 27.5, H 2.7%. ATR IR, solid (4000-650cm-1): 3480-2920 (br), 1680 (vw), 1636 (vw), 1564 (m), 1558 (m), 1516 (m), 1506 (m), 1496 (m), 1455 (s), 1435 (s), 1354 (m), 1318 (m), 1279 (m), 1245 (m), 1215 (s), 1124 (w), 1063 (vw), 998 (w), 902 (vw), 879 (m), 823 (m), 816 (m), 799 (vs), 778 (s), 739 (s), 705 (s), 656 (m) cm-1.
  • 60
  • [ 610-92-4 ]
  • Gd(3+)*3NO3(1-)*4.1H2O [ No CAS ]
  • [Gd2(2,5-dihydroxyterephthalato)(2,5-dioxidoterephthalato)(H2O)5]*2H2O}n [ No CAS ]
YieldReaction ConditionsOperation in experiment
88.2% With sodium hydroxide; In water; at 160℃; for 24h;Autoclave; High pressure; Gd(NO3)3·4.1 H2O (0.247 g, 0.592 mmol), H4L (0.118 g, 0.596 mmol) and 17.80 mL of a 0.1 M standard aqueous solution of NaOH (1.80 mmol NaOH) were introduced in a Teflon-lined stainless-steel autoclave. The vessel was sealed and transferred in an oven where it was heated at 160 C for 24 h. The green-yellow micro-crystalline product was filtered and air dried (0.217 g; 88.2 % yield).
  • 61
  • [ 610-92-4 ]
  • Gd(3+)*3NO3(1-)*2.9H2O [ No CAS ]
  • [ 68-12-2 ]
  • [Gd2(2,5-dihydroxyterephthalato)3(N,N-dimethylformamide)4]*2(N,N-dimethylformamide)}n [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With carbon dioxide; dibutylammonium dibutylcarbamate; In n-heptane; at 20℃; for 730.5h; A vial containing a solution of Gd(NO3)3·2.9 H2O (0.096g, 0.24mmol) and H4L (0.079g, 0.40mmol) in DMF (10mL) was introduced in a flask containing a solution of [NH2Bu2][O2CNBu2] in heptane (10mL, 0.594M), under carbon dioxide atmosphere. After 1 month at room temperature large pale yellow crystals, formed in the vial, were filtered. (0.150g, 93% yield).
  • 62
  • manganese(II) nitrate hexahydrate [ No CAS ]
  • [ 27318-90-7 ]
  • [ 610-92-4 ]
  • 0.5C8H4O6(2-)*0.5C12H6N2O2*0.5Mn(2+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
39.3% With sodium hydroxide; In methanol; water; at 159.99℃; for 120h;pH 6.5;Autoclave; Mn (NO3)26H2O (0.029 g, 0.1 mmol), PHDI (0.041 g, 0.2 mmol),DHTA (0.040 g, 0.2 mmol), and MeOH (3 mL) were mixed anddissolved in deionized water (20 mL), which was then adjusted tothe pH value to 6.5 by adding the NaOH solution. The mixture wassealed in a 30 mL Teflon-lined stainless steel and heated at 433.15 Kfor 5 days. Then cooled it to room temperature and obtained pinkblock crystals. The reagents were of analytical grade in this experiment.Yield: 39.3% based on Mn (II). Anal. Calcd. forC10H5NO4Mn0.50 (%): C, 52.03; H, 2.17; N, 6.07. Found (%): C, 51.77;H, 2.03; N, 5.89.
  • 63
  • [ 610-92-4 ]
  • dilithium (2,5-dilithium-oxy)-terephthalate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With lithium methanolate; In methanol; at 20℃; for 40h; The synthesis procedure was previouslyreported by Chen?s group.36 Into a homogeneous solution of H4-p-DHT (1.0 g, 5.1 mmol, 1 eq.) in anhydrous methanol (50 ml)was dripped 10.1 ml of lithium methoxide (2.2 M in methanol,22.4 mmol, 4.4 eq.). A yellow precipitate was formed after ?3 minunder stirring at room temperature. After reaction for 40 h, the aspreparedsolid was filtered and washed (3 × 6 ml) with anhydrousmethanol, and dried under vacuum at 100 C overnight. The finalcompound Li4-p-DHT was obtained by thermal treatment at 220 Cfor 24 h in a drying glass oven (Buechi B-585 glassoven for drying) inglovebox to afford Li4-p-DHT as orange powder (yield: 87%). Thedesolvation effectiveness was checked by thermal analysis and theabsence of MeOH traces in NMR and IR spectra. IR (KBr pellet,cm-1) 1570 (nuas COO-), 1467-1412 (nu C=C), 1363 (nus COO-),1232 (nu CO-Li ), 880-800 (nu C-H); 1H NMR (400 MHz, D2O) delta(ppm) 7.11 (2H, s); 13C NMR (100 MHz, D2O) delta (ppm) 175.97 (C,C=O), 152.78 (C, C-O-), 125.39 (C, C-COO-), 118.82 (C, C-H).
  • 64
  • [ 610-92-4 ]
  • [ 6018-89-9 ]
  • nickel(II) 2,5-dihydroxyterephthalate [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With 1,4-diaza-bicyclo[2.2.2]octane In tetrahydrofuran; water at 120℃; for 24h; 2.2. Synthesis of Ni-MOF-74 (Ni-4) Ni(OAc)24H2O (2.3 mmol, 572 mg) was dissolved in water(17.5 mL); 2,5-dihydroxyterephtalic acid (1.2 mmol, 232 mg) was dissolved in THF (10 mL); and DABCO (1.15 mmol, 130 mg) was dissolved in THF (7.5 mL). Afterwards, all the three solutions were mixed together in a tube and were stirred for 15 min at room temperature, followed by heating to 120 °C in the oven for 24 h. Then there action mixture was cooled to room temperature. A light-brown solid of Ni-4 was centrifuged and the liquid was poured out. The obtained solid of MOF was washed with 3 × 10 mL THF over 3 days. The resulting solid was dried under vacuum at room temperature for 2 days. The yield of Ni-4 was 57% (337 mg).
  • 65
  • [ 1336-21-6 ]
  • cobalt(II) nitrate hexahydrate [ No CAS ]
  • [ 14389-12-9 ]
  • [ 64-17-5 ]
  • [ 610-92-4 ]
  • 3Co(2+)*HO(1-)*1.5C8H2O6(4-)*3C6H5N5*H3N*H(1+)*3C2H6O*2.5H2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% Stage #1: ammonium hydroxide; cobalt(II) nitrate hexahydrate; 5-(4-pyridyl)tetrazole; ethanol; 2,5-dihydroxy-1,4-benzenedicarboxylic acid In water for 0.5h; Stage #2: In water at 150℃; for 48h; Sealed tube;
  • 66
  • [ 610-92-4 ]
  • [ 100-39-0 ]
  • [ 1060771-43-8 ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 2,5-dihydroxy-1,4-benzenedicarboxylic acid With sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 60℃; for 5h; 1.1 (1) Anhydrous DMF (5.0 mL) and NaHCO3 (530 mg, 6.31 mmol) were added to a round bottom flask containing 2,5-dihydroxyterephthalic acid (500 mg, 2.52 mmol), and the mixture was stirred at room temperature for 10 minute. Then, benzyl bromide (1.29 g, 7.57 mmol) was added, and the reaction mixture was heated to 60° C. and stirred for 5 h. The reaction was quenched with water (10 mL), and the organic compound was extracted with DCM (50 mL×3). Subsequently, the combined organic layer was washed with saturated brine, dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation to obtain the carboxyl protected product (800 mg, 84%).
  • 67
  • [ 6289-46-9 ]
  • [ 610-92-4 ]
YieldReaction ConditionsOperation in experiment
97% With 2-ethyl-9,10-anthraquinone; dihydrogen peroxide; potassium hydroxide In methanol Inert atmosphere; Reflux; 1-3 Example 1 400 parts of methanol, 100 parts of dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate (DMSS) and 35 parts of solid sodium hydroxide were sequentially added to the stirring,In the reactor of the temperature control and condensing device,Heat and stir and pass inert gas into the reactor, and then add 5 parts of 2-ethylanthraquinone to the reactor, in the reflux state, then add 60 parts of 30% hydrogen peroxide aqueous solution to the reactor. After the hydrogen peroxide aqueous solution is added, continue to keep stirring under reflux state, Until the suspended matter in the reactor completely disappears, the temperature is lowered, and 30% hydrochloric acid is added to the reactor until the pH of the reaction liquid in the reactor is 3.0-3.5,After cooling, filtering, the filter cake is the target after washing and drying, the yield is 95%, and the HPLC purity is 99% (area normalization method).
91% Stage #1: dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate With oxygen; sodium hydroxide In lithium hydroxide monohydrate at 130℃; for 72h; Stage #2: With sulfuric acid; hydrazine hydrate monohydrate In lithium hydroxide monohydrate 1 Add 11.4kg of dimethyl succinyl succinate, 16kg of sodium hydroxide (that is, the mol ratio of dimethyl succinyl succinate and sodium hydroxide is 1:8), pure aqueous solution 22.8kg, feed pure oxygen, stir and be heated to 130 , react for 72 hours, drop the temperature and add 0.12kg of 80% hydrazine hydrate solution, then add 1mol/L sulfuric acid to neutralize pH to 3.0, cool After filtering, 9.0 kg of yellow powdery solid after the filter cake was washed and dried was 2,5-dihydroxyterephthalic acid, and the yield was 91%.
  • 68
  • [ 610-92-4 ]
  • [ 161433-66-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: sulfuric acid / Reflux 2: potassium carbonate / N,N-dimethyl-formamide / 48 h / 60 °C 3: potassium hydroxide; water / ethanol / Reflux
  • 69
  • [ 610-92-4 ]
  • [ 114503-42-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: sulfuric acid / 8 h / Reflux 2: potassium carbonate / N,N-dimethyl-formamide / 8.5 h / 90 °C / Inert atmosphere; Sealed tube 3: hydrazine hydrate / ethanol / 15 h / Reflux
  • 70
  • [ 610-92-4 ]
  • [ 5870-37-1 ]
  • 71
  • [ 34981-10-7 ]
  • [ 610-92-4 ]
  • [ 169836-78-6 ]
YieldReaction ConditionsOperation in experiment
99.2% Stage #1: 2,5-dihydroxy-1,4-benzenedicarboxylic acid With sodium hydroxide In lithium hydroxide monohydrate at 50℃; for 0.5h; Inert atmosphere; Stage #2: 2,3,5,6-tetraaminopyridine trihydrochloride With disodium sulphide In lithium hydroxide monohydrate at 20℃; for 0.333333h; Inert atmosphere; 1-4 Example 2 Choose a two-necked bottle (fully dry),DHTA (1.32 g, 6.6 mmol) was added,Evacuate and change nitrogen three times and add deoxygenated water (50mL) (ultra-clean water is deoxygenated with nitrogen),Then weigh NaOH (0.8g, 19.8mmol) and dissolve it into 5mL aqueous solution,The solution was purged with nitrogen to remove oxygen.Add sodium hydroxide solution to DHTA solution,See the original solution gradually dissolve,reddish brown,The final black solution,heated to 50°C,React for 30 minutes.Take another two-necked flask and add TAP·3HCl (1.4g, 5.6mmol) and Na2S (0.055g, 0.71mmol) solid,Evacuate and change nitrogen three times,Add deoxygenated water (50mL),Dissolve at room temperature,The reaction time is 20min.The solution was completely dissolved and showed a yellowish brown color.Mix the above two reaction solutions,The reaction solution in step 2 is added to the mixed solution in step 1,add slowly,Bubbles are formed immediately when added,With solid precipitation,The solid is pale yellow,As the join progresses,The more solids are separated, the moreAfter joining,The reaction was carried out at 50°C for 30 minutes.Cool the reactants,Add dilute hydrochloric acid (bubbling),Make the pH value 3.Quickly transferred to suction filtration to obtain solid,At the same time with cold water (bubbling),and rinsed with cold ethanol (bubbling) to give a light green solid.Dry under vacuum at 60°C for 24h.get 2.28g,Yield 99.2%.
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  • [ 1206802-27-8 ]
  • [ 610-92-4 ]
  • [ 861533-46-2 ]
  • [ 10026-11-6 ]
  • [ 64-19-7 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
at 120℃;
Same Skeleton Products
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