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Chemical Structure| 66-71-7
Chemical Structure| 66-71-7
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Product Details of [ 66-71-7 ]

CAS No. :66-71-7 MDL No. :MFCD00011678
Formula : C12H8N2 Boiling Point : -
Linear Structure Formula :C2H2(C5NH3)2 InChI Key :DGEZNRSVGBDHLK-UHFFFAOYSA-N
M.W : 180.21 Pubchem ID :1318
Synonyms :
1,10-Phenanthroline
Chemical Name :1,10-Phenanthroline

Calculated chemistry of [ 66-71-7 ]

Physicochemical Properties

Num. heavy atoms : 14
Num. arom. heavy atoms : 14
Fraction Csp3 : 0.0
Num. rotatable bonds : 0
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 57.04
TPSA : 25.78 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -6.14 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.65
Log Po/w (XLOGP3) : 1.78
Log Po/w (WLOGP) : 2.78
Log Po/w (MLOGP) : 1.86
Log Po/w (SILICOS-IT) : 2.99
Consensus Log Po/w : 2.21

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -2.82
Solubility : 0.274 mg/ml ; 0.00152 mol/l
Class : Soluble
Log S (Ali) : -1.94
Solubility : 2.07 mg/ml ; 0.0115 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -5.0
Solubility : 0.00179 mg/ml ; 0.00000995 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.39

Safety of [ 66-71-7 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P264-P270-P273-P301+P310+P330-P391-P405-P501 UN#:2811
Hazard Statements:H301-H410 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 66-71-7 ]

* 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.

  • Upstream synthesis route of [ 66-71-7 ]
  • Downstream synthetic route of [ 66-71-7 ]

[ 66-71-7 ] Synthesis Path-Upstream   1~37

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[5] Russian Journal of Organic Chemistry, 2005, vol. 41, # 11, p. 1690 - 1693
[6] Recueil des Travaux Chimiques des Pays-Bas, 1935, vol. 54, p. 275,278
[7] Journal of the American Chemical Society, 1930, vol. 52, p. 397,400
[8] Journal of the American Chemical Society, 1950, vol. 72, p. 842
[9] Organic Letters, 2002, vol. 4, # 16, p. 2799 - 2801
[10] Journal of Physical Chemistry B, 2004, vol. 108, # 50, p. 19541 - 19549
[11] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2008, vol. 69, # 1, p. 49 - 55
[12] Dalton Transactions, 2008, # 28, p. 3701 - 3708
[13] Journal of Chemical Crystallography, 2009, vol. 39, # 6, p. 423 - 427
[14] Monatshefte fur Chemie, 2010, vol. 141, # 2, p. 157 - 168
[15] Inorganic Chemistry, 2017, vol. 56, # 3, p. 1366 - 1374
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  • [ 66-71-7 ]
  • [ 50890-67-0 ]
  • [ 4433-01-6 ]
  • [ 143825-63-2 ]
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[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1992, # 13, p. 1601 - 1606
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[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1992, # 13, p. 1601 - 1606
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  • [ 67-63-0 ]
  • [ 88111-63-1 ]
Reference: [1] Patent: US2003/65187, 2003, A1,
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YieldReaction ConditionsOperation in experiment
50% With potassium permanganate; potassium hydroxide In water for 5 h; Heating 1,10-Phenanthroline (4.0g, 22.2mmol) and KOH (4.0g, 71.3mmol) in water (250mL) were boiled for 1h. A hot solution of KMnO4 (10.0g, 63.3mmol) in water (150mL) was added drop wise over ca. 2h to the boiling mixture. The reaction mixture was boiled for another 2h and was filtered hot. The orange filtrate was cooled and extracted with chloroform. The combined organic extract was dried over anhydrous Na2SO4 and the solvent was removed to obtain a crude product. Further purification by column chromatography on silica gel using acetone/ petroleum ether (2:1) as eluent yielded pure 4,5-diazafluoren-9-one as a yellow solid (2g, 50percent). 1H NMR (CDCl3): δ=8.80 (d, 2H), 7.96 (d, 2H), 7.35 (d, 2H).
47.5% With potassium permanganate; potassium hydroxide In water for 9 h; Reflux In a 5L three-necked flask,Add o-phenanthroline (36g, 0.2mol)And freshly prepared potassium hydroxide solution (2.5L, 0.35M),Stir and heat to reflux.Dissolve 105.2g of potassium permanganate in 400mLAfter the water is heated and dissolved,Add a constant pressure dropping funnel to the reaction mixture.Control the dripping speed,About 4h finished,The reaction was continued at reflux for 5 h.Hot filter,Wash cake,Get orange filtrate,Let stand to cool to room temperatureExtract with dichloromethane (3 x 20 mL),Combine the extracts,Dry with anhydrous Na2SO4,Spin-evaporated to a light yellow solid,Finally recrystallized from methanol,Vacuum dryingYellow needle crystals (Compound 1)(17.3 g, 0.095 mol), yield 47.5percent.
47.5% With potassium permanganate; potassium hydroxide In water for 5 h; Reflux In a 5 L three-necked flask, phenanthroline (36 g, 0.2 mol) and a freshly prepared potassium hydroxide solution (2.5 L, 0.35 M) were added, stirred, and heated to reflux. 105.2 g of potassium permanganate was dissolved in 400 mL of water, dissolved by heating, and then added to the reaction mixture by a constant pressure dropping funnel to control the dropping rate. After about 4 hours, the reflux reaction was continued for 5 hours. The mixture was filtered while hot, and the filter cake was washed with water to give an orange-yellow filtrate, which was cooled to room temperature, and extracted with dichloromethane (3×20 mL). The extracts were combined, dried over anhydrous Na2SO4 and evaporated to give a pale yellow solid. Recrystallization of methanol, vacuum drying, to obtain yellow needle crystals (Compound 1)(17 · 3g, 0 · 095mol), yield 47 • 5percent mp: 213°C.
47.5% With potassium permanganate; potassium hydroxide In water for 9 h; Reflux In a 5L three-necked flask,Add phenanthroline (36g, 0.2mol) and freshly prepared potassium hydroxide solution (2.5L,0.35 M), stirred and heated to reflux.Dissolve 105.2 g of potassium permanganate in 400 mL of water.After heating and dissolving,Adding to the reaction mixture using a constant pressure dropping funnel,Control the drop rate,After about 4 hours,The reflux reaction was continued for 5 h.Hot filtered,Wash the filter cake,Obtaining an orange filtrate,Allow to cool to room temperature,Extracted with dichloromethane (3 x 20 mL),Combine the extracts,Dry with anhydrous Na2SO4,Evaporated to give a pale yellow solid.Finally recrystallized from methanol,Vacuum drying,Yellow needle crystals (compound 1)(17.3 g, 0.095 mol), yield 47.5percent
41% With potassium hydroxide; potassium permanganate In water at 80℃; for 0.5 h; A 2 L separable flask was charged with 18 g (99.9 mmol) of fenanthroline, 18 g (320.8 mmol) of potassium hydroxide and 900 g of water, and the content was heated to 80° C. A mixed liquid comprising 45 g of potassium permanganate and 720 g of water was dropwise added to the content while the content was stirred at that temperature. After the completion of addition, the stirring was further continued for 30 minutes and the reaction was terminated. The hot reaction liquid was filtered to remove manganese dioxide. Then the reaction liquid was allowed to cool to room temperature, and then extracted with chloroform. The extract was treated in the conventional manner, and concentrated to give a yellow powder. Recrystallization of the powder from acetone gave 7.54 g of a yellow needle crystal (yield: 41percent). The identification of the crystalline compound was conducted by 1H-NMR and 13C-NMR. 1H-NMR: (CDCl3, ppm); 8.80 (d, J=5.2, 2H), 8.05 (dd, J=7.6, 1.6, 2H), 7.36 (dd, J=7.6, 5.2, 2H) 13C-NMR: (CDCl3, ppm); 189.42, 163.31, 155.10, 131.45, 129.30, 124.69
39.3% at 125℃; for 13 h; In a 5-L three-necked flask, 1,10-phenanthroline (50 g, 0.28 mol) was added.2000mL new potassium hydroxide solution (0.36mol/L),The mixture was heated and dissolved with stirring, and 131.1 g of potassium permanganate (KMnO4) was weighed to form a saturated solution.The reaction warmed to 125°C.The saturated KMnO4 saturated solution was dropped into the reaction with a constant pressure dropping funnel, and was dripped for about 1 hour.Continue to react for more than 12h.After the end of the reaction, using a Buchner funnel hot filtration, cooling, and then extracted with dichloromethane (CH2Cl2, 3 x 20mL), the filtrate was dried over anhydrous sodium sulfate, rotary steam,Obtained pale yellow solid product 5H-cyclopenta[1,2-b:5,4-b']dipyridin-5-one (Compound 1) (20.8 g, 0.11 mol) in a yield of 39.3percent
35.5% With potassium permanganate; potassium hydroxide In water for 2 h; A mixture of 2. 5 g (13.75 mmol) of 1,10-phenanthroline,2. 5 g (44.65 mmol) of K0H was dissolved in 250 ml of water and heated to boiling.Another weighing 6.25 (39.5mmol) KMn04 dissolved in 200ml of hot water,The KMn04 solution was slowly added dropwise to the above-mentioned phenanthroline reaction solution,Control 2h drops finished,After dripping the reaction solution to continue boiling lOmin,Filter hot to remove Mn02,The filtrate was extracted with chloroform (3X200 ml)The organic phase was dried with anhydrous MnS04,The solvent was removed by distillation under reduced pressure on a rotary evaporator,The resulting solid was recrystallized from acetone to give a yellow crystal, 75 g,The yield was 35. 5percent
25% With potassium permanganate; potassium hydroxide In water for 2 h; Reflux Constant voltage dropping funnel in a 500 ml three-mouth bottle, sequentially adding a 1,10-O-phenan throline 5.9g in other words 0.03mol, potassium hydroxide 3.06g in other words 0.055mol, distilled water 200 ml, electromagnetic stirring under heating to reflux, the solid completely dissolved after to, self-constant-voltage dropping funnel dropping slowly added in an aqueous solution of potassium permanganate, the aqueous solution of potassium permanganate 15.2g potassium permanganate dissolved in 125 ml distilled water, after the add, to continue to reflux reaction 2h, hot filtering, cooling the filtrate after precipitation with yellow acicular crystal, pulls out worry, washing, drying to obtain light yellow crystal, yield 25percent,
23.02% With potassium permanganate; potassium hydroxide In water for 0.5 h; Reflux 1,10-Phenanthroline (0.025 mmol) and KOH (0.046 mmol) were added to 200 mL water and a resulting mixture was brought to a reflux followed by dropwise addition of aqueous solution of potassium permanganate (0.08 mmol) to it. After addition, the solution was refluxed for 30 min and filtered off to remove MnO2. When thesolution was cooled, crude 4,5-diazafluoren-9-one precipitated as yellow needles. Crystallization from water gives a desired ketone in pure form. Yield: 23.02percent, m.p.: 212-213 °C, chemical formula (mol.wt.): C11H6N2O (182.18 g/mol), elemental analysis: calc. (percent): C, 72.52; H, 3.32; N, 15.38, found (percent): C, 72.49; H, 3.34; N, 15.35. 1H NMR (CDCl3, 400 MHz) δ/ppm: 8.828, (dd, 2H, H3,6); 8.020, (dd, 2H, H1,8); 7.381, (dd, 2H, H2,7), 13C NMR (CDCl3, 100 MHz) δ/ppm: 188.42, (C9); 155.11, (C11,13); 152.38, (C3,6); 131.69, (C10,12); 129.40, (C1,8); 124.84, (C2,7), FT-IR (KBr, 4000-626 cm-1): ν(C-H), 3032; ν(C=O), 1713, ν(C=C), 1535; ν(C=N), 1497; ν(C=H), 710 (s).
23.5% With potassium permanganate; potassium hydroxide In water at 70 - 80℃; Weigh 5.00 g (25.3 mmol) of phenanthroline monohydrate and 5.00 g (89.3 mmol)Potassium hydroxide in water, heated to boiling,13.00 g (82.3 mmol) of potassium permanganate in hot water (150 mL water, stirring)70 ~ 80 °C) drip. After the addition was completed, the mixture was further stirred for 10 minutes while boiling, and filtered while hot.The solution was orange-red, and after cooling, it was extracted three times with chloroform, and the organic phases were combined and dried over anhydrous magnesium sulfate.Filter and finally distill off the solvent under reduced pressure. The acetone is recrystallized to give a pale yellow needle crystal product.The yield was 23.5percent (1.08 g).
71.6 mg With potassium permanganate; potassium hydroxide In water at 100℃; for 3.5 h; It is prepared by using 1,10-phenanthroline monohydrate as a raw material in an aqueous solution of potassium permanganate and potassium hydroxide. 1,10-phenanthroline monohydrate (5 g, 25.22 mmol) and potassium hydroxide (2.8 g, 49.91 mmol) were dissolved in 200 mL of distilled water and heated to 100 ° C under elevated temperature. Potassium permanganate (12.8 g, 80.99 mmol) was dissolved in 200 mL of distilled water, dissolved by heating, and slowly added dropwise to the above mixture over 1 hour, and the reaction was continued at 100 ° C for 2.5 h, and filtered while hot. After the filtrate was cooled, the pH was adjusted to 8-9 with 10percent hydrochloric acid and then extracted with dichloromethane (3×200mL), dried over anhydrous sodium sulfate and filtered. Concentrated organic phase,Silica gel column chromatography (dichloromethane as mobile phase)Purification to give a yellow-white solid a;

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YieldReaction ConditionsOperation in experiment
96% at 0 - 130℃; for 2.33333 h; Concentrated H2SO4 (35 ml) was added in a 250 ml three necked flask at 0 °C. 1,10-phenanthroline (2.5 g, 28 mmol) was slowly added in this three-necked flask. Then KBr (5 g, 42 mmol) and HNO3 (17.5 ml) were added at 5 °C. After stirring at room temperature for 20 min, the temperature was increased at 130 °C for 2 h. The hot yellow solution was poured over 150 g of ice and water and neutralized carefully with Na2CO3 until the pH of 6 7.The reaction mixture was extracted with CHCl3. The resultant solution was dried over anhydrous Na2SO4 and concentrated in vacuo. The precipitate was purified further by crystallization from absolute ethanol to give 2.4 g (96percent) of 1,10-phenanthroline-5,6-dione.
95% at 0 - 100℃; To a dry mixture of 1,10-phenanthroline (2 g, 0.011 mol) and KBr (10 g, 0.084 mol), H2SO4 (40 mL) followed by HNO3 (20 mL) were added dropwise at 0 °C. The resulting mixture was heatedat 100 °C until the bromine vapours disappeared. The solution was poured carefully onto ice and slowly neutralized to pH>7 with Na2CO3 (saturated solution and powder). The product was extracted with dichloromethane and dried over Na2SO4. The solvents were evaporated to give a yellow solid that was dried under vacuum (88-95percent).
92% Cooling with ice; Reflux Weigh 1,10-phenanthroline 2.0g, selenium dioxide 6.0g,Mix well in a flask and add 20 mL concentrated sulfuric acid with a concentration of 18 mol•L-1.10 mL of concentrated nitric acid with a concentration of 14 mol·L-1 was mixed and cooled in an ice water bath to form a cooled mixed acid. Slowly add the cooled mixed acid along the wall of the flask, add dropwise, heat and reflux, graduallyGenerate red-brown gas. The heating was stopped to obtain a reddish-brown transparent solution; a reddish-brown transparent solution was poured into ice water, and the acid was slowly neutralized with NaOH until the reaction mixture had PH=7. This process resulted in more yellow flocculent precipitates, which were filtered to obtain a yellow precipitate. Extract three times with methylene chloride, combine the organic phases, wash twice with water, and combine the organic phases. The organic phase is rotary evaporated to give a yellow powder as compound (II). Methanol is recrystallized and dried. The yield is 92percent.
90% Reflux Phenyl imidazo [5,6-f] o-phenanthroline: Weigh 1,0-phenanthroline 2.0 g, selenium dioxide 6.0 g, and mix well in a flask, 20 mL concentration is 18 mol•L-1 The concentrated sulfuric acid was mixed with 10 mL of concentrated nitric acid at a concentration of 14 mol·L-1 and cooled in an ice water bath to form a cooled mixed acid. The cooled mixed acid was slowly added dropwise along the wall of the flask. After the dropwise addition was completed, the mixture was heated under reflux and a reddish-brown gas gradually formed in the flask. The heating was stopped to obtain a reddish-brown transparent solution; a reddish-brown transparent solution was poured into ice water, and the acid was slowly neutralized with NaOH until the reaction mixture had PH=7. This process resulted in more yellow flocculent precipitates, which were filtered to obtain a yellow precipitate. Extract three times with dichloromethane, combine the organic phases, wash twice with water, and combine the organic phases. The organic phase is rotary evaporated to give a yellow powder as compound (II). Methanol is recrystallized for drying. The yield is 90percent.
87% at 0 - 130℃; for 3.33333 h; To a stirred concentrated sulfuric acid (60 mL) and concentrated nitric acid (30 mL) containing compound 1,10-phenanthroline (5.00 g, 27.76 mmol) and potassium bromide (9.91 g, 83.30 mmol) at 0 °C for 20 min, and then gradually heated up to 130 °C and reflux 3 h. After cooling to room temperature, the solution was poured into plenty of crushed ice, the resulting mixture was neutralized to pH 7.0 with sodium carbonate and then the extract was washed successively with water and brine. The organic extracts were concentrated, and recrystallized from methanol to give 5 as a yellow solid in 87percent yield. M.p. 260–261 °C. 1H NMR (400 MHz, CDCl3, TMS): δ 7.58–7.61 (m, 2H), 8.51 (d, 2H, J = 8.0 Hz), 9.11 (d, 2H, J = 8.0 Hz). IR (ν, KBr, cm−1): 739, 1459, 1561, 1576, 1686, 3061.
87% at 0 - 130℃; for 3 h; To a stirred concentrated sulfuric acid (60 mL) and concentratednitric acid (30 mL) containing compound 1,10-phenanthroline(5.00 g, 27.76 mmol) and potassium bromide (9.91 g, 83.30 mmol)at 0 °C for 20 min, and then gradually heated up to 130 °C and reflux3 h. After cooling to room temperature, the solution was pouredinto plenty of crushed ice, the resulting mixture was neutralizedto pH 7.0 with sodium carbonate and then the extract was washedsuccessively with water and brine. The organic extracts were concentrated,and recrystallized from methanol to give 5 as a yellowsolid in 87percent yield. M.p. 260–261 °C. 1H NMR (400 MHz, CDCl3, TMS): δ7.58–7.61 (m, 2H), 8.51 (d, 2H, J = 8.0 Hz), 9.11 (d, 2H, J = 8.0 Hz).IR (ν, KBr, cm−1): 739, 1459, 1561, 1576, 1686, 3061.
82% at 100℃; for 4 h; Cooling with ice; Inert atmosphere; Schlenk technique Concentrated sulphuric acid (98percent w/v, 40 ml) and concentrated nitric acid (69percent w/v, 20 ml) were added to a loosely stoppered round bottom flask equipped with a condenser and cooled in an ice bath. Finely ground 1,10-phenanthroline (4 g, 0.022 mol) and sodium bromide (4 g, 0.039 mol) were added slowly and reaction mixture was heated and stirred under a nitrogen atmosphere at 100 °C for 4 h. After cooling to room temperature the reaction mixture was poured into crushed ice (200 g). Sodium hydroxide pellets (18 g) were added slowly in small portions and further sodium hydroxide as an aqueous solution was slowly added to achieve neutrality (approximately 75 ml of a 40percent w/v solution was required). The solution was extracted with chloroform (3 150 ml), the combined organic layers were washed with saturated brine (100 ml) and dried (MgSO4) and the volatiles removed in vacuo, to yield a bright yellow solid (yield 3.80 g, 82percent).
80% at 100℃; for 3 h; Synthesis of 1,10-phenanthroline-5, 6-dione According to (J. Am. Chem. Soc. 1993, 115, 3448) method: 4.0 g of phenanthroline and 4.0 g of potassium bromide The mixture was stirred and placed in a 250 mL round bottom flask and then mixed with cold concentrated sulfuric acid (40 mL) and concentrated nitric acid (20 mL). After heating, the mixture was heated to reflux at 100 ° C for 3 h, cooled to room temperature, poured into 500 mL of ice water and then neutralized with lOmolL NaOH solution. The solution was extracted with 3 x 100 mL of chloroform and the organic phase , Washed with 50 mL of water, and finally dried over anhydrous sodium sulfate overnight. Filter, remove the chloroform under reduced pressure, solid product ethanol recrystallization, orange-yellow needle-like crystals, suction filtration, washing, drying, the yield of 80percent.
80% at 80℃; for 3 h; 5 g was added to a round bottom flask1,10-phenanthroline hydrate with25 g of potassium bromide in 100 mL concentrated sulfuric acid and50 mL of concentrated nitric acid (2: 1, ν: ν) at 80 ° C for 3 hours,After cooling, the reaction solution was neutralized with aqueous sodium hydrogencarbonate solution, and the organic phase was collected by extraction and extraction.And concentrated to give a diketone derivative of 1,10-phenanthroline.Yield: 80percent
78%
Stage #1: for 0.333333 h; Cooling
Stage #2: at 20℃; for 3 h; Reflux
The pdn ligand was prepared according to Yamada et al.[23]. To 40 cm3 of an ice-cold concentrated H2SO4 wasadded a mixture of 2.0 g 1,10-phenanthroline (10.1 mmol)and 12.0 g KBr (100.8 mmol). After the mixture wasstirred for 20 min, 20 cm3 of concentrated HNO3 wasadded dropwise at room temperature and the resultingsolution was heated at reflux for 3 h. The mixture was thencooled, poured on ice, neutralized with NaOH, and thenextracted with CHCl3. The collected yellow extract wasdried over MgSO4 and the solvent removed in vacuo. Aftercrystallization from ethanol, an orange–yellow solid wasobtained (1.66 g, 78 percent yield). M.p.: 263.5–264.2 C (Ref.[23] 271–272 C).
68% at -78 - 150℃; A well-ground mixture of 10.0 g (50mmol) phenanthroline monohydrate and 9.05 g (76.0 mmol) KBr in a round bottom flask fittingwith a dropping funnel was mounted in a cooling bath at -10 °C. A mixture of H2SO4 (91 mL,96percent) and HNO3 (42 mL, 65percent) at -78 °C maintained by ducking into liquid nitrogen was gently added to the first mixture during 30 min. The resulting reddish-orange suspension was left undisturbed for cooling to room temperature (rt) and refluxed at 150 °C until bromine evolution to cease (5-7 h). The obtained yellow suspension was cooled to rt, gradually poured into 1 kgice, and pH of the mixture was raised up to 6 by adding 30percent NaOH. The final yellow mixturewas extracted with dichloromethane, dried on anhydrous Na2SO4, recrystallized from hotmethanol, and dried in air [41]. Yield: 7.15 g (68percent), mp 257 °C.
67% With sulfuric acid; nitric acid; potassium bromide; sodium hydroxide In water at 90℃; for 4 h; Cooling with ice Preparing Example 1
Synthesis Of 1,10-Phenanthroline-5,6-Dione
1,10-phenanthroline (10.0 g, 55.5 mmol) and potassium bromide (15.0 g, 126 mmol) were in 250 ml two-neck bottle and the outlet of the condenser tube was introduced with a rubber pipe into NaOH aqueous solution.
Sulfuric acid (100 mL, 98percent) was poured under ice bath condition, and then fuming nitric acid (50.0 mL, 68percent w/w) was added after removing ice bath.
Then, the temperature was increased to 40° C. for three hours and further increased to 80˜90° C. for one hour.
And then, the temperature decreased and the condenser tube was removed, waiting for the dispersion of bromine gas which remained in the bottle.
After 1˜2 hours, the solution in the bottle was poured into ice water and NaOH aqueous solution was added slowly until pH of the mixed solution reached 6˜7.
At this time, a large number of yellow solid precipitations were produced, filtered with clean water and then collected as products.
Finally, the yellow solids of 7.81 g with a yield of 67percent were obtained by recrystallizing the said products with methanol.
1H NMR (400 MHz, CDCl3, δ): 9.11 (dd, J=4.4, 1.6 Hz, 2H), 8.49 (dd, J=7.6, 1.6 Hz, 2H), 7.57 (dd, J=4.8, 8 Hz, 2H),
13C NMR (100 MHz, CDCl3, δ): 178.5, 156.2, 152.7, 137.1, 127.9, 125.5.
66% at 85℃; for 3 h; Cooling with ice An ice cold mixture of concentrated H2SO4 (40 mL) and HNO3(20 mL) was added to 4.0 g of 1, 10-phenanthroline and 4.0 g of KBr.The mixture was heated at reflux for 3 h, andmaintaining the temperatureat 85 °C. The hot yellowsolutionwas poured over 500 mL of ice andneutralized carefully with NaOH until neutral to slightly acidic pHandextracted with CHCl3 for 3 times, then drying it with Na2SO4. The productwas followed by the process of removing the solvent and purifiedfurther by crystallization from ethanol, which gave a yellow needlecrystal 3.1 g (66percent).
62% With nitric acid; potassium bromide In sulfuric acid at 0 - 100℃; for 6 h; 5.0 g (25.2 mmol) of 1,10-phenanthroline monohydrate was dissolved in 60 mL of concentrated sulfuric acid and 2.9 g (25.2 mmol) of potassium bromide was slowly added at 0 °C. 30 mL of concentrated nitric acid was added dropwise to the mixture and the resulting mixture was stirred for 6 h at 100 °C. Then, the mixture was poured into the ice (400 g) and neutralized with aq 40percent KOH solution until the pH = 7. After cooled to room temperature, the turbid solution was filtered. The aqueous solutions were extracted with CH2Cl2, dried over anhydrous magnesium sulfate and filtered.
The solvent was evaporated under reduced pressure, and the product was recrystallized from methanol to give the pure dione (3.28 g, 62percent).
1H NMR(400 MHz, CDCl3): δ = 9.11-9.13 (dd, 2H), 8.50-8.52 (dd, 2H), 7.59-7.61 (dd, 2H). MS: m/z = 210.04 (M+).
60.8% at 110℃; for 2.5 h; Cooling with ice In a 250mL three-necked flask was added 10g 1,10-phenanthroline (55. 6mmol), ice salt bath was added rapidly 60mL concentrated sulfuric acid,After dissolving rapidly added 13. 2g KBr (11 lmmol),Slowly add 30mL concentrated nitric acid, warmed to 110 ° C reaction 2. 5h,The reaction was cooled to room temperature, the reaction solution was poured into 500g crushed ice, neutralized with 10mol / L NaOH solution, precipitationA large number of yellow solid, suction filtration, washed with a large amount of distilled water, recrystallized ethanol to give yellow needle crystal, filtration, vacuum drying,7. 7g was obtained, the yield of 60.8percent.
57%
Stage #1: With sulfuric acid; nitric acid; sodium bromide In water for 6 h; Reflux
Stage #2: With sodium hydroxide In water at 20℃;
1,10-Phenanthroline-5,6-dione was synthesized according to a modified literature procedure. 1,10-Phenanthroline monohydrate (10 g, 50.4 mmol) was dissolved in 60 mL of concentrated sulfuric acid. Sodium bromide (5.19 g,50.4 mmol) was then added, followed by 30 mL of 70 wtpercent nitric acid. The mixture was heated under reflux for 6 h. After 6 h, the temperature was reduced to 95 C, and the reflux condenser was removed to allow bromine vapors to escape overnight. After cooling, the mixture was poured onto 800 g of ice, carefully neutralized to pH 7 with 10 M sodium hydroxide, and cooled to room temperature. The resulting turbid solution was filtered. The aqueous phase was extracted with CH2Cl2, and the organic phase was dried over anhydrous magnesium sulfate and then evaporated under reduced pressure. The crystalline residue was recrystallized from 300 mL of methanol to give the pure dione. Yield: 57 percent (6.0 g). 1H NMR (400 MHz, CDCl3):9.11–9.13 (dd, 2H), 8.50–8.52 (dd, 2H), 7.59–7.61 (dd,2H).
50% at 80℃; for 1 h; 30 mL of concentrated sulfuric acid was charged into a three- necked flask, and 5.0 g of 1,10-phenanthroline was added with stirring, After being dissolved,to the solution was add 2.5 g of NaBr and 15 mL of 70percent HNO3 heated solution to boil, and reflux for 1 hour; then remove the reflux condenser and keep the micro-boiling for about 15 min. After cooling, the mixture was added to 400 g of crushed ice, about 150 mL of 5M NaOH, adjust the pH to 7, still, filter, the solid was extracted with 100 mL of boiling water, filtering out the insoluble matter; Then extracted with 100 mL of dichloromethane, the organic phase was washed with water, then dried over anhydrous sodium sulfate, the dichloromethane was removed by distillation, The solid was recrystallized from 400 mL of toluene to give an orange needle-like crystal, filter, dry, obtaining the intermediate product 1 (R1 is a hydrogen atom, 2.3 g, yield 50percent).
47% at 90℃; for 3 h; Reflux l,10-Phenanthroline-5,6-dione was synthesized following a literature procedure (Calderazzo, F.; Marchetti, F.; Pampaloni, G.; Passarelli, V. J. Chem. Soc, Dalt. Trans. 1999, 4389). Briefly, concentrated sulfuric acid (82 mL) was cooled with liquid nitrogen, to which a mixture of 1 , 10-phenanthroline (3.65 g, 20.3 mmol, 1 eq) and potassium bromide (24.85 g, 209 mmol, 10 eq) were added. The mixture was allowed to warm to RT in air and was then submerged in a water bath. Concentrated nitric acid (45 mL) was then added dropwise to the solution after which the reaction mixture was refluxed at 90 °C. After 3 h, the bromine evolved from the reaction was boiled off, and the reaction was quenched over ice such that the total volume of liquid after quenching was 500 mL. The solution was neutralized with sodium carbonate and extracted into chloroform. The chloroform solution was dried over MgS04 and filtered. The solvent was removed from the filtrate in vacuo, and the resulting crude product was recrystallized in ethanol to furnish compound 44 as a yellow solid in 47percent yield. The purity of the product was verified via ^-NMR. 1H-NMR (400 MHz, DMSO-d6) δ (ppm): 8.99 (dd, 2H), 8.39 (dd, 2H), 7.67 (dd, 2H).
41.7% With sulfuric acid; nitric acid; potassium bromide In water at 5 - 120℃; for 2.83333 h; 1,10-Phenanthroline-5,6-dione was obtained according to the previous report with slight modification [40]. 5.00 g (25 mmol) 1,10-Phenanthroline monohydrate was slowly added into a 250 mL three-necked flask of 60 mL concentrated sulfuric acid, cooled down with ice-water. 15 g (126 mmol) KBr and 30 mL concentrated nitric acid were added to the solution below 5 °C. The mixture was stirred for 20 min at room temperature and heated to 120 °C for 2.5 h. The reaction solution was neutralized to pH 6–7 with NaOH after pouring into 300 g trash ice, during which time a precipitate appeared, the precipitate was filtrated under vacuum, the filter liquor was extracted by using dichloromethane and concentrated and then recrystallized from methanol to yield yellow powder. Yield: 41.7percent. m.p.: 250.7–251.7 °C. 1H NMR (DMSO, d, ppm): 7.69 (s, 2H), 7.67–7.66 (d, 2H), 7.65 (s, 2H). ES-MS(M/z, M + 1): 211.2.
30% for 2 h; Reflux The ligand phenD was prepared by oxidation of commercially available phen according to the literature [23]. A mixture of potassium bromide (29.750g, 0.250mol) and phen (5.000g, 0.028mol) in 96percent sulfuric acid (75mL) and 65percent nitric acid (37.5mL) was refluxed and stirred for 2h. The reaction mixture was diluted with water (1000mL) and neutralized with sodium bicarbonate. The mixture was then extracted three times with dichloromethane (3×300mL). The organic phase was dried over sodium sulfate for 30min and the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized in methanol to obtain phenD as a yellow powder. Yield: 30percent. Anal. Elemental analysis: Calc.: C12H6N2O20.2 CH3OH (percent): C, 67.65; H, 3.16; N, 12.93. Found: C, 67.28; H, 2.95; N, 13.23. 1H NMR (400MHz, CDCl3): δ=7.59 (dd, 2Hphen, J=4.68Hz, J=7.87Hz); 8.50 (dd, 2Hphen, J=1.85Hz, J=7.87Hz); 9.12 (dd, 2Hphen, J=1.84Hz, J=4.70Hz) ppm. HR ESI-MS: m/z [M+H]+ Calc.: 211.0502, Found: 211.0533; [M+Na]+ Calc.: 233.0321, Found: 233.0365.

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YieldReaction ConditionsOperation in experiment
63% for 12 h; Reflux In a 500 ml bottle of the, adding 200mL1-chlorobutane, 1,10-O-phenan throline 5g in other words 27.8mmol, S2Cl212.3g in other words 91.1mmol, pyridine 7.10g in other words 89.8mmol and liquid bromine 14g in other words 87.6mmol, reflux reaction 12h, a large amount of solids in the reaction process to produce. Cooling to room temperature, the reaction the fluid pulls out worry, washing the solid with large quantities of sodium hydroxide, with the filtrate CHCl3extraction, the organic phase turns on lathe does and, combined with the solid pulls out worry, dry together CHCl3too short. The column after CHCl3concentrated to 60 ml, then adding bromine 3.0g in other words 19mmol stir at room temperature 30 min, to form a yellow Phen-Br2complex. pulls out worry, with solid dry 200-300 mesh silica gel as stationary phase, methylene chloride/ethyl acetate = 1/1 elution medicinal preparation column chromatographic analysis separation, then recrystallized with toluene to obtain white needle-like solid 5.9g, yield63percent,
5.9 g for 12 h; Reflux 1,10-phenanthroline (5 g, 27.8mmol), S2Cl2 (12.3 g, 91.1mmol), pyridine (7.10 g, 89.8mmol), Br2 (14 g, 87.6 mmol) in 1-chlorobutane (200 mL) and the mixture 12 heating time, the mixture was stirred. After the reaction was completed, a solid produced was separated lowering to room temperature. It was added an excess of NaOH and extracted with dichloro-menthane with water and dried over MgSO4. SiO2 column and recrystallized with dichloromethane to obtain the compound 1-A (5.9 g).
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  • [ 66127-01-3 ]
  • [ 100125-12-0 ]
Reference: [1] Journal of Materials Chemistry, 2001, vol. 11, # 7, p. 1769 - 1771
  • 19
  • [ 66-71-7 ]
  • [ 4199-88-6 ]
YieldReaction ConditionsOperation in experiment
99% at 160℃; for 3 h; 1,10-phenanthroline added slowly to fuming nitric acid (10ml) was dissolved 10g (55.49mmol) in concentrated sulfuric acid (20ml) at 160o C, the reaction was carried out for 3 hours at 160oC jundwi. After the reaction was completed, the reaction mixture was diluted with ice water and adjusted to pH 3 with a saturated aqueous sodium hydroxide solution. The resulting yellow solid was filtered, washed with water, and concentrated under reduced pressure to give 5-nitro-1,10-phenanthroline(6.2 g, 99percent).
90% at 0 - 150℃; for 3 h; In an ice-cooled solution of 5.0 g (27.8 mmol) 1,10-phenanthroline, 30 ml concentrated sulphuric acid was added. Fifteen millilitres of fuming nitric acid were then added dropwise while keeping the temperature at 0°C. The reaction mixture was then stirred at 150°C for 3 h and subsequently poured into 200-ml ice-cold distilled water. Subsequently the pH was brought to 3 by the slow addition of the concentrated solution of NaOH. The precipitate of 5-nitro-1,10-phenanthroline was filtered off, washed with water and brownish precipitates were formed, which were filtered and dried in vacuum. The filtrate was further extracted with chloroform to extract the residual traces of compound. The compound was obtained in 6.12 g, 90percentyield.
68%
Stage #1: With sulfuric acid; nitric acid In water at 100 - 110℃;
Stage #2: With sodium hydroxide In water at 20℃;
EXAMPLE 5; Synthesis of Compound 5 Step 1 Referring to Scheme 5, 237 ml sulfuric acid (concentrate) was first added to a 1 L three-necked flask. 35 g 1,10-phenanthroline was then added into the flask, and the temperature of mixture was kept lower than 100° C. Next, 2436 ml (67percent) HNO3 was added drop by drop, and the temperature of mixture was kept lower than 110° C. The mixture was subsequently heated to 100° C. and stirred overnight. After completion of reaction, the reaction mixture was cooled to room temperature and placed into 2 L water, and then NaOH(aq) was added to adjust pH value to a range from 6 to 7, so as to give solids. The solids were washed by water, and dried to obtain solids 5-nitro-1,10-phenanthroline 30 g (0.13 mol, yield 68percent).
65% at 120℃; for 3 h; 1,10- phenanthroline (1.23 g, 6 mmol) was dissolved in concentrated H2SO4 (10 mL) and concentrated HNO3 (5 mL) was added dropwise to this mixture. The mixture was heated to120 °C in an oil bath while stirring for 3 h. It was cooled to 0 °C before neutralization with NaOH to give yellow precipitates which were collected by filtration and thoroughly washed with ice-cold water. The solid part was further purified by recrystallization from 95 percent ethanol. 0.80 g, 65 percent yield,mp: 200–202 °C (lit. 197–198 °C). 1H NMR (400 MHz,CDCl3) δ = 9.40 (d, J = 4 Hz, 1H), 9.34 (d, J = 4 Hz, 1H),9.08 (d, J = 8.4 Hz, 1H), 8.74 (s, 1H), 8.47 (d, J = 8.4 Hz, 1H),7.88–7.81 (m, 2H); FTIR-ATR (cm−1): 3413,3082, 3028,2971,1738, 1639, 1517, 1356, 1106, 883, 807.
24% at 150 - 170℃; for 3 h; 1) 10.0 g (55.5 mmol) of 1,10-phenanthroline (Phen) was placed in a 250 ml three-necked flask,Then in a three-necked flaskAdd 15.0 mL of concentrated sulfuric acid and put it into magnet.2)The three-necked flask was mounted on a DF-101S heated thermostatic heated magnetic stirrer,In the three-necked flask on the installation of reflux condenser,And the glass plug with three plugs of the remaining two mouth.The oil bath temperature was set at 150 ° C and stirred,When the temperature reaches the set temperature,In the three-necked flask, 60 ml of a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1: 1 was slowly added dropwise (the temperature of the system at the time of dropping the mixture should be controlled below 170 ° C).Then reflux reaction 3h,After the reaction is finishedA three-necked flask was allowed to cool naturally to room temperature.3) Add the liquid from the three-necked flask to the deionized water of ice.Followed by neutralization with a concentration of 30percent NaOH solution to a pH of about 6.0.At this time precipitation of pale yellow precipitate,And then through the filter,Washed,Dried to give a yellow solid.The yellow solid was recrystallized from ethanol,After filtration and drying, 2.2 g of a yellow powder was obtained,This powder is 5-nitro-1,10-phenanthroline (Phen-NO2)The yield was 24percent.

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  • 26
  • [ 66-71-7 ]
  • [ 31535-89-4 ]
  • [ 24721-92-4 ]
  • [ 22426-14-8 ]
YieldReaction ConditionsOperation in experiment
75% With n-butyllithium In tetrahydrofuran; hexane 1.2.
Preparation of 2-bromo[1,10]phenanthroline
This was prepared according to the literature from 1-methyl-1H-[1,10]phenanthrolin-2-one: S.
Ogawa et al.; J. Chem. Soc. Perkin Trans.
1; 1974; 976-978, or alternatively via the following synthetic route:
10.0 ml (0.016 mol) of a 1.6 M solution of butyllithium in hexane was cooled to 0° C. and a solution of 0.72 g (0.008 mol) of N,N-dimethylaminoethanol in 10 ml of hexane was added dropwise over a period of 15 minutes.
The reaction mixture was cooled to -78° C. and a solution of 0.72 g (0.004 mol) of [1,10]phenanthroline in 5 ml of hexane was subsequently added dropwise.
After one hour, a solution of 3.32 g (0.010 mol) of CBr4 in 25 ml of THF was added.
After one hour at -78° C., the reaction mixture was admixed with 20 ml of a 10percent strength aqueous HCl solution.
The aqueous phase was extracted twice with 20 ml of diethyl ether.
The combined organic phases were dried over MgSO4, filtered and the solvent was distilled off at reduced pressure.
Column chromatography (eluent: ethyl acetate/hexane) gave 0.78 g (0.003 mol) of the product in a yield of 75percent.
Reference: [1] Patent: US2010/234548, 2010, A1,
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Reference: [1] Patent: US2007/83053, 2007, A1, . Location in patent: Page/Page column 7
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  • [ 71-36-3 ]
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Reference: [1] Patent: US2003/65187, 2003, A1,
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  • [ 42906-19-4 ]
Reference: [1] Patent: US2013/1521, 2013, A1,
  • 32
  • [ 66-71-7 ]
  • [ 591-50-4 ]
  • [ 620-93-9 ]
  • [ 20440-95-3 ]
YieldReaction ConditionsOperation in experiment
67% With KOH In toluene 4-Methyl-N-phenyl-N-p-tolylaniline (G)
4,4'-dimethyldiphenylamine (0.99 g, 5.0 mmol), KOH (2.52 g, 45.0 mmol), CuCl (99 mg, 1.0 mmol) and 1,10-phenanthroline (180 mg, 1.0 mmol) were charged in a two-necked bottle.
The bottle was deoxygenated and purged with nitrogen, and added dried toluene (12 mL) and iodobenzene (0.67 ml, 6.0 mmol).
The reaction was heated to 120° C., and stirred for 12 hours.
The resulting was filtered to remove metal and then concentrated under reduced pressure and the residue was purified by column chromatography (hexanes/CH2Cl2=1/1) to afford G (916 g, 67percent) as white solid.
1H NMR (400 MHz, CDCl3): δ 7.22-7.18 (m, 2H), 7.07-6.91 (m, 11H), 2.31 (s, 6H).
13C NMR (100 MHz, CDCl3): δ 148.3, 145.4, 132.3, 129.8, 129.0, 124.4, 122.9, 121.7, 20.8.
HRMS (m/z): [M+] calcd. for C20H19N, 273.1517.
Found, 273.1516.
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Reference: [1] Patent: US5648542, 1997, A,
  • 34
  • [ 66-71-7 ]
  • [ 4023-34-1 ]
  • [ 372-09-8 ]
  • [ 118431-88-2 ]
YieldReaction ConditionsOperation in experiment
54% With n-butyllithium In tetrahydrofuran; water; ethyl acetate EXAMPLE 1
3-Cyclopropyl-3-oxopropanenitrile
To a mechanically stirred solution of 15.0 g (176 mmol) 2-cyanoacetic acid and 100 mg 1,10-phenanthroline in 500 mL THF at -78° C. was added 141 mL (352 mmol) 2.5M n-butyllithium in hexanes.
The solution was warmed in a water bath to 0° C.
After 15 minutes at 0° C. most of the brown color had faded.
The mixture was cooled to -78° C. and to it was added a solution of 8.0 mL (88 mmol) cyclopropanecarbonyl chloride in 8 mL THF.
The mixture was warmed to RT and stirred 15 minutes, was poured into 300 mL 5percent HCl solution in water, and was extracted three times with ether.
The combined organic material was washed with saturated aqueous sodium bicarbonate then with brine, was dried over magnesium sulfate, was stripped of solvent in vacuo, and was chromatographed on silica gel under medium pressure using 30percent ethyl acetate in hexanes to give 6.5 g (54percent yield) of the title compound.
The title compound was stored with 1percent w/w BHT in 40 mL CH2 Cl2 at -5° C. Rf 0.12 in 20percent EtOAc/hexane, visualized by ninhydrin stain (green tint); 1 H-NMR (300 MHz, CDCl3): δ3.63 (s, 2H), 2.10 (m, 1H), 1.20 (m, 2H), 1.10 (m, 2H).
54% With n-butyllithium In tetrahydrofuran; water; ethyl acetate EXAMPLE 1
3-Cyclopropyl-3-oxopropanenitrile
To a mechanically stirred solution of 15.0 g (176 mmol) 2-cyanoacetic acid and 100 mg 1,10-phenanthroline in 500 mL THF at -78° C. was added 141 mL (352 mmol) 2.5M n-butyllithium in hexanes.
The solution was warmed in a water bath to 0° C.
After 15 minutes at 0° C. most of the brown color had faded.
The mixture was cooled to -78° C. and to it was added a solution of 8.0 mL (88 mmol) cyclopropanecarbonyl chloride in 8 mL THF.
The mixture was warmed to RT and stirred 15 minutes, was poured into 300 mL 5percent HCl solution in water, and was extracted three times with ether.
The combined organic material was washed with saturated aqueous sodium bicarbonate then with brine, was dried over magnesium sulfate, was stripped of solvent in vacuo, and was chromatographed on silica gel under medium pressure using 30percent ethyl acetate in hexanes to give 6.5 g (54percent yield) of the title compound.
The title compound was stored with 1percent w/w BHT in 40 mL CH2 Cl2 at -5° C. Rf 0.12 in 20percent EtOAc/hexane visualized by ninhydrin stain (green tint); 1 H-NMR (300 MHz, CDCl3): δ3.63 (s, 2H), 2.10 (m, 1H), 1.20 (m, 2H), 1.10 (m, 2H).
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