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CAS No. : | 51762-67-5 | MDL No. : | MFCD00191558 |
Formula : | C8H3N3O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UZJZIZFCQFZDHP-UHFFFAOYSA-N |
M.W : | 173.13 | Pubchem ID : | 162652 |
Synonyms : |
|
Num. heavy atoms : | 13 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 44.69 |
TPSA : | 93.4 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -6.83 cm/s |
Log Po/w (iLOGP) : | 0.88 |
Log Po/w (XLOGP3) : | 0.74 |
Log Po/w (WLOGP) : | 1.34 |
Log Po/w (MLOGP) : | -0.32 |
Log Po/w (SILICOS-IT) : | -0.37 |
Consensus Log Po/w : | 0.45 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.66 |
Solubility : | 3.83 mg/ml ; 0.0221 mol/l |
Class : | Very soluble |
Log S (Ali) : | -2.28 |
Solubility : | 0.908 mg/ml ; 0.00524 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.95 |
Solubility : | 1.96 mg/ml ; 0.0113 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.05 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With potassium carbonate In dimethyl sulfoxide for 240h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | A solution of 103.7 g (600 mmol) of 3-nitro-phthalonitrile and 800 mL of dimethyl sulfoxide was added to the three-necked flask. After the powder was dissolved, 85.7 g (620 mmol) of potassium carbonate, 41.4 g (600 mmol) of sodium nitrite,160 C heating reflux, the reaction 3 hours, cooled to room temperature and then poured into a lot of water, concentrated HC1 rhoEta = 3, precipitation of yellow solid, filtered at 110 C vacuum drying, 3 - hydroxy phthalonitrile 76.4g, Yield: 88% | |
60% | With potassium carbonate; sodium nitrite; In dimethyl sulfoxide; at 130℃; for 0.5h; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.0 g, 5.8 mmol), potassium carbonate (0.9 g, 6.35 mmol) and sodium nitrite (0.4 g,5.8 mmol) was dissolved in 15 mL of dimethylsulfoxide in a 25 ml round bottom flask, and the oil bath was heated to 130 C and stirred and refluxed. TLC thin layer chromatography analysis to detect the progress of the reaction, 30 minutes after the completion of the reaction to cool to room temperature, slowly adding distilled water (45mL) dilution reaction solution, dilute hydrochloric acid (2M) adjusted to pH 3, precipitation, and then decompression pumping, filter cake washed three times with distilled water, acetic acid in the recrystallization to get brown needle-like crystals. The crystals were filtered and dried in a vacuum drier for one night to give the product 3-hydroxyphthalonitrile. Yield: 0.51g. Yield 60%. |
54% | In a 50 ml round bottom flask, <strong>[51762-67-5]3-nitrophthalonitrile</strong> (2.0 g, 11.6 mmol), K2CO3 (1.8 g, 12.7 mmol) and NaN02 (0.8 g, 11.6 mmol) were dissolved in dimethylsulfoxide ( 30mL), 130 C oil bath stirred reflux 30min, the reaction is complete. After cooling to room temperature, the reaction solution was diluted with 90 ml of distilled water, acidified with 2M hydrochloric acid to give RhoEta = 3, a precipitate was formed, and the precipitate was filtered off with suction. The filter cake was washed with distilled water and methanol, vacuum-dried, and further purified by glacial acetic acid recrystallization to obtain brown crystals. This gives the intermediate 3-hydroxyphthalonitrile. Yield: 0.9g. Yield 54%. |
48% | With potassium carbonate; sodium nitrite; In dimethyl sulfoxide; for 0.5h;Reflux; | 3-Hydroxypthalonitrile was synthesized according to the literature method [22]. To a 50 mL round-bottom flask were added 3-nitropthalonitrile (2.0 g, 11.6 mmol), K2CO3 (1.8 g, 12.7 mmol) and NaNO2 (0.8g, 11.6 mmol) in DMSO (30 mL), and the reaction mixture was stirred under reflux for 30 min. After cooling to room temperature, the reaction mixture was diluted with water (90 mL) and subsequently acidified with 2M HCl to pH=3 to produce a precipitate. Then, the solid was collected by filtration and washed successively with water and methanol. The pure product was obtained by recrystallization in acetic acid as a brown crystal (0.8 g, 48%). Mp: 263-265C. |
With potassium carbonate; sodium nitrite; In dimethyl sulfoxide; at 20 - 160℃; | The K2CO3 (18.24 g) and NaNCh (8.27 g) were added to a stirring solution of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1, 20.8 g, 120 mmol) in DMSO (90 mL) at ambient temperature. The resulting suspension was gently refluxed (oil bath) for 1.5 h. After the resulting hot black reaction mixture was poured into cold water (750 mL), pH was adjusted to 3 with concentrated HC1 (~25 mL) to give an orange suspension, which was kept in freezer for 30 min. The precipitate was collected by vacuum filtration, raised with H20/EtOH and kept under vacuum for overnight to give crude 3-hydroxylphthalonitrile. The product was used for next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | 3-(2,4-Dimethyl-3-pentyloxy)phthalonitrile (1) was preparedas described previously with some modifications [41].Sodium hydride (1.92 g, 48 mmol, 60% dispersion in mineraloil) was added portion-wise to a cooled DMF (30 mL, 0 C)under argon, and then 2,4-dimethyl-3-pentanol (4.53 g, 39mmol) was added drop-wise, followed by stirring for 1 h. Asolution of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (5.19 g, 30 mmol) in DMF(10 mL) was added slowly to the above solution over 1 h. The resulting solution was warmed to room temperature, andstirred for 1 h. After the reaction, the reaction mixture waspoured into water (500 mL) and stirred for 1 h. The solidformed was recovered by filtration and washed with water(50 mL×3). This crude product was purified by columnchromatography on silica gel using CHCl3 as eluent to givea white solid (4.83 g, 66% yield). 1H NMR (CDCl3, 500MHz): 0.95 (d, 6H), 1.01 (d, 6H), 2.13 (m, 2H), 4.05 (t, 1H),7.26 (d, 1H), 7.28(d, 1H), 7.57 (t, 1H). | |
A quantity of 30 ml of DMF was added to the 150 ml reaction flask and the ice bath was kept at a temperature of 3C. Under argon protection, NaH was weighed into DMF and stirred for 10 min.2,4-Dimethyl-3-pentanol was weighed into the above solution and stirred for 1.5 h. After the 3-nitrophthalic dinitrile was dissolved in 10 ml of DMF, the solution was added dropwise to the above reaction solution for 1 h, and the ice-water bath was removed. Let stand for a while, pour 500ml of water, a large number of brown solids precipitated. Vacuum filtration under reduced pressure and washing three times. The resulting solid was dissolved in chloroform and dried over sodium sulfate. The product was dried and purified by column chromatography using chloroform as eluent. The purified colored product was added with petroleum ether, filtered under reduced pressure, and washed with petroleum ether to remove noise, dried, and weighed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 30h; | was prepared according to the procedure for the synthesis of 4-methoxybenzene-1,2-dicarbonitrile.5 To the solution of <strong>[51762-67-5]3-nitrophthalonitrile</strong> 6 (3.46 g,20 mmol) in DMF (25 mL) K2CO3 (5.52 g, 40 mmol) and MeOH (5 mL) were added. After stirring the suspension for 30 h at ambient temperature,500 mL of distilled water were added with continued stirring. The precipitate was collected by filtration, washed with distilled water, dried andcrystallized from MeOH (20 mL). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium hydride; In 1-methyl-pyrrolidin-2-one; mineral oil; at 0 - 4℃; | 51 NMP werden in dem trockenen Reaktionsgef vorgelegt und mit N2berschleiert. Unter stndigem Stickstoffstrom wird auf 4C abkhlt und mit 660g NaH (60 %ig in Minerall) versetzt. Dann werden 2025g 2-Ethylhexanol rasch zugegeben und auf 0C gekhlt Bei dieser Temperatur werden 2622g 3-Nitrophthalodinitril in 101 NMP zudosiert. Der Ansatz wird auf Eis ausgetragen und abgesaugt. Das Produkt wird zuerst mit einem Gemisch aus MeOH und Wasser (2:1) in Portionen und dann mit Wasser gewaschen und trocken gesaugt. Nach dem Trocknen im Vakuum bei 30C erhlt man 3517g ( =? 91% der Theorie) Produkt. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With lithium hydroxide monohydrate; In dimethyl sulfoxide; at 20℃; for 24h; | 3-Nitrophthalonitrile 1 (6.92 g, 40 mmol) and n-octanol (7.5 mL,48 mmol) were added to 60 mL anhydrous DMSO at RT. The reaction mixturewas stirred and LiOH.H2O (4.2 g,100 mmol) was interfused over a 2-h period and the mixture was then stirred for 1 day. Reaction was monitored by TLC analysis. Then the reaction mixture was poured into 10% NaCl solution (400 mL) and stirred till precipitate appeared. The reaction product was collected by vacuum filtration. The crude product was purified by flash column chromatography with chloroform as the mobile phase to afford white power 3-octyloxy-phthalonitrile 3: 8.4 g, yield: 82%; 1H NMR (500 MHz, CDCl3): delta 7.70 (dd, 1H, ArH), 7.24 (d, 1H, ArH), 7.15 (d, 1H,ArH), 4.47 (m, 2H, OCH2),1.73 (m, 2H, CH2),1.27-1.34 (m, 8H, (CH2)4),0.88 (m, 3H, CH3); MS (CHCl3): m/z calcd for [M + Na+]: 279.3,found: 279.6 (an isotopic cluster peak) [M + Na+]; IR (KBr, numax,cm-1): 2231 vs (C^N), 1253 vs (C-O-C); Anal. Calcd for C16H12N2O(256.3): C 74.97, H 7.86, N 10.93, Found: C 74.93, H 7.63, N 10.85. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With lithium hydroxide; In dimethyl sulfoxide; at 50℃; for 24h;Inert atmosphere; | 3-Nitrophthalonitrile (1.73 g, 0.01 mol) and 4-tert-butylphenol (1.50 g, 0.01 mol) were dissolved in DMSO (30 mL), LiOH (0.42 g,0.01 mol) was then added. The resulted mixture was then stirred at 50 C for 24 h under N2 atmosphere. The product solution was cooled and then poured into NaCl solution (10% aqueous, 100 mL), the precipitated solid was filtered, washed with water and dried under vacuum. White needles were obtained after recrystallization in toluene. Yield: 51%. m.p. 116-118 C. IR (KBr), nu(cm-1): 3083, 3014, 2232 (C?N), 1695, 1632, 1563, 1506, 1485, 1465, 1429, 1386, 1351, 1275 (C-O-C), 1258, 1222, 1165, 1142, 1015, 938, 917. 1H NMR (400 MHZ, CDCl3, ppm): delta 1.353 (s, 9H, t-butyl), 6.992 (d, 2H, J=7 Hz, Ar-H), 7.245 (d, 1H, J=6 Hz, Ar-H), 7.510 (d, 2H, J=7 Hz, Ar-H), 7.799 (m, 2H, Ar-H), 7.835 (m, 1H, Ar-H). MS, m/z: 298.95 [M+Na]+. |
With potassium carbonate; In dimethyl sulfoxide; | Ligand two In a 150 mL reaction vial, <strong>[51762-67-5]3-nitrophthalonitrile</strong>, p-tert-butylphenol, K2CO3, and 20 ml of DMSO were mixed. The color of the solution changes from orange to orange. After the reaction was over, the product was added with DMSO, magnetically stirred for 1 hour, suction filtered, washed with water, chloroform, and dried over sodium sulfate. The product was dried and purified by column chromatography using chloroform as eluent. Dry and weigh. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In water; dimethyl sulfoxide; | Example 6 Preparation of 1,4-bis-(2,3-dicyanophenoxy)-2,5-di-tert-butyl benzene The same apparatus as was used in Example 5 was used in this example. 8.8 g (0.051 moles) of 3-nitrophthalonitrile, prepared according to Example 4, was dissolved in 75 ml of anhydrous dimethyl sulphoxide in the three-necked flask. 5.55 g (0.025 moles) of 2,5-di-tert-butyl hydroquinone and 10 g of potassium carbonate were added to the reaction mixture. The mixture was stirred at room temperature with a stream of dry, oxygen-free nitrogen passing through the flask for 26 hours. The product was isolated by pouring the reaction mixture into 500 ml of water. The resultant solid precipitate was filtered and washed until the effluent was neutral. The product was further washed with boiling methanol until it became a greyish-white powder 10.6 g (90.2% yield). After recrystallisation from boiling acetonitrile white crystals of 1,4-bis-(2,3-dicyanophenoxy)-2,5-di-tert-butyl benzene were obtained having the formula: The melting point of this product was above 300C. Theoretical analysis of C30H26N4O2: C,75.94%; H,5.48%; N,11.81%; found: C,75.61%; H,5.48%; N,11.98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 30h;Inert atmosphere; | p-Hydroxybenzoic acid (15mmol) and 3-nitro-phthalonitrile (15mmol) as reactants, the solvent is anhydrous DMSO (30ml), under nitrogen, and the presence, the reaction mixture was stirred at room temperature potassium carbonate (45mmol) 30 hours, by thin layer chromatography to monitor the end of reaction.The reaction mixture was diluted with sand core funnel filtration, the filtrate was collected, and the filtrate was added to 500ml of ice water mixture, adjusted with 1M hydrochloric acid solution until the solution was acidic precipitation heavy precipitate, was allowed to stand, an organic microporous membrane, repeated washing more times until the solution was neutral, the solid was collected and lyophilized to give a white solid, further use DMF- water purified by recrystallization to give a white desired product, a yield of about 78%. |
65% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and p-hydroxybenzoic acid (20-70 mmol, preferably 60 mmol) as a reactant and dimethyl sulfoxide (40-200 mL, preferably 140 mL) as a solvent in potassium carbonate ( 30-90 mmol, preferably 80 mmol) is present and the reaction is stirred at room temperature to 60 C. (preferably 60 C.) for 24 to 72 hours under nitrogen protection and monitored by thin layer chromatography. After the reaction was completed, the reaction solution was poured into ice water to precipitate a light yellow precipitate, which was filtered to collect the residue. The filtrate was extracted with CHCl 3 , and the extract was back-extracted with water. The CHCl 3 extract was evaporated and vacuum dried at room temperature to give a yellow solid. The filter residue was combined with the product obtained by extraction in a yield of 65%. |
65% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and p-hydroxybenzoic acid (20-70 mmol, preferably 60 mmol) as reactants and dimethyl sulfoxide (40-200 mL, preferably 140 mL) as solvent in potassium carbonate ( 30-90 mmol, preferably 80 mmol) are present and incubated under nitrogen for 24 to 72 hours at room temperature to 60C (preferably 60C) and monitored by thin layer chromatography. After the reaction was completed, the reaction solution was poured into ice water to precipitate a light yellow precipitate, which was filtered to collect the residue. The filtrate was extracted with CHCl 3 , and the extract was back-extracted with water. The CHCl 3 extract was evaporated and vacuum dried at room temperature to give a yellow solid. The filter residue was combined with the product obtained by extraction in a yield of 65%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85 - 89% | With sodium hydride; In 1-methyl-pyrrolidin-2-one; mineral oil; at 0 - 40℃; for 1.33333h; | 2623.5 g 3-Nitrophthalodinitril und 15 1 NMP werden in dem trockenen Reaktionsgef vorgelegt und mit N2berschleiert. Unter stndigem Stickstoffstrom wird auf 4C abkhlt und mit 660g NaH (60 %ig in Minerall) versetzt. Dann werden 1 kg 2,4-Dimethyl-3-pentanol rasch zugegeben. Innerhalb von 1h steigt die Temperatur bis auf 23C an. Danach werden weitere 2024g 2,4-Dimethyl -3-pentanol zugegeben. Die Temperatur steigt dabei auf 40C an und wird 20 min gehalten. Der Ansatz wird auf 10C abgekhlt, auf Eis ausgetragen und abgesaugt. Das Produkt wird zuerst mit Gemisch aus MeOH und Wasser (2:1) in Portionen und dann mit Wasser gewaschen und trocken gesaugt. Nach dem Trocknen im Vakuum bei 30C erhlt man 3080g (=? 85 der Theorie) ProduktBeispiel 3 7.41 DMF werden in dem trockenen Reaktionsgef vorgelegt und mit N2berschleiert. Dann werden 2047g 2,4-Dimethyl-3-pentanol rasch zugegeben und auf 0C gekhlt. Unter stndigem Stickstoffstrom wird 669g NaH (60 %ig in Minerall) zugegeben. Bei dieser Temperatur werden 2623g 3-Nitrophthalodinitril in 2.31 DMF zudosiert. Der Ansatz wird auf Eis ausgetragen und abgesaugt. Das Produkt wird zuerst mit einem Gemisch aus MeOH und Wasser (2:1) in Portionen gewaschen und dann mit Petrolether gewaschen und trocken gesaugt. Nach dem Trocknen im Vakuum bei 30C erhlt man 3275g (=? 89% der Thoerie) Produkt der Formel: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; cyclohexane; N,N-dimethyl-formamide; | -benzenedicarbonitrile carbonitrile STR9 3-Nitro-1,2-benzenedicarbonitrile (1.731g, 0.01M), 1-octadecanethiol (2.866 g, 0.01M), anhydrbus K2 CO3 (7.0g) and DMF (20 ml) were stirred together at 75 to 80 C. for 6h, then allowed to stand cooling overnight. A solid mass formed on standing, which was dissolved in CH2 Cl2 /H2 O. An intermediate emulsion was removed by taking off as much of the organic phase as possible, then repeatedly extracting the residue with small portions of CH2 Cl2. The combined CH2 Cl2 extracts were washed with water (3 times), dried (MgSO4), and evaporated in vacuo to give a solid (3.71g). Recrystallisation of the crude product from cyclohexane (150 ml) gave 3-(n-octadecylthio)-1,2-benzenedicarbonitrile as a faintly-coloured microcrystalline powder which was collected, washed with a little cold petrol, and dried in vacuo (3.220g, 78%). 1 H NMR (CDCl3) Chemical shift 7.59 (m,3), 3.07 (t,2, J=7Hz), 1.26 (m, 35). IR(Nujol)=2234 cm-1 (C N). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium carbonate; In dimethyl sulfoxide; at 40℃; for 2h; | EXAMPLE 1; a) Synthesis of 3-(4-N,N-dimethylamino-phenoxy)phthalonitrile; To a solution of 3-nitrophthalonitrile (140 g, 0.81 mol) in dry DMSO (2 I), 3-(dimethylamino)phenol (165 g, 1.2 mol) and dry K2CO3 (370 g, 2.68 mol) were added and the suspension stirred and warmed at 400C for 2h. After cooling to room temperature, the reaction mixture was poured in water (5 I) and, after 1 h of EPO <DP n="14"/>stirring, the obtained suspension was filtered. The solid was dissolved in CH2CI2 (650 ml) and washed with NaOH 0.5M (650 ml). The organic phase was treated with charcoal and Na2SO4, filtered and the solvent eliminated at reduced pressure. The residue was finally treated with diisopropyl ether (550 ml) at 35 0C for half an hour, then cooled at 4°C for 48 h and filtered to give 204 g of 3-(4-N1N- dimethylamino-phenoxy)phthalonitrile as a yellow solid (yield:96percent). 1H-NMR (200 MHz, DMSO-d6) delta , ppm 7.83-7.80 (m, 2H), 7.33-7.21 (m, 2H), 6.67 (dd, J = 8.3 Hz, J = 2.3 Hz, 1H), 6.57-6.54 (m, 1 H)1 6.43 (dd, J = 7.9Hz, J = 2.0 Hz, 1 H), 2.93 (s, 6H).13C- NMR (75 MHz, DMSO-d6) delta, ppm 161.12, 155.53, 152.95, 136.57, 131.31 , 128.39, 122.22, 116.38, 116.35, 114.19, 110.39, 107.43, 105.10, 104.35, 40.59. EI-MS m/z 263 [M+]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1% | With hydrogenchloride; In N,N-dimethyl-formamide; | Comparative Example 5 In 60 ml of N,N-dimethylformamide were dissolved 20 g of <strong>[3219-63-4]trimethylsilylmethanol</strong>. This was maintained at 5C in a water bath and 4.6 g of sodium hydride were added thereto in the atmosphere of argon. The resulting mixture was stirred at 5C for 1 hour. Thereafter, 33.3 g of 3-nitrophthalonitrile dissolved in 160 ml of N,N-dimethylformamide were added dropwise to the mixture. After completion of the addition, the ice bath was removed and the mixture was stirred at room temperature for 24 hours. The reaction product was then added with 200 ml of dilute hydrochloric acid and extracted with 1 liter of toluene. The organic layer was washed well with water, followed by the removal of water with magnesium sulfate and the purification with a toluene/silica gel column. However, the desired compound shown by the above formula (XV) was hardly obtained. The yield was about 1 % and 3-methoxyphthalonitrile as a by-product was yielded in an amount of several times that of the compound (XV). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; In dimethyl sulfoxide; at 60℃; for 3h; | To a mixture of 3-nitrophthalonitrile (25 g, 0. 144 mol). DMSO (200 ml), and sodium 3- mercaptopropanesulfonate (32 g. 0.18 mol), was added sodium carbonate ( 16.5 g, 0. 156 mol), and the resultant mixture was heated to 6O0C followed by stirring for 3 hours. The reaction mixture was poured into a 10% brine (300 g). and the thus-precipitated solids were collected through filtration and washed with a mixed liquid of isopropanol/water (3/1 ). To the thus-obtained solids, were added water (200 ml), acetic acid (3 ml), and Na2WO.* (2 g). and then a 3 1 % hydrogen peroxide aqueous solution (50 ml) was added thereto. The resultant mixture was heated to 6O0C followed by stirring. Thus, the reaction mixture was stirred for 4 hours, and then poured into isopropanol (500 ml). The thus- precipitated solids were collected through filtration, and washed with a mixed liquid of isopropanol/water (3/1 ). The thus-obtained solids were dried, to thereby obtain Phthalonitrile compound 105 (24 g. yield 49% from 3-nitrophthalonitrile). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 72h;Product distribution / selectivity; | Example 3[0107] To prepare the bis-phthalonitrile used in scheme 2, the nitrogen of serinol was Boc-protected, and the serinol was then reacted with 3-nitrophthalonitrile on a multi-gram scale, to give the desired tethered bis-phthalonitrile, in 70% yieldExample 5[0109] Boc-serinol Bisphthalonitrile. Finely ground K2CO3 (4.32 g, 31.2 mmol,4 equiv.) was added to /V-Boc-serinol (1.45 g, 7.8 mmol, 1 equiv.) in 20 mL DMSO under argon; then 3-nitrophthalonitrile (3.38 g, 19.5 mmol, 2.5 equiv.) was added. The reaction mixture first turned pink, and then orange upon addition of the 3- nitrophthalonitrile. The reaction mixture was stirred at room temperature and monitored periodically by TLC (9:1 benzene:CH3CN). After 72 h, the reaction mixture was partitioned between EtOAc and water. The two layers were separated, and the aqueous layer was extracted 3 times with 50 mL EtOAc. The organic layer from the original partitioning was added to the organic extract. This mixture was then washed twice with 50 mL of saturated NaHCO3, and twice with 50 mL of water, and was then dried over Na2SO4. The solvent was removed at reduced pressure, and the resulting crude orange solid was recrystallized from methanol/water to give 2.43g (70% yield) of a slightly EPO <DP n="32"/>pink/tan solid. [ Rf: 0.25 (9:1 benzene:CH3CN); melting point 167-169C; 1H NMR (200 MHz, CD3CN) delta 7.85-7.4 (m, 6H, ArH), 5.76 (br s, 1 H, NH), 4.39 (s, 5H, (-CH2J2CH-), 1.42 (s, 9H, C(CH3)3).] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | 25 g (0.144 mole) of 3-nitrophthalonitrile and 22.4 g (0.145 mole) of 4-mercaptobezoic acid were dissolved in 125 ml of N-methylpyrrolidone, followed by stirring at room temperature (20 to 28C). To this solution was added portionwise 30.7 g of sodium carobonate. After completion of the addition, the reaction liquid was heated at 40C to 45C, followed by stirring for 2 hours to complete the reaction. This reaction liquid was poured into 1000 ml of water under stirring, and then a 35% by mass aqueous hydrochloric acid was added thereto adjust the pH to 3. The deposited crystal was filtered, washed with water, and dried. This crystal was dispersed in 300 ml of methanol, followed by stirring. This crystal was filtered and dried to obtain 35.5 g (yield: 88.0% by mass) of an intermediate J. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | (Synthesis of Intermediate A)Sodium carbonate (16.5 g, 0.156 mol) was added to a mixture of 3-nitrophthalonitrile (25 g, 0.144 mol), DMSO (200 ml), and <strong>[17636-10-1]sodium 3-mercaptopropanesulfonate</strong> salt (32 g, 0.18 mol), and the mixture was stirred as heated to 60 C. for 3 hours. The reaction mixture was poured into 10% sodium chloride water (300 g), and the precipitated solid was collected by filtration and washed with a mixed liquid of isopropanol/water (3/1). Water (200 ml), acetic acid (3 ml) and Na2WO4 (2 g) were added to the solid: 31% hydrogen peroxide solution (50 ml) was added thereto; and the mixture was stirred while heated at 60 C. After stirring fro 4 hours, the reaction mixture was poured into isopropanol (500 ml), and the precipitated solid was collected by filtration and washed with a mixed liquid of isopropanol/water (3/1). The solid obtained was dried, to give an intermediate A24 g (yield from 3-nitrophthalonitrile: 49%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.18% | With potassium carbonate; In dimethyl sulfoxide; at 50℃; for 24h;Inert atmosphere; | 3-Nitrophthalonitrile (1) (0.86 g, 5 mmol) and 7-hydroxy-4-(4-methoxyphenyl)-8-methylcoumarin (2) (1.41 g, 5 mmol) were dissolved in anhydrous DMSO (20 mL). After stirring for 10 min; finely ground anhydrous K2CO3 (2.07 g, 15 mmol) was added by stirring. The reaction mixture was stirred at 50 C for 24 h under N2 2.1 Synthesis of 3-[4-(4-methoxyphenyl)-8-methylcoumarin-7-oxy]phthalonitrile (3) atmosphere. The mixture was poured into ice water and the obtained precipitate was filtered off, washed by using water and dried in vacuum at 50 C. Then it was also purified by column chromatography with silica gel eluting with CHCl3 a gradient of CHCl3-tetrahydrofuran (THF) up to 5% THF. Compound 3 is soluble in DCM, CHCl3, THF, dimethylformamide (DMF), DMSO and acetic acid. Mp: 214-215 C Yield: 1.86 g (91.18%). Anal calculated for C25H16N2O4 C, 73.52%; H, 3.95%; N, 6.86%; found C, 73.41%; H, 4.08%; N, 6.72%. IR (KBr pellet) numax/cm-1: 597, 798, 895, 950, 1027, 1087, 1174, 1249, 1283, 1366, 1422, 1461, 1487, 1512, 1572, 1603, 1732, 2228, 2854, 2922, 3066. 1H NMR (500 MHz, CDCl3): delta, ppm 2.42 (s, 3H), 3.87 (s, 3H), 6.38 (s, 1H), 6.89 (d, J = 8.98 Hz, 1H), 7.02 (dd, J = 8.99 Hz, J = 1.95 Hz, 1H), 7.06 (dd, J = 8.59 Hz, J = 1.95 Hz, 2H), 7.41 (dd, J = 8.98 Hz, J = 1.95 Hz, 2H), 7.49 (d, J = 8.98 Hz, 1H), 7.54 (dd, J = 8.59 Hz, J = 1.95 Hz, 1H), 9.76 (t, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1,3-dimethyl-1H-imidazol-3-ium hydrogen carbonate; water In ethanol at 80℃; for 6h; Green chemistry; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | General procedure: A mixture of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.72 g, 0.01 mol), methyl hydroxybenzoate (0.01 mol), and potassium carbonate (13.90 g, 0.1 mol) in DMF (80 mL) was heated at 80 C overnight. Then the reaction mixture was poured into ice water. After filtration, the solid product was purified by silica-gel chromatography using CH2Cl2 as eluent to give a white solid product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.2% | A solution of methyl 3-hydroxybenzoate (1.52 g, 10 mmol) in DMF (20 mL) was added anhydrous K2CO3 (2.8 g, 20.29 mmol) and the mixture was stirred for 30 min. Then <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.73 g, 10 mmol) was added, the mixture was continually stirred at 50 C for 24 h under nitrogen atmosphere. After the reaction mixture was cool down to indoor temperature, K2CO3 was filtered off, the filtrate was poured into water of roughly 2 C (450 mL). After that, a pale yellow solid was gained through a filtration work, which was washed by water and dried in air. Yield: 2.20 g (79.20%). | |
76% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | General procedure: A mixture of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.72 g, 0.01 mol), methyl hydroxybenzoate (0.01 mol), and potassium carbonate (13.90 g, 0.1 mol) in DMF (80 mL) was heated at 80 C overnight. Then the reaction mixture was poured into ice water. After filtration, the solid product was purified by silica-gel chromatography using CH2Cl2 as eluent to give a white solid product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | The synthetic procedure was adopted from Mayukh etal. with some modifications [37]. A mixture of 4-mercaptophenol (1.26g, 0.01mol) and K2CO3 (4.15g, 0.03mol) in dry dimethylformamide (DMF) (25mL) was stirred vigorously in nitrogen atmosphere for 30min and then <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.75g, 0.01mol) was added into the reaction mixture followed by a stirring for 16h at 90C. The reaction mixture was allowed to cool room temperature and poured into 1M HCl and the precipitate formed was filtered off and washed with water until the filtrate was neutral and dried in vacuum. The precipitate was extracted with ethyl acetate. The combined organic phases were treated with distilled water, dried with anhydrous sodium sulfate and solvent removed under reduced pressure to obtain solid orange colored powder. The product was further purified by chromatography over a silica gel column using Ethyl acetate and hexane (3:1) mixture as eluent. Yield: 1.73g, (68%); m.p. 162-164C. FT-IR numax/cm-1; 3403 (Ar-OH), 3077-2923 (Ar-H), 2241 (C?N). 1H NMR (DMSO-d6) delta/ppm: 10.18 (s, 1H, Ar-OH), 7.84 (d, 1H, Ar-H), 7.68 (t, 1H Ar-H), 7.42 (d, 2H, Ar-H), 7.09 (d, 1H, Ar-H), 6.91ppm (d, 2H, Ar-H); 13C NMR (DMSO-d6) delta/ppm: 160.21 (aromatic C-O), 147.51, 137.76, 134.51, 130.96, 117.97, 116.40 (C?N), 114.57, 110.27. Anal. Calcd. for C14H8N2OS (252.291g/mol); C 66.65, H 3.20, N 11.10; Found: C 66.56, H 3.09, N 11.08. MS (GC/MS): m/z: 252 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 24h;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.99 g, 5.90 mmol) was dissolved in 15.0 ml DMF under argon atmosphere and 3,4-dimethoxythiophenol (1.00 g, 5.90 mmol) was added at room temperature. After stirring for 30 min at room temperature, finely ground anhydrous potassium carbonate (3.94 g, 28.4 mmol) was added portion wise for over 1 h and the reaction mixture was stirred at room temperature for 24 h. Then the mixture was poured into 100.0 ml ice water, and the precipitate was filtered off, washed with water and methanol, and then dried. The crude product was recrystallized from ethanol. Finally the pure product was dried in vacuum. Yield: 3.12 g (90%). FT-IR (cm-1) (KBr): 3070, 3004 (Ar-CH), 2960, 2934, 2840 (CH), 2230 (C?N), 1583, 1567, 1505 (C=C), 1461, 1439, 1417, 1401, 1328, 1259 (C-O-C), 765 (C-S-C). 1H NMR (CDCl3): delta = 7.65-7.06 (6H, m, Ar-H), 3.92 (3H, s, C-H), 3.82 (3H, s, C-H). Calcd for C16H12N2O2S: C, 64.90; H, 4.10; N, 9.45; S, 10.80; Found: C, 64.85; H, 4.14; N, 9.52; S, 10.85. MS (GC-MS) m/z: Calc.: 296.35, Found: 296 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 48h;Inert atmosphere; | General procedure: A mixture of 2-hydroxybenzothiazole (1.00g, 6.6mmol) and 3-nitrophthalonitrile (1.14g, 6.6mmol) in DMF (10ml) was stirred under an argon atmosphere at room temperature. K2CO3 (10.07g, 72.4mmol) was added portion-wise to the reaction mixture which was then stirred at room temperature for 48h. The reaction mixture was subsequently poured into ice water, and the precipitate filtered off, washed with water and methanol and dried. The crude product was recrystallized from an ethanol:water (1:1) and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 122h;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.500 g, 2.888 mmol) was dissolved in anhydrous dimethylformamide (75 mL) under Ar and hydroxymethyl-EDOT (0.500 g, 2.903 mmol) was added. After stirring for 10 min, finely ground anhydrous K2CO3 (1.200 g, 8.682 mmol) was added in portions over 2 h with efficient stirring. The reaction mixture was stirred at room temperature for 120 h under Ar. Then the solution was poured into ice-water. The resulting white solid was collected by filtration and washed first with water and then with hexane. Yield 0.493 g (57%). Mp: 192 C. FT-IR: numax, cm-1 3116.56 (CH, aromatic), 2963.20 (CH, aliphatic), 2230.15 (C?N). 1H NMR (400 MHz, DMSO-d6, 298 K): delta, ppm 7.88-7.69 (3H, benzene -CH), 6.64 (2H, thiophene -CH), 4.63-4.13 (5H, -CH and -CH2). 13C NMR (400 MHz, CDCl3, 298 K): delta, ppm 160.38, 141.00, 140.83, 135.87, 126.21, 118.72, 115.71, 115.35, 113.48, 103.10, 100.16, 71.49, 68.00, 64.77. GC-MS: m/z 298 [M]+. C15H10N2O3S (298.04): calcd. C 60.39, H 3.38, N 9.39; found C 60.37, H 3.37, N 9.40. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 24h;Inert atmosphere; | A mixture of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.87g, 5mmol), 3-hydroxybenzoic acid (0.69g, 5mmol), and anhydrous K2CO3 (2.07g, 15mmol) in dry DMSO (20mL) was stirred at room temperature for 24h under nitrogen atmosphere. The reaction mixture was filtered by sand core funnel and the filtrate was poured into ice water (200mL). Subsequently, HCl aqueous solution (2M) was added to the filtrate until pH=1-3 to give white precipitate, which was collected by filtration, washed with water until pH=7 and dried in vacuum. The crude product was purified by recrystallization with DMF/water to afford white solid (1.11g, 84%). Rf=0.53 (EtOH). IR (KBr, cm-1): 3078.4 (Ar-H); 1585.6, 1466.7, 1450.9 (C=C, Ar); 1303.7, 1278.7, 1208.9 (Ar-O-Ar); 2232.9 (C?N); 1688.8 (C=O). MS (ESI): m/z 263.1 [M-H]-. 1H NMR (DMSO-d6, ppm): delta 13.16 (br., 1H), 7.81-7.88 (m, 3H), 7.62-7.67 (m, 2H), 7.52 (t, J=0.6Hz, 1H), 7.32 (d, J=4.2Hz, 1H). Anal. Calcd for C15H8N2O3: C, 68.18; H, 3.05; N, 10.60. Found: C, 67.99; H, 3.27; N, 10.86. |
78% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 30h;Inert atmosphere; | With 3-hydroxybenzoic acid (15mmol) and 3-nitro-phthalonitrile (15mmol) as reactants, the solvent is anhydrous DMSO (30ml), potassium carbonate (45mmol) under nitrogen and the presence, stirred at room temperature The reaction 30 hours, by thin layer chromatography to monitor the end of reaction.The reaction mixture was diluted with sand core funnel filtration, the filtrate was collected, and the filtrate was added to 500ml of ice water mixture, adjusted with 1M hydrochloric acid solution until the solution was acidic precipitation heavy precipitate, was allowed to stand, an organic microporous membrane, repeated washing more times until the solution was neutral, the solid was collected and lyophilized to give a white solid, further use DMF- water purified by recrystallization to give a white desired product, a yield of about 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | 3-Nitrophthalonitrile (4.40 g; 25.4 mmol) and thiocyanuric acid (1.50 g; 8.46 mmol) were added to round a bottom flask (100 mL). After 10 min of purging with argon, DMF (50 mL) was added to the mixture. The mixture was stirred for another 10 min and then potassium carbonate (3.50 g; 25.42 mmol) was added all at once before heating the mixture at 65 C for 48 h as explained by Senet al. [25]. The reaction mixture was cooled to room temperature and then poured into ice water before slowly filtering and washing with water. The obtained product was washed four times with ethanol. The crude yellow product was dried in open air. Yield: 59%. IR: [KBr, v, cm-1] 1002, 1147, 1199, 1278, 1429, 1445 (Benzene ring), 1570, 1666, 1729 (-CN-), 2232 (C?N), 3075 (CH). 1H NMR (DMSO-d6): d, ppm 8.14-8.12 (3H, d, Ar-H), 7.85-7.84 (3H, t, Ar-H), 7.82-7.81 (3H, d, Ar-H). 13C NMR (CHCl3-d1): d, ppm 113.21 (3C, s, Ar-C), 114.56 (3C, s, Ar-C), 118.61 (3C, s, Ar-C), 119.45 (6C, s, C?N), 133.55 (3C, s, Ar-C), 133.70 (3C, s, Ar-C), 137.84 (3C, s, S-Ar-C), 138.42 (3C, s, N-CN). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium carbonate; In N,N-dimethyl-formamide; at 50 - 60℃; for 96h; | The compounds 4-hydroxy-3-methoxybenzoic acid (0.97g, 5.78mmol) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.0g, 5.78mmol) were dissolved in dry DMF (30ml) and anhydrous K2CO3 (1.59g, 11.56mmol) was added in portions over 2h. After stirring for 4 days at 50-60C, the reaction mixture was treated with diluted HCl under ice cooling. The pure precipitate that formed was filtered, washed with water to neutralize and dried. Yield: 1.15g (68%). M.p. 238-240C. Anal. Calc. for C16H10N2O4: C, 65.31; H, 3.43; N, 9.52; O, 21.75. Found: C, 65.20; H, 9.19; N, 3.23; O, 21.58%. FT-IR (KBr), numax/(cm-1): 3084 (Ar-CH), 2921-2851 (aliphatic CH), 2231 (C?N), 1675 (C=O), 1574-1458 (C=C), 1277 (Ar-O-Ar), 1247, 1182, 983, 756, 650, 509, 456. 1H NMR (d-DMSO 500MHz, delta ppm): 7.81 (dd, 1H, Ar-H), 7.76 (t, 1H, Ar-H), 7.49 (dd, 1H, Ar-H), 7.12 (dd, 1H, Ar-H), 7.64 (dd, 1H, Ar-H), 7.69 (s, 1H, Ar-H), 3.79 (s, 3H, OCH3). UV-Vis lambdamax (nm) (log epsilon) in DMSO: 297 (4.35). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In dimethyl sulfoxide; at 150℃; for 0.166667h;Microwave irradiation; | Eugenol (0.625 g, 3.81 mmol) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.640 g, 3.69 mmol) was dissolved in dry dimethylsulphoxide (3 ml). After stirring for 15 min, newly ground anhydrous K2CO3 (0.76 g, 5.50 mmol) was added to this solution. The reaction flask was heated under microwave irradiation at 150 C for 10 min, with stirring and air-jet cooling. After reaction completed, the mixture was filtered and poured in ice. The formed solid material was filtered off and the crude product was purified by recrystallization from dry ethanol. Yield: 240 mg (85%); m.p. 101 C. Single crystals were obtained by slow evaporation from ethanol. Yield: 770 mg (% 90); m.p. 89-90 C. FTIRnumax/cm-1. 3070 (Ar-CH), 2966, 2939, 2917, 2227 (CN), 1636, 1599, 1583, 1570, 1506, 1465, 1417, 1279, 1257, 1155, 1034, 794. 1H NMR (DMSO-d6) delta, ppm: 7.746-7.729 (2H, m, ArCH), 7.204-7.184 (1H, d, ArCH), 7.069-7.065(1H, d, ArCH), 7.069-6.965 (1H, m, ArCH), 6.872-6.847 (1H, d.d, ArCH), 6.026-5.958 (1H, m, =CH), 5.145-5.059 (2H, m, =CH2), 3.71 (3H, s, OCH3), 3.412-3.395 (2H, d, -CH). 13C NMR (DMSO-d6) delta, ppm: 160.993, 151.105, 140.157, 139.696, 137.684, 136.335, 127.810, 122.656, 121.596, 120.217, 116.682, 116.104, 115.967, 114.255 (CN), 113.843 (CN), 103.452, 56,260 (OCH3), 39.706. Anal. Calcd. For C18H14O2N2: C, 74.46; H, 4.86; N, 9.64 Found: C, 74.50; H, 4.58; N, 9.50. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 168h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.2% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 45℃;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (5 mmol) and sodium 4-hydroxybenzenesulfonate (5-7.5 mmol, 5mmol) is the reactant, in the presence of dimethyl sulfoxide (10~25mL, preferably 10mL) as solvent, in the presence of potassium carbonate (7.5~15mmol, preferably 10mmol, added in three batches) and under nitrogen protection, room temperature ~45 C The reaction was stirred for 48 to 96 hours (preferably 45 C) and monitored by thin layer chromatography to terminate the reaction when the 3-nitrophthalic acid was substantially consumed.The reaction mixture was filtered through a microporous organic membrane, and the filtrate was collected. The filtrate was added to 100 ml of ice chloroform, stirred, and a large amount of milky white precipitate was precipitated, allowed to stand, and filtered, and the filter cake was washed thoroughly with ethanol and acetone to collect solids at 60 C. Drying in vacuo gave 1.55 g of product as a white powder, yield 96.2%. |
92% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and sodium p-hydroxybenzenesulfonate (20-70 mmol, preferably 60 mmol) as reactants and dimethyl sulfoxide (40-200 mL, preferably 140 mL) as solvent in carbonic acid Potassium (30 to 90 mmol, preferably 80 mmol) is present and under nitrogen protection, the reaction is stirred at room temperature to 60C (preferably 60C) for 24 to 72 hours and monitored by thin layer chromatography. After the reaction was completed, the reaction solution was poured into ice chloroform to precipitate a yellow-white precipitate, which was filtered, washed with ethanol and acetone until the filtrate was colorless, and dried in vacuum at 50 C. to obtain a pale yellow product with a yield of 92%. |
64% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and 2,4,6-tris(dimethylaminomethyl)-phenol (20-70 mmol, preferably 60 mmol) as reactants, dimethyl sulfoxide (40) -200 mL, preferably 140 mL, is the solvent, and the reaction is stirred at room temperature ~ 60C (preferably 60C) for 24 to 72 hours in the presence of potassium carbonate (30 to 90 mmol, preferably 80 mmol) and nitrogen, and monitored by thin layer chromatography. Should be filtered to remove the reaction mixture was insoluble potassium carbonate, evaporated to dryness, adding 50 ~ 100mL of chloroform, stirred and filtered to remove insolubles, evaporated to dryness, add 50 ~ 100mL of water to the solid and 15 ~ 45mL HCl (1mol/L) stirred and filtered to remove insolubles. NaOH was added to the filtrate. The solids were precipitated and filtered. The solids were washed with water and dried in vacuo at 50C to give 3-(2,4,6-tris(dimethylamino). Methyl)-phenoxy)phthalonitrile, yield 64%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | 3-nitrophthalicnitrile (20 mmol) and dipotassium 2-naphthol-6,8-disulfonate (20-70 mmol, preferably 60 mmol) as reactants, dimethyl sulfoxide (40-200 mL) , preferably 140 mL) is a solvent, and the reaction is stirred at room temperature ~ 60C (preferably 60C) for 24 to 72 hours in the presence of potassium carbonate (30 to 90 mmol, preferably 80 mmol) and nitrogen, monitored by thin layer chromatography. The insoluble potassium carbonate was removed from the reaction mixture by filtration, and the filtrate was added with 30 mL of ice-cold chloroform to precipitate a yellow-white precipitate which was filtered, washed with ethanol and acetone until the solution was colorless, and dried at 50 C. in vacuo to give 3-(6,8-bis). Sulfo-2-naphthyloxy)phthalodinitrile dipotassium salt, 93% yield. |
93% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | 3-nitrophthalicnitrile (20 mmol) and dipotassium 2-naphthol-6,8-disulfonate (20-70 mmol, preferably 60 mmol) as reactants, dimethyl sulfoxide (40-200 mL) , preferably 140 mL) is a solvent, and the reaction is stirred at room temperature ~ 60C (preferably 60C) for 24 to 72 hours in the presence of potassium carbonate (30 to 90 mmol, preferably 80 mmol) and nitrogen, monitored by thin layer chromatography. The insoluble potassium carbonate was removed from the reaction mixture by filtration, and the filtrate was added with 30 mL of ice-cold chloroform to precipitate a yellow-white precipitate that was filtered, washed with ethanol and acetone until the solution was colorless.Vacuum dried at 50CdryGet 3-(6,8-disulfo-2-naphthyloxy)phthalimide dipotassium saltThe yield is 93%. |
92.9% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 45℃;Inert atmosphere; | Taking <strong>[51762-67-5]3-nitrophthalonitrile</strong> (5mmo) and l2-naphthoic acid-6,8-dipotassium dipotassium (5~7.5mmo, preferably 5mmo) as the reactant, dimethyl sulfoxide ( 10 to 25 mL, preferably 10 m) L is a solvent,In the presence of potassium carbonate (7.5~15mm, o excellent l selected lOmm, divided into three l), and under nitrogen protection, stir the reaction at room temperature ~ 45 C (preferably 45 C) for 48 to 96 hours, through thin layer chromatography monitor,The reaction was terminated when the 3-nitrophthalic acid was substantially consumed. The reaction mixture was filtered through a microporous organic membrane, and the filtrate was collected. The filtrate was added to 100 ml of ice chloroform, stirred, and a large amount of milky white precipitate was precipitated, allowed to stand, and suction filtered. The filter cake was washed thoroughly with ethanol and acetone to collect a solid, 60. C was vacuum dried to give 2.35 g of product as a creamy white powder, yield 92.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium carbonate; In N,N-dimethyl-formamide; for 48h;Inert atmosphere; | General procedure: Vanillylacetone (2.0 g, 0.010 mol for 1 and 2; 2.91 g, 0.0150 mol for 3) and 4-nitrophthalonitrile (1.70 g, 0.010 mol)/3-nitrophthalonitrile (1.70 g, 0.010 mol)/4,5-dichlorophthalonitrile (2.56 g, 0.005 mol) were dissolved in dry DMF (50 mL) under a nitrogen atmosphere and anhydrous K2CO3 (2.76 g, 0.020 mol for 1 and 2; 1.38 g, 0.01 mol for 3) was added. This mixture was stirred for 48 h at room temperature and then poured into cold HCl (pH 5). The resulting solid was filtered, washed with water and dried. The crude product was purified by column chromatography, passing through silica gel 60 with chloroform as the eluent, and a pure yellow product was obtained. The compounds are soluble in tetrahydrofuran (THF), chloroform (CHCl3), dichloromethane (CH2Cl2), dimethylformamide (DMF) and dimethylsulfoxide (DMSO). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 10h;Inert atmosphere; | A mixture of <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.692g, 4mmol), 8-hydroxyquinoline-5-sulfonic acid monohydrate (0.972g, 4mmol), and K2CO3 (2.76g, 20mmol) in DMSO (30ml) was stirred at room temperature for 10h. The reaction mixture was poured into 50ml 0.01M HCl to give a white-brown precipitate. The precipitate formed was filtered off and then recrystallized with methanol to give a white solid (1.00g, 71%). 1H NMR (DMSO-d6, 400MHz, ppm): delta 9.26 (dd, J1=8.4Hz, J2=1.6Hz, 1H), 8.80 (dd, J1=4.4Hz, J2=2.0Hz, 1H), 8.06 (d, J=7.6Hz, 1H), 7.77 (d, J=7.2Hz, 1H), 7.61-7.68 (m, 3H), 6.95 (d, J=8.8Hz, 1H). FT-IR (KBr): 2232.6, 1634.1, 1551.8, 1451.9, 1255.2, 1384.3, 1192.8, 1047.8. HRMS (ESI): m/z calcd for C17H8N3O4S [M-H]-, 350.0241; found 350.0240. Elemental analysis (%) calcd. for C17H9N3O4S: C 58.12, H 2.58, N 11.96; Found C 58.10, H 2.65, N 11.98. |
67% | General procedure: 8-hydroxyquinoline-5-sulfonic acid (1.30 g, 5.78 mmol) was dissolved in dry DMF (8.00 mL) at 45 C and anhydrous K2CO3(1.5 g, 11.56 mmol) was added. After stirring for 15 min, <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1) was added dropwise in 2 h with efficient stirring. The reaction mixture was stirred under nitrogen at 45C for 4 days. After being cooled to room temperature, the mixture was poured into ca. 200 mL ice-water media and 1 M HCl (50 mL)was added in it. After completion of the precipitation approximately in 0.5 h, the creamy precipitate that formed was filtered and then washed with ca. 100 mL water until the washings became neutral. Column chromatography with methanol/dichloromethane (5:1) eluent on silica gel was employed to obtain the pure product. As expected, the yellow products were soluble in DMF and DMSO. Yield of 1: 1.36 g (67%); m.p.: Anal. Calc. for C17H9N3O4S (Mw:351.34): C, 58.12; H, 2.58; N, 11.96. Found: C, 57.90; H, 2.56; N,11.81%. FT-IR (KBr disc) n/cm-1: 3082, 3027, 2980 (Ar H), 2240 (CN), 1590, 1574, 1550 (Ar), 1273 (ArOAr), 1191, 1154 (SO2),789, 774, 674. 1H NMR (DMSO-d6): d ppm = 7.10-9.50 (m, 8H, ArH). UV/vis (DMSO): lambdamax = 299, 259. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.30% | With potassium carbonate; In dimethyl sulfoxide; at 45℃; for 36h;Inert atmosphere; | General procedure: 3-/or 4-Nitrophthalonitrile (3.50 g, 20 mmol), 2,4,6-trimethylphenol (2.78 g, 21.40 mmol) and anhydrous K2CO3 (14 g, 100 mmol) were added in 35 mL dimethylsulfoxide (DMSO). The mixture was stirred at 45 C for 36 h under inert atmosphere. Then the reaction mixture was poured into cold water. The light yellow solid was filtered off and washed using cold water and dried in room temperature. The crude products were purified by column chromatography using silica gel eluting with CHCl3. 3-(Mesityloxy) phthalonitrile (1): Solubility: Dichloromethane (DCM), CHCl3, tetrahydrofuran (THF), DMSO and dimethylformamide (DMF). Mp: 160 C. Yield: 4.45 g (84.30%). Anal. calculated for C17H14N2O C, 77.84%; H, 5.38%; N, 10.68%; found C, 77.65%; H, 5.54%; N, 10.83%. IR (ATR) numax/cm-1: 728, 774, 795, 802, 854, 908, 986(C-C str.), 1035(C-C str.), 1125, 1138, 1173, 1196, 1269(C-O str.), 1312(C-O str.), 1453(C-H bend.), 1480(C-H bend.), 1575(C=C str.), 1596(C=C str.), 2226(C?N str.), 2853(>CH2 str.), 2920(>CH2 str.), 3032(=C-H str.), 3084(=C-H str.). H-NMR (CDCl3): d, ppm 2.08 (s, 6H), 2.32 (s, 3H), 6.95 (s, 2H), 6.76 (dd, J = 8.67 Hz, J = 2.36 Hz, 1H), 7.4 (dd, J = 7.56 Hz, J = 2.05 Hz, 1H), 7.5 (t, J = 8.50 Hz, J = 7.85 Hz, 1H. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: 3-hydroxymethyl-thiophene; 3-nitrobenzene-1,2-dicarbonitrile In N,N-dimethyl-formamide at 40℃; for 1h; Inert atmosphere; Stage #2: With potassium carbonate In N,N-dimethyl-formamide at 30℃; for 72.5h; Inert atmosphere; | 2.2.1. 3-(Thiophen-3-ylmethoxy)phthalonitrile (1) and 4-(thiophen-3 ylmethoxy)phthalonitrile(2) General procedure: Thiophen-3-ylmethanol (1.15 g, 10.64 mmol) and 3- or 4-nitrophthalonitrile (1.00 g, 5.78 mmol) were dissolved in dry DMF (10 mL) and heated at 40 °C in N2 for 1 h. Then, finely ground anhydrous potassium carbonate (~1.0 g excess) was added portionwiseto mixture over the period of 0.5 h at 30 °C. After the reaction mixture was keptat this temperature under N2 for 3 days, it was cooled to room temperature (rt.) and pouredinto 200 mL ice-water. The creamy precipitate formed was filtered and dissolved in CHCl3and washed with % 5 NaHCO3 to remove starting unreacted compounds. The creamy solution was then dried with anhydrous Na2SO4 and filtered. It was chromatographed overa silica gel column using a mixture of CHCl3 : MeOH (100/5) as eluent, giving blue powder, 1. Finally, the pure powder was dried in a vacuum.Yield of 1: 1.32 g (66%); m.p. = 96 °C; Anal. Calcd for C13H8N2OS (240 g mol-1): C,64.98; H, 3.36; N, 11.66. Found: C, 64.21; H, 3.32; N, 10.98. FT-IR (cm-1); 3084 (w,Ar-CH), 2887 (w, Alip-CH), 2227 (C≡N, st), 1604(C=C), 1591 (C=N), 1471(st), 1249(Ar-O-Alip-CH), 1266, 1184, 1035, 916, 858, 827, 800, 729, 768. 1H-NMR (DMSO-d6)Σ: 7.80 (t 1H, meta to Ar-OR and CN, Phenyl H5), 7.65 (d, 1H, ortho to Ar-OR, PhenylH4), 7.59 (d, 1H ortho to S, thiophene) 7.20 (d, 1H, ortho to CN, Ar-H6), 6.45, 6.44 (m2H ortho to S and meta to S thiophene) 5.21(s, 2H, CH2OAr). 13C-NMR (DMSO-d6) δ:192.38, 161.22, 116.45, 116.12, 136.77, 136.42, 128.07, 127.88, 125.65, 119.62, 103.84,67.26, 56.71, EI/MS m/z: 241.02 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium carbonate; In N,N-dimethyl-formamide; at 60℃; for 98h;Inert atmosphere; | 2,3-Bis[3-(diethylamino)phenoxy]propan-1-ol (1) (1g, 2.59mmol) was dissolved in dry DMF (10mL) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> (3) (0.45g, 2.59mmol) was added to the solution. After stirring 10min, finely ground anhydrous K2CO3 (1.07g, 7.77mmol) was added to portion wise within 2h with efficient stirring. The reaction mixture was stirred under a nitrogen atmosphere at 60C for 96h. Then, this mixture was poured into water (100mL) and the aqueous phase was extracted with chloroform (3×50mL). The combined extracts were dried over anhydrous MgSO4 and then filtered off. Solvent was evaporated and the crude product was purified by passing through an aluminum oxide column using chloroform as eluent. Yield: 0.5g (38%). IR (KBr pellet) nu (cm-1): 3086 (Ar-H), 2971-2872 (Aliph. C-H), 2230 (C?N), 1611 (C=N), 1584, 1564, 1502, 1455, 1376, 1355, 1269, 1196, 1138, 1073, 1024, 940, 794. 1H NMR (400MHz, CDCl3), (delta: ppm): 7.54 (t, 2H, J=6.2, Ar-H), 7.43 (d, 2H, J=7.8, Ar-H), 7.25-7.21 (m, 2H, Ar-H), 7.15 (d, 2H, J=8.1, Ar-H), 6.58 (s, 1H, Ar-H), 6.38-6.31 (m, 2H, Ar-H), 4.25-4.20 (m, 5H, CH2-O, CH-O), 3.36 (m, 8H, CH2-N), 1.18 (m, 12H, -CH3). 13C NMR (100MHz, CDCl3), (delta: ppm): 167.80, 161.54, 155.04, 149.83, 134.16, 132.44, 130.91, 130.79, 128.81, 126.41, 122.13, 121.19, 120.39, 116.98, 115.32, 112.93, 109.26, 108.96, 105.48, 103.37, 68.16, 66.26, 44.45, 12.45. MS (ESI), (m/z) calc. 512.64; found: 512.48 [M]+. Elemental Analysis: (Found: C 72.82, H 7.23, N 10.69%, C31H36N4O3 (512.64) requires C 72.63, H 7.08, N 10.93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.29% | With potassium carbonate; In dimethyl sulfoxide; at 25℃; for 72h;Inert atmosphere; | General procedure: 2.60g (15.00mmol) <strong>[51762-67-5]3-nitrophthalonitrile</strong> or 4-nitrophthalonitrile and 2.39g (15.50mmol) 2,6-dimethoxyphenol were dissolved in 30mL anhydrous dimethylsulfoxide (DMSO). After stirring for 15min, finely ground 5.39g (39mmol) anhydrous K2CO3 was added to this solution. The reaction mixture was stirred at 25C for 72h under nitrogen atmosphere. Then the mixture was poured into ice-water. The precipitated white product was filtered off, washed with water, and then dried in vacuum at 50C. The crude product was purified by column chromatography using silica gel eluting with chloroform (CHCl3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h;Inert atmosphere; | 3-nitrophthalonitrile (3.46 g, 0.02 mol) and <strong>[617-05-0]ethyl 4-hydroxy-3-methoxybenzoate</strong> (5.89 g, 0.03 mol) were dissolvedin anhydrous DMF (60 mL) and anhydrous K2CO3(13.82 g, 0.1 mol) was added in portions during 30 min.The reaction mixture was stirred for 12 h at 80 C. Afterfiltering the reaction mixture, the residue was extractedwith CH2Cl2 and H2O and then was dried by rotaryevaporation. After removal of the solvent, the crude productwas purified by column chromatography using silicagel and CHCl3:MeOH (15:1) as eluent to give 1, a whitesolid. Yield: 6.38 g (99 %). 1H NMR (500 MHz, DMSOd6):d 7.84 (d, 1H, Ar-H), 7.78 (t, 1H, Ar-H), 7.71 (s, 1H,Ar-H), 7.68 (d, 1H, Ar-H), 7.42 (d, 1H, Ar-H), 7.16 (d,1H, Ar-H), 4.37 (m, 2H, -CH2O-), 3.82 (s, 3H, Ar-OCH3), 1.35 (t, 3H, -CH3). 13C NMR (126 MHz, DMSOd6):d 164.36, 158.94, 150.19, 144.73, 135.37, 128.33,127.55, 122.22, 121.60, 120.13, 115.15, 114.97, 113.42,112.60, 103.34, 60.49, 55.57, 13.58. HRMS (EI?): (m/z) = calcd for 322.0953, found: 322.0954. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 24h;Inert atmosphere; | A mixture of compound 1 (1.73 g, 7.29 mol) and 3-nitrophthalonitrile (1.26 g, 7.28 mol) in DMSO (30 mL) was stirred at room temperature for 10 min, and K2CO3 (2.52 g, 1.82 mol) was added with further stirring for 24 h. The reaction mixture was poured into 200 mL ice-water to give a great deal of yellow precipitate, which was collected by filtration and then washed with water. After dryness in vacuo, the product was obtained as a yellow solid (2.04 g, 94%). 1 H NMR (400 MHz, acetone-d6, ppm): d 7.85 (t, J 8.2 Hz, 1 H), 7.75 (d, J 7.6 Hz, 1 H), 7.40 (d, J 8.2 Hz, 2 H), 7.26 (d, J 8.7 Hz, 1 H), 7.19 (d, J 8.2 Hz, 2 H), 3.34 (t, J 7.0 Hz, 2 H), 2.86 (t, J 7.2 Hz), 1.40 (s, 9 H). MS (ESI): m/z 386.12 [M Na]. |
93.6% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 12h;Inert atmosphere; | Step 1) the resultant product (6.0mmol) and 3-nitro-O- benzene two nitrile (6.0mmol) dissolved in 30mLDMSO in, stirring the mixture at room temperature under the protection of nitrogen for 10 min later, by adding K 2 CO 3 (18.0mmol), to continue reaction 12h; after the reaction, the reaction liquid Buchner funnel for filtration, the filtrate collected; the filtrate is poured into 200 ml of ice water mixture, precipitating a large amount of purple-red precipitation, filtration, washing, collecting filter cake, shall after drying 2.04g, yield 93.6%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 96h;Inert atmosphere; | A mixture of 3-nitro-phthalonitrile (5mmol) and hydroxy pivalic acid (5mmol) was dissolved in DMSO (20ml), and reacted at room temperature under nitrogen, after 10min was added anhydrous potassium carbonate (10mmol), 24h and then adding hydroxypivalic acid (5mmol) and anhydrous potassium carbonate (10mmol), the reaction 72h, the end of the reaction monitored by thin layer chromatography.The reaction mixture was diluted with sand core funnel filtration, the filtrate was collected, and the filtrate was added to 500ml of ice water mixture, adjusted with 1M hydrochloric acid solution until the solution was acidic precipitation heavy precipitate, was allowed to stand, an organic microporous membrane, repeated washing more times until the solution was neutral, the solid was collected and lyophilized to give a white solid, further use DMF- water purified by recrystallization to give a white desired product, a yield of about 50percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With potassium carbonate; In dimethyl sulfoxide; at 20℃; for 74h;Inert atmosphere; | 3-Nitrophtalonitrile (1 g, 5.78 mmol) was dissolved in 40 mL of dry DMSO and 2-morpholinoethanol (1.07 mL, 8.67 mmol) was added. After stirring for 15 min, 3.2 g of finely ground anhydrous K2CO3 (23.10 mmol) was added in small portions for 2 h with efficient stirring. The reaction mixture was stirred under nitrogen at room temperature for 72 h. Then, the mixture was poured into 250 mL of ice-water mixture and, the precipitate was filtered off, washed with water until the filtrate was neutral, and dried in vacuo. Finally, a white product was obtained by column chromatography on alumina using 1:1 ethylacetate:hexane as eluent Yield: 0.86 g, (58%). m.p.: 119 C; anal. calcd. for C14H15N3O2: C, 65.35; H, 5.88; N, 16.33%; found: C, 65.10; H, 5.70; N, 16.40%; IR upsilonmax/cm-1: 3084 (Ar-H), 2939-2804 (Aliph-CH), 2228 (C?N), 1583, 1469, 1294, 1255, 1113 cm-1; 1H NMR (CDCl3): delta, ppm: 7.67-7.63 (t, 1H, Ar-H), 7.38-7.36 (d, 1H, Ar-H), 7.25-7.18 (d, 1H, Ar-H), 4.29-4.27 (t, 2H, O-CH2), 3.73-3.71 (t, 4H, O-CH2), 2.91-2.88 (t, 2H, N-CH2), 2.64-2.62 (t, 4H, N-CH2). |
34% | With potassium carbonate; In dimethyl sulfoxide; at 60℃; for 14h; | A mixture of N-(2-hydroxyethyl) morpholine (1) (0.656 g, 5.0 mmol), <strong>[51762-67-5]3-nitrophthalonitrile</strong> (2a) (0.866 g, 5.0 mmol), and anhydrous K2CO3 (1.380 g, 10 mmol) in dimethyl sulfoxide (DMSO) (20 ml) was stirred at 60 C for 14 h. The reaction mixture was poured into ice water (200 ml) to give light yellow precipitate, which was collected by filtration, washed with water until pH 7, and dried in vacuo. The crude product was further purified by chromatography on a silica gel column using acetone as eluent to give a white solid, which was redissolved in acetone (5 ml) and precipitated with ethanol (ca. 20 ml), followed by filtration to give a white solid 3a (0.440 g, 34%). Rf = 0.45 (acetone). IR (KBr, cm-1): 3084.4 (Ar-H), 2939.6, 2874.8, 2805.0 (CH2), 2238.5, 2227.8 (C?N), 1585.8, 1471.1 (C=C, benzene), 1305.9, 1154.4, 1114.0, 1059.6, 1015.9 (Ar-O-C, C-O-C, C-N, C-C), 918.24, 866.63, 803.62, 733.45, 690.04 (Ar-H). MS (ESI): m/z 258.1 [M+H]+. 1H NMR (300 MHz, DMSO-d6, ppm): delta = 7.82-7.87 (m, 1H, Ar-H); 7.64-7.69 (m, 2H, Ar-H), 4.34 (t, J = 5.7 Hz, 2H, O-CH2), 3.54 (t, J = 4.5 Hz, 4H, CH2-O-CH2), 2.74 (t, J = 5.7 Hz, 2H, CH2-N), 2.47-2.50 (m, 4H, CH2-N-CH2). HRMS (ESI): m/z calcd for C14H16N3O2 [M+H]+, 258.1243; found, 258.1232 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and triethylene glycol (20-70 mmol, preferably 60 mmol) as reactants and dimethyl sulfoxide (40-200 mL, preferably 140 mL) as solvent in potassium carbonate ( 30 to 90 mmol, preferably 80 mmol) are present and the reaction is stirred at room temperature to 60 C. (preferably 60 C.) for 24 to 72 hours under nitrogen protection and monitored by thin layer chromatography. After the reaction was completed, the reaction solution was poured into ice water to precipitate a light yellow precipitate, which was filtered to collect the residue. The filtrate was extracted with CHCl 3 , and the extract was back-extracted with water. The CHCl 3 extract was evaporated and vacuum dried at room temperature to give a yellow solid. The filter residue was combined with the product obtained by extraction in a yield of 65%. |
65% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and triethylene glycol (20-70 mmol, preferably 60 mmol) as reactants and dimethyl sulfoxide (40-200 mL, preferably 140 mL) as solvent in potassium carbonate ( 30-90 mmol, preferably 80 mmol) are present and incubated under nitrogen for 24 to 72 hours at room temperature to 60C (preferably 60C) and monitored by thin layer chromatography. After the reaction was completed, the reaction solution was poured into ice water to precipitate a light yellow precipitate, which was filtered to collect the residue. The filtrate was extracted with CHCl 3 , and the extract was back-extracted with water. The CHCl 3 extract was evaporated and vacuum dried at room temperature to give a yellow solid. The filter residue was combined with the product obtained by extraction in a yield of 65%. |
58% | In acetonitrile; at 90℃; for 18h;Inert atmosphere; | (. 3. 18 g, 21 17 mmol), anhydrous potassium carbonate (. 15.20 g, 0 11 mol) was added to the IJ IOOml round-bottomed flask, dissolved in acetonitrile and heated to 90 C under nitrogen; 3- nitro-phthalonitrile (. 1.83 g, 10 58 mmol) dissolved in acetonitrile after transfer to constant pressure dropping funnel and slowly added dropwise to the flask, continued after the addition was complete the reaction at 90 C at 18 h; After completion of the reaction, acetonitrile was removed by rotary evaporation under reduced pressure, the residue was extracted with methylene chloride; the resulting crude product with dichloromethane - methanol 30: 1 (v / v) as eluent, separated by silica gel column chromatography to give a pale after yellow oily liquid Technology Xhttp://www.technology-x.net/A61K/201410486382_2.html |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21.7 g | 26.3 g of diethylene glycol benzyl ether was dissolved in 140 mL of DMF, 5.4 g of 60% NaH was added at 0 to 5 C., and the mixture was stirred for 30 minutes. Then, a solution of 17.3 g of 3-nitrophthalonitrile in 60 mL of DMF was added dropwise and the mixture was stirred at 0 to 5 C. for 2 hours. The reaction solution was discharged into 2500 mL of diluted hydrochloric acid, stirred for 30 minutes, and the precipitate was collected by filtration, washed with water and dried. The obtained solid was recrystallized from 80% isopropyl alcohol aqueous solution to obtain a yellowish white solid 21.7 g (melting point 98.5 to 100.5 C) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h; | (8) A mixture of 2-phenyl-5,5-dihydroxymethyl-1,3-dioxane (2.2 g, 0.01 mol)3-nitrophthalonitrile (1.73 g, O. Olmol),Potassium carbonate (6.9 g, 0.05 mol)Add N, N-dimethylformamide, 50 mL;(9) The reaction was heated at 80 C for 12 hours;(10) After the reaction was stopped, the potassium carbonate was filtered off, the solvent was removed,Column chromatography using methanol / dichloromethane = 1/200 phase gave a white solid which was recrystallized from n-hexane / methylene chloride in a yield of 37% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.97% | With potassium carbonate; In dimethyl sulfoxide; at 50℃; for 120h;Inert atmosphere; | General procedure: 10mmol <strong>[51762-67-5]3-nitrophthalonitrile</strong> (or 4-nitrophthalonitrile or 4,5-dichlorophthalonitrile) 10.44mmol (1.42g), 2,3,5-trimethylphenol and 30mmol (3.18g) anhydrous K2CO3 were added in 20mL anhydrous dimethylsulfoxide (DMSO). The reaction mixture was hold by stirring at 50?C for 5days under inert atmosphere. It was poured into cold water and a white colour with a grey solid precipitated. The obtained precipitate was filtered and washed using cold water and dried in the open air. The raw product was purified by column chromatography using silica gel eluting with CHCl3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | 3-Nitrophthalonitrile (0.86 g, 5.0 mmol) was dissolved in 10.0 cm3 of dry DMF at 45 C andsodium 4-hydroxybenzenesulfonate (0.87 g, 5.0 mmol) was added. After stirring for 30 min,1.50 g nely ground anhydrous K2CO3 (10.0 mmol) was added portion wise in 2 h with e-cient stirring. The reaction mixture was stirred under nitrogen at 50 C for a further 72 h. Themixture was cooled to room temperature and then was filtered, and the filtrate was pouredinto cold chloroform to give a white precipitate, which was collected by filtration, washedwith ethanol and acetone. Then, the crude product was acidied with 100 mL of 1 M hydrochloricacid. After completion of the precipitation in about 24 h, the product was collectedby vacuum ltration and washed with cold ethanol and then with diethyl ether. Yield: 1.44 g,85%. FTIR, cm-1 3089, 3034 (Ar-H), 2239 (CN), 1236, 1246 (Ar-O-Ar),1H NMR (500 MHz,DMSO-d6): delta, ppm 7.15-7.18 (2H, dt, Ar-H), 7.29-7.31 (1H, dd, Ar-H), 7.69-7.72 (2H, dt, Ar-H),7.81-7.86 (1H, dd, Ar-H), 7.85-7.86 (1H, dd, Ar-H), 13C NMR 105.81, 113.80, 116.08, 116.35,119.48, 122.83, 128.46, 128.89, 136.56, 146.30, 154.52, 160.04. MS: m/z 378 [M + 2 K]+.Elemental analysis, Anal. Calcd for C14H8N2O4S: C, 56.00; H, 2.69; N, 9.33; O, 21.31; S, 10.68;found C, 56.88; H, 2.92; N, 8.83 m.p.: > 250 C. | |
74% | Compound 1 (0.86 g, 5.0 mmol) was dissolved in 10.0 cm3of dry DMSO at 50 C and sodium 4-hydroxybenzenesulfonate(0.87 g, 5.0 mmol) was added. After stirring for20 min, 1.50 g finely ground anhydrous K2CO3 (10.0 mmol)was added portion wise in 2 h with efficient stirring. Thereaction mixture was stirred under nitrogen at 50 C forfurther 72 h. After being cooled to room temperature, themixture was poured into 100 mL of 1 M hydrochloric acid.After completion of the precipitation in approximately24 h, the crude product was collected by vacuum filtrationand washed with cold ethanol and then diethyl ether.This compound was soluble in methanol, DMF, and DMSO.Yield: 1.25 g, 74%. FTIR, cm-1 3089, 3034 (Ar-H), 2239 (CN),1236, 1246 (Ar-O-Ar),1H-NMR (500 MHz, DMSO-d6): delta, ppm7.15-7.18 (2H, dt, Ar-H), 7.29-7.31 (1H, dd, Ar-H), 7.69-7.72 (2H, dt, Ar-H), 7.81-7.86 (1H, dd, Ar-H), 7.85-7.86 (1H,dd, Ar-H), 13C-NMR 105.81, 113.80, 116.08, 116.35, 119.48,122.83, 128.46, 128.89, 136.56, 146.30, 154.52, 160.04. MS: m/z 378 [M+2 K]+ Elemental analysis, Calcd. For C14H8N2O4SC, 56.00; H, 2.69; N, 9.33; O, 21.31; S, 10.68; found C, 56.88;H, 2.92; N, 8.83 m.p.: >250 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and 2,4,6-tris(dimethylaminomethyl)-phenol (20-70 mmol, preferably 60 mmol) as reactants, dimethyl sulfoxide (40) -200 mL, preferably 140 mL, is the solvent, and the reaction is stirred at room temperature ~ 60C (preferably 60C) for 24 to 72 hours in the presence of potassium carbonate (30 to 90 mmol, preferably 80 mmol) and nitrogen, and monitored by thin layer chromatography. Should be filtered to remove the reaction mixture was insoluble potassium carbonate, evaporated to dryness, adding 50 ~ 100mL of chloroform, stirred and filtered to remove insolubles, evaporated to dryness, add 50 ~ 100mL of water to the solid and 15 ~ 45mL HCl (1mol/L) stirred and filtered to remove insolubles. NaOH was added to the filtrate. The solids were precipitated and filtered. The solids were washed with water and dried in vacuo at 50C to give 3-(2,4,6-tris(dimethylamino). Methyl)-phenoxy)phthalonitrile, yield 64%. |
64% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | <strong>[51762-67-5]3-nitrophthalonitrile</strong> (20 mmol) and 2,4,6-tris(dimethylaminomethyl)-phenol (20-70 mmol, preferably 60 mmol) as reactants, dimethyl sulfoxide (40) -200 mL, preferably 140 mL, is the solvent, and the reaction is stirred at room temperature ~ 60C (preferably 60C) for 24 to 72 hours in the presence of potassium carbonate (30 to 90 mmol, preferably 80 mmol) and nitrogen, and monitored by thin layer chromatography. Should be filtered to remove the reaction mixture was insoluble potassium carbonate, evaporated to dryness, adding 50 ~ 100mL of chloroform, stirred and filtered to remove insolubles, evaporated to dryness, add 50 ~ 100mL of water to the solid and 15 ~ 45mL HCl (1mol/L) stirred and filtered to remove insolubles. NaOH was added to the filtrate. The solids were precipitated and filtered. The solids were washed with water and dried in vacuo at 50C to give 3-(2,4,6-tris(dimethylamino). Methyl)-phenoxy)phthalonitrile, yield 64%. |
With potassium carbonate; In N,N-dimethyl-formamide; at 45℃; for 24h;Inert atmosphere; | 1) with 25 mmol of 3-nitro phthalonitrileAnd 13.5 mmol of 2,4,6-tris (dimethylaminomethyl) -phenol as reactants,To 50 mL of N-N-dimethylformamide as solvent A, 50 mmol of potassium carbonate was added to three batches,The reaction was stirred at 45 C for 24 hours under nitrogen atmosphere,Using thin layer chromatography to monitor, when the 3-nitro phthalonitrile consumption is completed to terminate the reaction,The reaction mixture was filtered and the filtrate was collected,Drying the solvent, dissolving the solid with aqueous hydrochloric acid, removing the insoluble matter by suction filtration,And then to the filtrate by adding sodium hydroxide, precipitate a large number of precipitation after standing, suction filtration,Filter cake with water to wash, collect solid,60 C in vacuo to give a pale yellow powder of 3- [2,4,6-tris (dimethylaminomethyl) -phenoxy] phthalonitrile. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 72h;Inert atmosphere; | Under inert N2 atmosphere, 5-Methyl-1,3,4-thiadiazole-2-thiol(1) (2.00 g, 15.13 mmol) and 3-nitrophthalonitrile (2) (2.62 g.15.13 mmol) were dissolved in dry DMF (15 mL). Finely powderedanhydrous K2CO3 (6.26 g 45.39 mmol) was added portion wisewithin 2 h to reaction mixture at 50 C. The mixture was stirred for3 days at this temperature. Then it was poured into 250 mL icewater,stirred for 1 h at room temperature and filtered off. Thesolid product was crystallized from ethanol. Yield 2.15 g (55%), mp137e139 C, C11H6N4S2. IR (KBr tablet) ymax/cm1: 3076, 3055,2924, 2231 (C^N), 1614, 1574, 1446, 1379, 1331, 1186, 1041, 1027,818, 732.1H NMR (DMSO-d6), (d: ppm): 8.25e8.23 (d, 1H, ArH),8.14e8.12 (d, 1H, Ar-H), 7.99e7.95 (t, 1H, Ar-H), 2.72 (s, 3H, CH3). 13CNMR (DMSO-d6), (d: ppm): 169.21 (C]N), 161.52 (C]N), 139.22,137.07, 135.14, 130.99, 119.29, 117.25, 115.69 (C^N), 114.62 (C^N),16.93 (CH3).MS (ESI), (m/z): Calculated: 258.00; Found: 259.11[MH]. |
With potassium carbonate; In N,N-dimethyl-formamide; | The phthalonitrile compund ( 5) was synthesized by the reaction between 5-Methyl-1,3,4-thiadiazole-2-thiol (1) and 3-nitrophthalonitrile (3) in dry DMF in the presence of K2CO3 according to literature [25]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium carbonate; In N,N-dimethyl-formamide; at 40℃;Inert atmosphere; | 4-(methylthio)phenol (0.809 g, 5.78 mmol) was dissolved in10 cm3 dry DMF and thenfinely dried K2CO3 (~2.00 g, excess) wasadded to this mixture. Then <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.00 g,5.78 mmol) was added to this mixture dropwise by stirringeffectively at 40 C under the N2 atmosphere. The reaction mixturewas kept for 3 day at this temperature under N2 atmosphere. Afterthe reaction mixture was cooled to room temperature, it waspoured into ca. 200 cm3 ice-water media. The occured precipitatewasfiltered and then washed with ca. 100 cm3 water up to thewashings became neutral. The occured precipitate wasfiltered anddissolved in CHCl3 and washed with%5 NaHCO3 to eliminate thebeginning residual compounds. The creamy solution was thentreated with anhydrous Na2SO4 until become dry andfiltered. Itwas purified by chromatography over a silica gel column by using aeluent that is a mix of CHCl3: MeOH (100/5), giving white powder,(1). Finally, the pure powder was dried in a vacuo. Yield of (1): 1.28 g (83%); m.p. = 119 C; Anal. Calcd forC15H10N2OS (266 g mol1C, 67.65; H, 3.78; N, 10.52 Found: C,67.58; H, 3.52; N, 10.30. FT-IR (cm1); 3068 (w, Ar-CH), 2922 (w,Alip-CH), 2228 (CRN, st), 1610(CC), 1567 (CN), 1484(st), 1273(Ar-S-Alip-CH), 1088, 1009, 985, 847, 795. 1H NMR (DMSO-d6) delta:8.11 (t, 1H, meta to Ar-O-Ar and CN), 7.88 (d, 1H, ortho to Ar-O-Ar),7.52 (d,1H, ortho to CN), 7,367.01 (m, 4H, O-Ar-S) 2.23(s, 3H, CH3-S-Ar). 13C NMR (DMSO-d6) delta: 165.4, 156.7, 141.4, 141.1, 133.5, 133.4,127.1, 126.3, 121.2, 121.1, 118.8, 110.2, 20.4. EI/MS m/z: 266.12 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | The 2-hydroxymethyl-1,4-benzodioxane (0.52?g, 2.89?mmol) was dissolved in N,N'-dimethylformamide (DMF) (30?ml) under nitrogen atmosphere, and <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.5?g, 2.89?mmol) was added to the solution. After stirring for 25?min at room temperature, finely grinded anhydrous potassium carbonate (K2CO3) (1.96?g, 14.45?mmol) was added to this mixture in small portions for 2?h with efficient stirring. The reaction mixture was then stirred in nitrogen atmosphere for a total of 24?h at 45?C. Following that, it was cooled to room temperature and poured into 250?ml ice-water. The precipitate formed was filtered off and washed by successive with water, n-hexane and diethylether before drying. The creamy crude product was purified by recrystallization in methanol (MeOH). Finally, the pure powder obtained was dried in vacuum. This compound is soluble in ethanol (EtOH), MeOH, acetone, dichloromethane (DCM) and chloroform (CHCI3). Yield: 87% (734?mg). Mp: 136-137?C. Anal. calc. for C17H12N2O3: C, 69.86; H, 4.14; N, 9.58. Found: C, 69.52; H, 4.01; N, 9.32%. FT-IR (ATR, cm-1): 3086.68 (Ar-CH); 2976.41, 2935.69, 2880.29 (Aliphatic-CH, CH2); 2230.94 (C?N); 1578.41, 1495.09, 1471.57 (C=C), 1253.67, 1242.82 (C-O-C), 1054.34; 847.13, 755.61. 1H·NMR (Acetone-d6), (delta: ppm): 7.81-7.78 (t, 1H, Ar-H), 7.64-7.63 (d, 1H, Ar-H), 7.53-7.52 (d, 1H, Ar-H), 6.79-6.73 (m, 4H, Ar-H), 4.62-4.51 (s, 1H, Aliphatic-CH), 4.42-4.18 (m, 4H, Aliphatic-CH2). 13C·NMR (CDCl3), (delta: ppm): 160.61, 142.99, 142.35, 132.67, 125.12, 122.12, 121.99, 117.54, 117.43, 117.30, 117.00, 115.16 (C?N), 112.69 (C?N), 105.50, 70.77, 67.55, 64.52. MS (GC-MS) m/z, Calc.: 292.08, Found: 292 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With potassium carbonate; In N,N-dimethyl-formamide; at 25℃; for 170h;Inert atmosphere; | 1-Benzylpiperidin-4-ol (1) (1.59 g, 8.33 mmol) and 3-nitrophthalonitrile (2) (1.44 g, 8.33 mmol) were dissolvedin dry DMF. Then anhydrous K2CO3 (11.50 g, 83.37 mmol) was added over 2 h. The reaction media werestirred under N2 at 25 C for 7 days. After the completeness of the reaction that was controlled by TLC, themixture was poured into ice-water and the precipitate was ltered and washed with distilled water. The pureproduct was obtained by crystallization in ethanol. Yield: 1.32 g (50%), mp: 105{107 C. IR vmax /cm1 :3082 (Ar{H), 2950-2828 (Aliph. C{H), 2223 (CN), 1582{1470 (C=C), 1283 (Ar{O{C), 1043 (N{CH2) , 797,749. 1H NMR (CDCl3) ( : ppm): 7.06 (t, J =6.4 Hz, 1H, Ar{H), 7.32{7.30 (m, 5H, Ar{H), 7.25{7.21 (m,2H, Ar{H), 4.58{4.56 (m, 1H, CH{CH2) , 3.54 (s, 2H, CH2 {Ar), 2.71 (t, J =8 Hz, 2H, CH2 {N), 2.41 (t, J =8Hz, 2H, CH2 {N), 2.00{1.98 (m, 2H, CH2 {CH), 1.93-1.91 (m, 2H, CH2 {CH). 13C NMR (CDCl3) ( : ppm):160.25, 138.47, 129.01, 128.24, 127.08, 125.03, 118.07, 117.23, 115.33, 115.22, 113.24, 105.93, 75.11, 62.86 (2C),49.56, 30.53 (2C). Elemental analysis: calcd (%) for C20H19N3 O: C, 75.69; H, 6.03; N, 13.24. Found: C, 75.66;H, 6.00; N, 13.30. MS (ES+) : m/z: calcd. 317.38; found 318.13 [M + H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 48h; | General procedure: To a solution of ethyl 7-hydroxy-4,8-dimethylcoumarin-3-propanoate (1 g, 3.5 mmol) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> or 4-nitrophthalonitrile (0.605 g, 3.5 mmol) in anhydrous N,N-dimethylformamide (DMF, 20 mL) was added ground anhydrous K2CO3(0.713 g, 5.16 mmol) at 50 C. The solution was stirred for 48 h atthis temperature. The purity of product was tested by thin-layerchromatography(TLC). The mixture was precipitated on ice thenthe white precipitated was filtered off and washed three times withwater (3 20mL) until neutral and dried under vacuum at 60 C. Itwas purified by column chromatography using silica gel elutingwith chloroform (CHCl3). 2.2.1.1. Ethyl 7-(2,3-dicyanophenoxy)-4,8-dimethylcoumarin-3-propanoate (1). The compound (1) is soluble in ethyl acetate,CHCl3, dichloromethane (DCM), tetrahydrofuran (THF), dimethylsulphoxide(DMSO) and DMF. Yield: 1.26 g (88%). M. p.:175 C.Anal calculated for C24H20N2O5: C, 69.22; H, 4.84; N, 6.73; found: C,69.21%; H, 4.62%; N, 6.82%. IR (ATR) numax/cm1: 3084-3028 (Ar-CH), 2983e2932 (aliphatic-CH), 2237 (Ar-C^N), 1712 (lactoneeC]O), 1622 (Ar-C]C-), 1261 (Ar-O-Ar). UV-vis (DMF,1 105 M): lambdamax (nm), (log epsilon): 318 (4.89). Fluorescence emission(DMF,1 105 M): lambdaEm (nm): 462. 1H NMR delta; ppm (CDCl3): 7.58 (dd,1H, J 8.24, 8.21 Hz), 7.55 (d, 1H, J 8.89 Hz), 7.50 (d, 1H,J 7.82 Hz), 6.95 (d, 1H, J 8.63 Hz), 6.94 (d, 1H, J 8.74 Hz), 4.13(q, 2H), 3.02 (t, 2H), 2.64 (t, 2H), 2.49 (s, 3H), 2.33 (s, 3H), 1.26 (t,3H). MS (MALDI-TOF) [m/z]: Calculated: 416.43; found: 417.72[MH]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With potassium carbonate In N,N-dimethyl-formamide at 30 - 40℃; for 48h; Inert atmosphere; | Synthesis of 3-(4-(methoxymethyl) phenoxy) phthalonitrile (1)and 4-(4-(methoxymethyl) phenoxy) phthalonitrile (2) General procedure: 4-(Methoxymethyl)phenol (1.60 g, 11.57 mmol) was dissolvedin dry DMF and then finely ground anhydrous K2CO3(2.00 g,excess) was added. Then 3-nitrophthalonitrile or 4-nitrophthalonitrile(2.00 g of 11.56 mmol) was added to this mixture dropwise at30 C with effective stirring under N2 atmosphere. The reaction mixture was stirred under N2 atmosphere at ca.40 C for 2 days and monitored by TLC. After the reaction mixture was cooled to room temperature, it was poured into ca. 200 ml ice-water. Thecreamy precipitate was filtered and washed with water until washings became neutral. The crude product was dissolved in THF andfiltered again. Final product was chromatographed over gel columnusing a mixture of CHCl3:MeOH (5/1) as eluent. Finally pure powder was dried in vacua.Yield of (1): 1.74 g (57%) m.p.: 89 C. Anal. Calcd for C16H12N2O2(264.28 g mol1): C, 72.72; H, 4.58; N, 10.60. Found: C, 68.12; H,4.44; N, 9.62. IR (thin film) m/cm1: 3090 (w, Ar-CH), 2937-2824(w, Aliph-CH2), 2227 (C„N, str.), 1576 (CC), 1451 (CAH bend.),1210 (Ar-O-r), 1116, 984, 803. 1H NMR ([d6]-CDCl3) d: 7.62 (t,1H, meta to Ar-O-Ar and CN), 7.45 (d, 1H, ortho to Ar-O-Ar),7.33 (d, 1H, ortho to CN), 7.18 (d, 2H meta to ArCH2OCH3), 7.05(d, 2H ortho to ArCH2OCH3), 4.18 (s, 2H, -CH2-), 3.62 (s, 3H,-CH3). 13C NMR ([d6]-CDCl3) d: 160.7, 152.9, 137.6, 131.5, 128.7,122.4, 120.5, 116.5, 116.3, 114.1, 105.5, 73.2, 58.5. EI/MS m/z:264.046 [M]+.Yield of (2): 2.11 g (69%) m.p.: 54 C. Anal. Calcd for C16H12N2O2(264.28 g mol1): C, 72.72; H, 4.58; N, 10.60. Found: C, 71.52; H,4.24; N, 9.87. IR (thin film) m/cm1: 3073 (w, Ar-CH), 2983-2864(w, Aliph-CH2), 2228 (C„N, str.), 1591 (CC), 1481 (CAH bend.),1246 (Ar-O-Ar), 1196, 967, 836, 520. 1H NMR ([d6]-CDCl3) d:7.75 (d, 1H, meta to Ar-O-Ar and ortho to CN), 7.44 (d, 1H, orthoto Ar-O-Ar and meta to CN), 7.33 (s, 1H, ortho to Ar-O-Ar andortho to CN), 6.98 (d, 2H meta to ArCH2OCH3), 6.91 (d, 2H ortho to ArCH2OCH3), 4.20 (s, 2H, -CH2-), 3.66 (s, 3H, -CH3). 13C NMR([d6]-CDCl3) d: 162.2, 151.9, 137.6, 135.6, 131.2, 121.6, 121.4,120.8, 117.7, 115.7, 115.3, 108.7, 73.4, 59.0. EI/MS m/z: 264.102[M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With potassium carbonate; In dimethyl sulfoxide; at 0 - 60℃;Inert atmosphere; | 3-nitrophthalicnitrile (20 mmol) and N,N-dimethyl-m-hydroxyaniline (20-30 mmol, preferably 25 mmol) as reactants, dimethyl sulfoxide (60-80 mL, preferably 70 mL) The solvent is stirred in the presence of potassium carbonate (30-60 mmol, preferably 50 mmol) and nitrogen, and the reaction is stirred at room temperature to 60C (preferably 60C) for 24-72 hours and monitored by thin layer chromatography. After the completion of the reaction, after the reaction was completed, water was allowed to stand for 4 to 12 hours and precipitated. The double-layer filter paper was suction filtered at room temperature and freeze-dried to obtain a brown-yellow powdery solid with a yield of 61%. |
61.15% | With potassium carbonate; In dimethyl sulfoxide; at 60℃;Inert atmosphere; | Using <strong>[51762-67-5]3-nitrophthalonitrile</strong> and N,N-dimethyl-m-hydroxyaniline as reactants,The feed ratio of the two is 1:1 to 1.5 with dimethyl sulfoxide as the solvent.The amount of solvent required is 3 to 4 mL per mmol of <strong>[51762-67-5]3-nitrophthalonitrile</strong>.In the presence of potassium carbonate and nitrogen protection,The reaction is stirred at room temperature ~60C for 48-72 hours.The amount of potassium carbonate used is 1.5 to 3 mmol per mmol of 3-nitro-phthalonitrile.Monitored by thin layer chromatographyThe reaction was terminated when the 3-nitro-phthalonitrile was almost consumed, and water was allowed to stand for 4 to 8 hours.Precipitate, double filter paper atmospheric pressure filtration,Freeze-drying gave a brown-yellow powdery solid, yield 61.15%. |
61% | With potassium carbonate; In dimethyl sulfoxide; at 20 - 60℃;Inert atmosphere; | 3-nitrophthalicnitrile (20 mmol) and N,N-dimethyl-m-hydroxyaniline (20-30 mmol, preferably 25 mmol) as reactants, dimethyl sulfoxide (60-80 mL, preferably 70 mL) The solvent is stirred in the presence of potassium carbonate (30-60 mmol, preferably 50 mmol) and nitrogen, and the reaction is stirred at room temperature to 60C (preferably 60C) for 24-72 hours and monitored by thin layer chromatography. After the completion of the reaction, after the reaction was completed, water was allowed to stand for 4 to 12 hours and precipitated. The double-layer filter paper was suction filtered at room temperature and freeze-dried to obtain a brown-yellow powdery solid with a yield of 61%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | (1R,2R)-1,2-Diphenylethane-1,2-diol 1 (1.5?g, 7.0?mmol) and 22.5?mL of DMSO were placed in two-neck flask under a nitrogen atmosphere at room temperature. To this reaction mixture was added <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.2?g; 7.0?mmol) and stirred for 15?min under inert atmosphere. Finely ground anhydrous K2CO3 (0.97?g; 7.0?mmol) was then added to the resulting mixture at room temperature. The reaction was monitored by thin layer chromatography and completed in 2?h. The reaction mixture was poured into water-ice (1:3 v/v) resulting in the formation of light-yellow precipitate and then extracted with dichloromethane. The combined organic layer was dried over anhydrous Na2SO4 and the solvent was evaporated under reduced pressure to give a crude product that was purified by silica gel chromatography. The elution was carried out with dichloromethane-ethylacetate (95:5). The product was obtained as a white solid. Yield: 1.55?g, (65%); mp: 128-130?C. Found: C, 77.34; H, 4.58; N, 8.19%; 'molecular formula C22H16N2O2' requires C, 77.63; H, 4.74; N, 8.23%. +237.67 (c?=?1, CHCl3); retention time 15.93?min, Chiral ART Amylose-C, 30:70 n-hexane-iPrOH, flow rate of 0.5?mL/min, 254?nm, t?=?40?C; IR (KBr disc) vmax/cm-1: 3500 (OH), 3064, 3033, 2910, 2232 (C?N), 1734, 1579, 1462, 1285, 1043, 793, 764, 701; 1H NMR (400?MHz, CDCl3, ppm) delta: 7.43 (t, J?=?8.3?Hz, H), 7.29 (dd, J?=?7.8?Hz, J?=?0.8?Hz, H), 7.25-7.20 (m, 6H), 7.11 (m, 2H), 7.05 (m, 3H), 5.27 (d, J?=?7.5?Hz, H), 5.10 (d, J?=?7.5?Hz, H), 3.09 (br, OH); 13C NMR (100?MHz, CDCl3, ppm) delta: 160.3, 137.9, 135.0, 134.3, 128.9, 128.7, 128.4, 128.2, 127.3, 127.1, 121.1, 125.7, 119.0, 117.0, 115.2, 113.1, 105.8, 87.4, 77.9; MS (ESI-) MS calculated [M+Cl]- for C22H16N2O2Cl: 375.1 found: 375.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | 2-(3,4-Dimethoxyphenyl)ethanol (2.10?g, 11.56?mmol) was stirred in dry DMSO in the presence of finely ground anhydrous K2CO3 (?2.00?g, excess). After stirring for 30?min under an N2 atmosphere, <strong>[51762-67-5]3-nitrophthalonitrile</strong> (2.00?g, 11.56?mmol) was added to this mixture dropwise. The reaction mixture was monitored by TLC (CHCl3) for 3?days at ca. 50?C. The mixture was then cooled to ambient temperature and poured into ca. 250?mL ice-water. After completion of the precipitation, the solid product was filtered and purified by column chromatography using a mixture of CHCl3:MeOH (2:1 v/v) as the eluent. The obtained products are excellently soluble in CHCl3, THF, DMF and DMSO. Yield of 2: 0.69?g (78%), m.p.: 138?C. Anal. Calc. for C18H16N2O3 (308.33?g/mol): C, 70.12; H, 5.23; N, 9.09. Found: C, 70.09; H, 5.20; N, 9.05%. FT-IR (thin film) nu/cm-1: 3094, 2968, 2832, 2241, 1608, 1582, 1530, 1464, 1405, 1378, 1269, 1159, 1033, 960, 813, 459. 1H NMR ([d6]-DMSO) delta, ppm: 8.10, 7.80, 7.62, 6.85, 6.80, 6.65, 4.40, 3.80, 3.00. 13C NMR ([d6]-DMSO) delta, ppm: 161.5, 149.1, 148.1, 137.1, 130.7, 121.3, 119.1, 116.4, 116.0, 113.6, 113.4, 112.4, 71.1, 63.1, 56.1, 55.9, 34.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 120h;Inert atmosphere; | General procedure: 4-Nitrophthalonitrile or <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.6g, 3.44mmol) and compound 1 (1.0g, 3.44mmol) were dissolved in 30mL dry DMF and stirred for 10min and anhydrous K2CO3 (0.95, 6.88mmol) was added in portions over 2h by stirring. After stirring for 5days at 50C under N2 atmosphere, the reaction mixture was poured into cold water. The precipitate formed was filtered, washed with water and dried. The crude product was purified by column chromatography using petroleum ether:ethyl acetate (1:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | A solution of 9 (1H-benzo[d][1,2,3]triazol-1-yl)methanol (1) (4g, 26.82mmol) and 26 3-nitrophthalonitrile (4.64g, 26.82mmol) in dry 27 DMF (15mL) was stirred at 60C for 10min under a nitrogen atmosphere. And then, finely ground anhydrous 28 K2CO3 (14.80g, 107.28mmol) was added to this mixture as portionwise over a period of 2h with stirring at this temperature. After stirring for 120h at 60C, the reaction mixture was poured over crushed ice and the resulting white 29 precipitate was filtered off, washed with distilled water, and then dried in vacuo. (0019) Yield: 1.20g (16%). M.p.: 228-229C. FT-IR numax/cm-1: 3093 (Aromatic-CH), 2911-2950 (Aliphatic-CH), 2223 (C?N), 1579 (Aromatic-C=C), 1475, 1287, 1266 (C-O-C), 1168, 1039, 989, 806, 741. 1H NMR (DMSO-d6, 200MHz, delta, ppm): 8.15 (d, J=7.8Hz, 1H, ArH), 8.05 (t, J=7.2Hz, 1H, ArH), 7.79 (d, J=7.2Hz, 1H, ArH), 7.72 (t, J=7.8Hz, 1H, ArH), 7.68 (d, J=7.8Hz, 1H, ArH), 7.53 (t, J=7.8Hz, 1H, ArH), 7.49 (d, J=7.2Hz, 1H, ArH), 7.07 (s, 2H, CH2). 13C NMR (DMSO-d6) (delta: ppm): 158.84, 146.00, 136.47, 133.35, 129.42, 128.39, 125.69, 121.27, 120.26, 116.39, 116.20, 113.71, 111.34, 105.18, 74.98. MALDI-TOF, m/z: Calc.: 275.27 for C15H9N5O; Found: 276.17 [M+H]+. Anal. Calc. for C15H9N5O: C, 65.45; H, 3.30; N, 25.44%, Found: C, 65.41; H, 3.34; N, 25.40%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.11% | With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 72h;Inert atmosphere; | General procedure: 7-Hydroxy-4-(pyridin-3-yl)coumarin (1.00 g, 4.2 mmol), 4-nitrophtahlonitrileor <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.72 g, 4.2 mmol), and dryK2CO3 (0.87 g, 6.3 mmol) were solved in anhydrous DMF (20 mL). Themixture was blended for 72 h at 50 C under argon atmosphere. At theend of reaction, the mixture was drained into cold water to precipitate the crude product. Precipitated product was filtered, and dried on anhydrousCaCl2. Silica gel column (eluent: CHCl3) was used to purified the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With potassium carbonate; In N,N-dimethyl-formamide; at 0.4℃; for 72h;Inert atmosphere; | General procedure: <strong>[56718-71-9]4-(2-Methoxyethyl)phenol</strong> (1.93 g, 12.71 mmol) was stirred indry DMF in the presence of finely ground anhydrous K2CO3(~2.00 g,excess). After stirring for 30 min under N2 atmosphere, 3-nitrophthalonitrile or 4-nitrophthalonitrile (2.00 g of 11.56 mmol)was added to this mixture dropwise. The reaction mixture wasmonitored by TLC (CHCl3) for 3 days at ca.40 C. Then, the mixturewas cooled to ambient temperature and poured into ca. 250 mL icewater.After completion of the precipitation, the solid product wasfiltered and purified by column chromatography using mixture ofCHCl3:MeOH (10:5 v/v) as eluent. Finally, the solid product wascrystallized from ethanol. The obtained products are excellentsoluble in MeOH, CHCl3, THF, DMF, DMSO. Yield of (1): 1.67 g (52%) m.p.: 91 C Anal. Calcd for C17H14N2O2(278.31 g mol1): C, 73.37; H, 5.07; N, 10.07 Found: C, 73.40; H,5.05; N, 10.01. FT-IR (thin film) nu/cm1: 3082 (w, Ar-CH), 2980-2816(w, Aliph-CH2), 2243 (C^N, str.), 1575 (C]C), 1503, 1462 (C-Hbend.), 1281 (Ar-O-Ar), 1115, 990, 855. 1H NMR ([d6]-DMSO) delta: 8.00-7.73 (m, 2H, ortho to Ar-O-Ar and meta to CN), 7.38 (d, 2Hmeta to -CH2CH2OCH3), 7.23 (d, 1H, ortho to CN), 7.18 (d, 2H ortho to-CH2CH2OCH3), 3.50 (t, 2H, -CH2-OCH3), 3.21 (s, 3H, -CH3), 2.82 (t,2H, -CH2-CH2OCH3). 13C NMR ([d6]-DMSO) delta: 160.7, 152.9, 137.6,136.7, 131.5, 128.7, 122.4, 120.5, 116.5, 116.3, 114.1, 105.5, 73.2, 58.5,35.2. MALDI-TOF-MS, (Dithranol): m/z: 300.215 [M Na-H],316.184 [M K-H], 324.433 [M2Na]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; In N,N-dimethyl-formamide; at 45 - 50℃; for 72h;Inert atmosphere; | Firstly, Ferulic acid (2.89 mmol, 0.56 g)was dissolved in dry DMF(50 mL) and then <strong>[51762-67-5]3-nitrophthalonitrile</strong> (2.89 mmol, 0.5 g) wasadded into the solution. The solution was mixed to obtain a homogenousmixture for 15 min. Then, anhydrous K2CO3 (11.56 mmol,1.59 g) was added into the solution for 2 h. The mixture was heatedunder nitrogen atmosphere at the range of 45-50 C for 72 h. At theend of the reaction, the mixture was cooled to the room temperatureand diluted HCl solution (0.1M) was added to arrange of pH as2e3. The solid particles were obtained in an hour. The particleswere filtered and then washed with water, hexane and diethylether. After the drying process, light brown particles were recrystallizedin MeOH. The final product was soluble in various solventssuch as DMSO, MeOH, EtOH, acetone, chloroform, and THF. Yield85% (784.9 mg), M.p. 230-231 C, Anal. Calc. for C18H12N2O4 (MW:320.30 g/mol): C, 67.50; H, 3.78; N, 8.75. Found: C, 67.25; H, 3.68; N,8.59%. FT-IR (ATR), nmax/(cm1): 3300-2500 (broad peak, carboxylicacid-COOH), 3085-3012 (AreCH), 2976e2943 (aliphatic eCH,eCH3), 2233 (eC^N), 1678 (C]O), 1633 (AliphaticeC]C),1585e1463 (AreC]C), 1290 (AreOeAr). 1H NMR (DMSO-d6,500 MHz, d:ppm): 12.47 (s, 1H, eOH), 7.82-7.75 (m, 2H, AreH), 7.63-7.61 (dd, 2H, AreH), 7.38-7.37 (dd, 1H, AreH), 7.33 (d, 1H, AreCH]C), 7.15-7.11 (dd, 1H, AreH), 6.66-6.61 (d, 1H, CHeCOO), 3.80 (s,3H, OeCH3). 13C NMR (DMSO-d6, 500 MHz, d:ppm): 167.73(eCOOH), 160.21, 151.24, 143.23, 142.77 (AreC]C), 136.13, 134.02,127.96, 122.70, 122.33, 120.46, 120.23 (CeCOOH), 115.82 (eC^N),115.79 (-C^N),113.51,113.00,103.60, 56.32 (OeCH3). MS (LC-MS QTOF)m/z. Calculated: 320.30 Found: 338.31 [MNH4] and 641.17[2MH]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.1% | With potassium carbonate; In N,N-dimethyl-formamide; at 50 - 60℃; for 48h;Inert atmosphere; | General procedure: 7-Hydroxy-3(p-thiomethylphenyl) coumarin (1) (1.42g, 5mmol) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> or 4-nitrophthalonitrile (0.86g, 5mmol) were dissolved in 50mL of dry dimethylformamide (DMF) under an argon atmosphere and anhydrous K2CO3 (1.04g, 7.5mmol) was added and this mixture was stirred for 48h at 50-60C. After cooling to room temperature, the reaction mixture was treated with diluted HCl. The solid product was filtered, washed with water and dried. The crude product was purified by silica gel column chromatography using CHCl3 as an eluent. 7-(2,3-Dicyanophenoxy)-3(p-thiomethylphenyl) coumarin (2) Yield 1.87g (91.1%). Mp 268-269C. Anal. calcd. for C24H14N2O3S: C, 70.23; H, 3.44; N, 6.83%; Found: C, 70.19; H, 3.41; N, 6.89%. 1H-NMR (500MHz, CDCl3): deltaH, ppm 8.29 (s, 1H, lactone-H), 7.94 (dd, 1H, J=7.78 and 1.07Hz, Ar-H), 7.87 (dd, 1H, J=8.59 and 8.64Hz, Ar-H), 7.86 (dd, 1H, J=7.77 and 1.07Hz, Ar-H), 7.67 (d, 2H, J=8.65Hz, Ar-H), 7.50 (dd, 1H, J=8.56 and 1.14Hz, Ar-H), 7.35 (d, 1H, J=2.35Hz, Ar-H), 7.33 (d, 2H, J=8.69Hz, Ar-H), 7.23 (dd, 1H, J=8.55 and 2.42Hz, Ar-H), 2.49 (s, 3H, -SCH3). FT-IR (ATR): upsilonmax, cm-1: 3094-3038 (Ar-CH), 2923 (Aliphatic-CH), 2227 (Ar-CN), 1720 (lactone-C=O), 1614-1573 (Ar-C=C), 1278 (Ar-C-O) and 808 (Ar-SCH3). UV-vis (THF): lambdamax=348nm. Florescence (THF): lambdaem=461nm. MS (MALDI-TOF) m/z: calcd. 410.44, found 411.58 [M+H]+, 429.16 [M+H+H2O]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 32℃; for 10h; | Bisphenol F and 3-nitrophthalonitrile were dissolved together in 20 mL of NMP solvent, and then potassium carbonate was added to the solution, and the reaction was kept at 32 C for 10 hours. After the reaction, the reaction solution was washed twice with deionized water and methanol, and the filter cake was collected. The filter cake was dried to constant weight to obtain bisphenol F-derived phthalonitrile monomer. : |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | The <strong>[51762-67-5]3-nitrophthalonitrile</strong> (1.00 g 5.8 mmol) was dissolved in dryDMF (15 ml) under inert argon atmosphere and 4-4 (bromophenoxy)phenol (1.55 g 5.84 mmol) was added. After stirring for4e30 min at room temperature, finely ground anhydrous potassiumcarbonate (2.0 g 14.47 mmol) was added in portions during2 h with efficient stirring. The reaction mixture was stirred underargon atmosphere at room temperature for 24 h. Then the mixturewas dumped into 100ml could water, and the precipitate wasfiltered off, and crystallized in methanol and then dried. Finally, thepure powder was dried in a vacuum. Yield: 1.93 g (85%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | General procedure: The 3-nitrophthalonitrile (1.00 g 5.8 mmol) was dissolved in dryDMF (15 ml) under inert argon atmosphere and 4-4 (bromophenoxy)phenol (1.55 g 5.84 mmol) was added. After stirring for4e30 min at room temperature, finely ground anhydrous potassiumcarbonate (2.0 g 14.47 mmol) was added in portions during2 h with efficient stirring. The reaction mixture was stirred underargon atmosphere at room temperature for 24 h. Then the mixturewas dumped into 100ml could water, and the precipitate wasfiltered off, and crystallized in methanol and then dried. Finally, thepure powder was dried in a vacuum. Yield: 1.93 g (85%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | General procedure: (1R,2R)-1,2-bis(3-phenylphenyl)ethane-1,2-diol 1 (1.0 mmol,1.0 equiv.) and 4mL of DMSO were placed in two-neck flask under anitrogen atmosphere at room temperature. To this reaction mixturewas added 3- or 4-nitrophthalonitrile (1.0 mmol, 1.0 equiv.) andstirred for 15 min under inert atmosphere. Finely ground anhydrousK2CO3 (1.0 mmol, 1.0 equiv.) was then added to the resultingmixture at room temperature. The reaction was monitored by thin layer chromatography and completed in 2 h. The reaction mixturewas poured into water-ice (1:3 v/v) resulting in the formation oflight-yellow precipitate and then extracted with dichloromethane.The combined organic layer was dried over anhydrous Na2SO4 andthe solvent was evaporated under reduced pressure to give a crudeproduct that was purified by silica gel chromatography. The elutionwas carried out with dichloromethaneeethyl acetate (95:5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.9% | With potassium carbonate; In acetonitrile; at 60℃; | To a 500 ml four-neck separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile, 15.7 g (0.095 mol) of 2,6-dichlorophenol, 23.9 g (0.17 mol) of potassium carbonate and 60.0 g of acetonitrile were injected, and stirred at 60 C overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to perform recrystallization. The obtained crystals were filtered and 17.5 g (yield 69.9%) of 3-(2,6-dichlorophenoxy)phthalonitrile was obtained by vacuum drying. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.1% | With potassium carbonate In N,N-dimethyl-formamide at 60 - 65℃; for 48h; Inert atmosphere; | 2.1.1. General synthesis procedure for phthalonitriles (1-2) 2-Benzylphenol (1 g, 5.43 mmol) and 4-nitrophthalonitrile/3-nitrophthalonitrilecompounds (0.94 g, 5.43 mmol) were stirred in 25 mLanhydrous DMF. After stirring, anhydrous K2CO3 was slowly added tothe reaction. The mixture was stirred at 60-65 °C for 48 h. At the end ofthis time, the reaction mixture was poured into ice water, then filteredand dried. The crude product was purified by column chromatographyon silica gel using chloroform as eluent. |
Tags: 51762-67-5 synthesis path| 51762-67-5 SDS| 51762-67-5 COA| 51762-67-5 purity| 51762-67-5 application| 51762-67-5 NMR| 51762-67-5 COA| 51762-67-5 structure
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