Structure of N-Hydroxyphthalimide
CAS No.: 524-38-9
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Nanoporous synthetic metal: A nickel MOF with an amino-functionalized macrocyclic ligand
Pham, Hoai TB ; Fang, Xiaoyu ; Choi, Ji Yong ; Huang, Shaofeng ; Park, Jihye ;
Abstract: Integrating metallic charge transport with high porosity in a single material can unlock significant advancements in energy storage, electrocatalysis, and chemiresistive sensing. However, these properties rarely coexist due to the conflicting need for a high charge carrier density and the presence of voids. Herein, we report a new macrocyclic ligand, 2,3,8,9,14,15-hexaaminotribenzocyclyne (HATC) and its electrically conductive metal-organic framework (EC-MOF), coordinated with nickel nodes to render Ni-HATC as nanoporous synthetic metal. HATC provides intrinsic pockets for extra porosity, while its six amino and three alkyne groups significantly enhance electron density for realizing metallic behaviors in Ni-HATC. Consequently, Ni-HATC achieves exceptional conductivities of 20 S/cm in thin films and 3 S/cm in bulk, with a high surface area of 1000 m2 /g. Our findings showcase a unique material combining metallic charge transport and high porosity, opening new possibilities for future synthetically nanoporous metallic materials.
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CAS No. : | 524-38-9 |
Formula : | C8H5NO3 |
M.W : | 163.13 |
SMILES Code : | O=C(N1O)C2=CC=CC=C2C1=O |
MDL No. : | MFCD00005891 |
InChI Key : | CFMZSMGAMPBRBE-UHFFFAOYSA-N |
Pubchem ID : | 10665 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 12 |
Num. arom. heavy atoms | 6 |
Fraction Csp3 | 0.0 |
Num. rotatable bonds | 0 |
Num. H-bond acceptors | 3.0 |
Num. H-bond donors | 1.0 |
Molar Refractivity | 42.64 |
TPSA ? Topological Polar Surface Area: Calculated from |
57.61 ?2 |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
1.07 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
0.82 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
0.29 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
1.21 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
0.46 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
0.77 |
Log S (ESOL):? ESOL: Topological method implemented from |
-1.74 |
Solubility | 2.98 mg/ml ; 0.0183 mol/l |
Class? Solubility class: Log S scale |
Very soluble |
Log S (Ali)? Ali: Topological method implemented from |
-1.61 |
Solubility | 3.99 mg/ml ; 0.0244 mol/l |
Class? Solubility class: Log S scale |
Very soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-1.48 |
Solubility | 5.44 mg/ml ; 0.0333 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
No |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-6.71 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
2.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
1.4 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; for 1h; | [91] A solution of diisopropylazodicarboxylate (DIAD, 0.52 mL, 2.8 mmol) prepared in 2 mL anhydrous THF) was slowly added to a stirred mixture of benzyl 3-hydroxy-2,2- dimethylpropanoate (590 mg, 2.8 mmol), triphenylphosphine (820 mg, 3.1 mmol) and N- hydroxyphthalimide (510 mg, 3.1 mmol) prepared in 20 mL anhydrous THF at 0 C. After stirring the mixture at room temperature under a nitrogen atmosphere for 24 h, THF was removed under reduced pressure and the residue re-dissolved in 40 mL of ethyl acetate. The ethyl acetate mixture was washed with water (10 mL) three times, brine and dry-loaded onto a 40-g silica column. The final product was obtained in 73% yield (730 mg) as a white solid after FCC purification (hexane/ethyl acetate). [92] NMR (CDCh, 400 MHz): 5 7.84 (m, 2H), 7.76 (s, 2H), 7.39 (m, 5H), 5.19 (s, 2H), 4.32 (s, 2H), 1.42 (s, 6H); 13C NMR (CDC13, 100 MHz): 5 175.0, 163.1, 136.0, 134.4, 129.0, 128.5, 128.1, 123.5, 83.6, 66.7, 43.2, 22.2, MS (ESI+): m/z (intensity), 354.4 ([M+H]+, 100%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With acetic acid; | Example D8 A mixture of 1.64 grams (10 millimoles) of <strong>[702-79-4]1,3-dimethyladamantane</strong>, 0.13 gram (0.8 millimole) of N-hydroxyphthalimide, 0.015 gram (0.06 millimole) of Co(AA)2 and 10 milliliters of acetic acid was stirred under oxygen atmosphere at a temperature of 70 C. for six hours. As a result, with a transformation rate for <strong>[702-79-4]1,3-dimethyladamantane</strong> of 99%, 1-hydroxy-3,5-dimethyladamantane (yield 39%), and 1,3-dihydroxy-5,7-dimethyladamantane (yield 58%) were obtained. The selectivity for the alcohols was 97%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With Nitrogen dioxide; | EXAMPLE 9 In a flask, 1 mmol of <strong>[702-79-4]1,3-dimethyladamantane</strong>, 15 mmol of nitrogen dioxide, 0.1 mmol of N-hydroxyphthalimide, and 3 ml of trifluoromethylbenzene were placed, and the resulting mixture was reacted at 60C in an oxygen atmosphere (1 atm) for 5 hours with stirring. A gas chromatographic analysis of reaction products revealed that 1,3-dimethyl-5-nitroadamantane was formed in a yield of 60% on the basis of <strong>[702-79-4]1,3-dimethyladamantane</strong>. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Step 7d. Preparation of 2- (6-Pyrazol-1-yl-pyridin-3-ylmethoxy)-isoindole-1, 3-dione (Compound of formula (XI-d)); To a solution of N-hydroxyphthalimide 6 (19.2g, 115. 2mmol) in anhydrous DMF (80ml) is added NaH (3.12g, 0.13 mol) and the resulting reaction mixture was stirred for 0.5 hr. The compound of Step 8c (11.15g, 57. 6mmol) was added and the resulting mixture was stirred and heated to a temperature of 40-50C for a period of 3 h. The reaction mixture was then allowed to cool to a temperature of approximately 25C and subsequently quenched with cold water prior to filtering the quenched solution. The precipitate was washed with cool water, dried, and redissolved in a mixture of ethyl acetate and CH2Cl2. The solution was subsequently washed with brine, concentrated in vacuo to yield a yellow solid in quantitative yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0℃; for 6h;Inert atmosphere; | General procedure: To a solution of 3-quinuclidinol 2 (1.00 g, 7.86 mmol) in THF (39 mL) cooled to 0 °C were added diethyl azodicarboxylate (2.47 mL, 15.7 mmol), N-hydroxyphthalimide (2.05 g, 12.6 mmol), and triphenylphosphine (4.12 g, 15.7 mmol). After the reaction mixture was stirred for 6 h (monitored by TLC), it was treated with H2O (40 mL) and extracted with chloroform (3 × 30 mL). The combined organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude oil was purified by column chromatography on silica gel (ethyl acetate/hexane = 15:1) to yield 2-(quinuclidin-3-yloxyisoindoline-1,3-dione 3 (1.80 g, 85percent) as an oil |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium carbonate; In N,N-dimethyl-formamide; for 96h; | To a stirred solution of <strong>[78385-26-9]3-(bromomethyl)-3-methyloxetane</strong> (1) (10.0 g, 61.0 mmol) andN-hydroxyphthalimide (14.9 g, 91.4 mmol) in DMF (250 mL) was added K2CO3 (25.3 g, 183 mmol). The reaction was stirred vigorously at room temperature under N2and the progress of the reaction was monitored by 1H NMR and TLC (1:1 EtOAc/heptane).Upon completion of the reaction (complete consumption of 1) after 96 h, DMF wasremoved under reduced pressure at 30-35C to afford an oily solid residue to whichCH2Cl2 (250 mL) and H2O (125 mL) were added. The resultant biphasic mixture wasstirred until two homogeneous layers were obtained. The layers were separated and theaqueous layer was extracted with CH2Cl2 (3 £ 125 mL). The combined organic solutionswere washed successively with H2O (125 mL) and saturated aq. NaHCO3 (125 mL) untilthe aqueous layer changed from red-orange to colorless. The organic layer was thenwashed with saturated aq. NaCl (125 mL) and dried (Na2SO4). Removal of the solventusing rotary evaporation afforded an off-white solid, which was dissolved in Et2O(375 mL). The resultant solution was washed with H2O (6 £ 150 mL), saturated aq.NaCl (100 mL) and dried (Na2SO4). Removal of the solvent using rotary evaporationafforded 2 as a white solid (11.4 g, 75%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | General procedure: To a solution of alcohol (1mmol) in freshly distilled THF (5ml) was added triphenylphosphine (1.1mmol) and N-hydroxylphthalimide (1.1mmol). After the solution was cooled to 0°C diisopropylazodicarboxylate (1.1mmol) was added dropwise. The solution was allowed to warm to room temperature over 3h. Reaction progress was monitored by TLC (1:1 heptanes:ethyl acetate). Hydrazine monohydrate (1.1mmol) was then added and the solution was allowed to stir for 30min. The resulting reaction mixture was filtered to remove the white precipitate. The filtrate was concentrated and subjected to flash chromatography (1:1 heptanes/ethyl acetate). The resulting product was dissolved in ether and treated with HCl (2.0M solution in ether) to afford the HCl salt of the O-alkylhydroxylamine. Contaminating diisopropyl hydrazinodicarboxylate could be washed away from the HCl salt with dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | General procedure: To a solution of alcohol (1mmol) in freshly distilled THF (5ml) was added triphenylphosphine (1.1mmol) and N-hydroxylphthalimide (1.1mmol). After the solution was cooled to 0C diisopropylazodicarboxylate (1.1mmol) was added dropwise. The solution was allowed to warm to room temperature over 3h. Reaction progress was monitored by TLC (1:1 heptanes:ethyl acetate). Hydrazine monohydrate (1.1mmol) was then added and the solution was allowed to stir for 30min. The resulting reaction mixture was filtered to remove the white precipitate. The filtrate was concentrated and subjected to flash chromatography (1:1 heptanes/ethyl acetate). The resulting product was dissolved in ether and treated with HCl (2.0M solution in ether) to afford the HCl salt of the O-alkylhydroxylamine. Contaminating diisopropyl hydrazinodicarboxylate could be washed away from the HCl salt with dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | General procedure: To a solution of alcohol (1mmol) in freshly distilled THF (5ml) was added triphenylphosphine (1.1mmol) and N-hydroxylphthalimide (1.1mmol). After the solution was cooled to 0C diisopropylazodicarboxylate (1.1mmol) was added dropwise. The solution was allowed to warm to room temperature over 3h. Reaction progress was monitored by TLC (1:1 heptanes:ethyl acetate). Hydrazine monohydrate (1.1mmol) was then added and the solution was allowed to stir for 30min. The resulting reaction mixture was filtered to remove the white precipitate. The filtrate was concentrated and subjected to flash chromatography (1:1 heptanes/ethyl acetate). The resulting product was dissolved in ether and treated with HCl (2.0M solution in ether) to afford the HCl salt of the O-alkylhydroxylamine. Contaminating diisopropyl hydrazinodicarboxylate could be washed away from the HCl salt with dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 0.5h; | [0056] 4-[[1.3-bis(oxidanylidene)isoindol-2-yl1oxymethvHbenzenesulfonamide (3') [0057] 4-sulfonamido-benzylbromide (Guillon et al., 2011) (460 mg, 1.84 mmol) and N- hydroxyphthalimide (360 mg, 1.2 eq) were dissolved in DMF (4 mL). K2C03 (276 mg, 2 mmol) was added and the mixture was stirred at 80 °C for 30 min then diluted with ethyl acetate, acidified with HC1, washed with water, concentrated to give copious precipitate (520 mg, 85percent). NMR (498 MHz, methanol-c 4) delta ppm 7.92 (d, 2 H, J 8.1 Hz , arom.), 7.82 (s, 4 H, arom.); 7.71 (d, 2 H, arom.), 4.82 (s, 2 H, CH2). 13C NMR (126 MHz, methanol-c 4) delta ppm 164.87, 145.69, 139.89, 135.90, 131.16, 130.22, 127.32,124.39, 79.72. ESI-MS calculated for Ci5H13N205S (M+H)+: 333.0540, found: 333.0549. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26.2% | With N-ethyl-N,N-diisopropylamine; triphenylphosphine; In tetrahydrofuran; at 0 - 20℃; for 12h; | Cooling to 0 ° C, 2-hydroxyisoindole-1,3-dione 2a (2.5 g, 15.33 mmol), 3-(pyrrolidin-1-yl)propanol 2b (1.98 g, 15.33 mmol, well known Method of "Catalysis Communications, 2007, 8 (11), 16711674 "Prepared" and triphenylphosphine (4.02 g, 15.33 mmol) were dissolved in 50 mL of tetrahydrofuran, and N,N-diisopropylethylamine (3.1 g, 15.33 mmol) was added dropwise, and the mixture was stirred at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure. The obtained residue was concentrated under reduced pressure, and then filtered, and then filtered.The resulting residue was purified by eluent system A using a CombiFlash rapid preparation apparatus.The title compound 2c (1.1 g) was obtained.Yield: 26.2percent. |