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Chemical Structure| 16433-88-8
Chemical Structure| 16433-88-8
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Product Details of [ 16433-88-8 ]

CAS No. :16433-88-8 MDL No. :MFCD00019048
Formula : C13H8Br2 Boiling Point : -
Linear Structure Formula :- InChI Key :AVXFJPFSWLMKSG-UHFFFAOYSA-N
M.W : 324.01 Pubchem ID :140073
Synonyms :

Calculated chemistry of [ 16433-88-8 ]

Physicochemical Properties

Num. heavy atoms : 15
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.08
Num. rotatable bonds : 0
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 70.29
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.52 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.11
Log Po/w (XLOGP3) : 5.29
Log Po/w (WLOGP) : 4.78
Log Po/w (MLOGP) : 5.06
Log Po/w (SILICOS-IT) : 5.29
Consensus Log Po/w : 4.71

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -5.77
Solubility : 0.000546 mg/ml ; 0.00000168 mol/l
Class : Moderately soluble
Log S (Ali) : -5.04
Solubility : 0.00295 mg/ml ; 0.00000911 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -6.87
Solubility : 0.000044 mg/ml ; 0.000000136 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.23

Safety of [ 16433-88-8 ]

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:

Application In Synthesis of [ 16433-88-8 ]

* 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 [ 16433-88-8 ]
  • Downstream synthetic route of [ 16433-88-8 ]

[ 16433-88-8 ] Synthesis Path-Upstream   1~24

  • 1
  • [ 86-73-7 ]
  • [ 1133-80-8 ]
  • [ 16433-88-8 ]
Reference: [1] Synthetic Communications, 2008, vol. 38, # 12, p. 1888 - 1895
[2] Chemische Berichte, 1920, vol. 53, p. 1236
[3] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1927, vol. 184, p. 608[4] Bulletin de la Societe Chimique de France, 1927, vol. <4> 41, p. 60
[5] Anales de la Asociacion Quimica Argentina (1921-2001), vol. 15, p. 198 Anm. 26[6] Chem. Zentralbl., 1928, vol. 99, # I, p. 1410
[7] Annales de Chimie (Cachan, France), 1930, vol. <10> 14, p. 52,55, 95
  • 2
  • [ 86-73-7 ]
  • [ 16433-88-8 ]
YieldReaction ConditionsOperation in experiment
98% With CuBr2-Al2O3 In tetrachloromethane for 5 h; Reflux To a solution of fluorene (1.5 g, 9.0 mmol) in CCl4 (80 mL) was added 30 g of copper-(II) bromide on alumina. The mixture was stirred at reflux for 5 h. After cooling the solution at room temperature, the solid material was filtered and washed with CCl4 (50 mL). The organic solution was dried over magnesium sulfate. Removal of solvent produced 2.87 g (98percent) of the title product as yellow solids. Recrystallization was made in a mixture of ethyl acetate/ hexane (5:95 v/v) to give pale yellow crystals as pure product 1.
97% With iron(III) chloride; bromine In chloroform at 0 - 20℃; for 3.25 h; Darkness To a 250 cm3 round-bottom flask, wrapped in aluminumfoil, was added 10.00 g fluorene (60 mmol) and 50 cm3CHCl3. The solution was cooled to 0 C and 0.14 g ferricchloride (0.9 mmol) was added. Bromine (6.52 cm3,126 mmol) was added slowly over 15 min at which pointthe ice bath was removed and the solution allowed to warmslowly over 3 h. The mixture was washed with Na2SO3(aq) and extracted with CHCl3 followed by drying withMgSO4, and the solvent was evaporated in vacuum toafford the desired product (19 g, 97 percent yield) as whitepowder without further purification. m.p.: 162–164 C(Ref. [40] 161–164 C).
95% With bromine In chloroform at 0℃; Darkness In a 250 mL round bottom flask,Will be 5 g(30.1 mmol)Fluorene solutionTo 50 mL of dry chloroform,13.25 g 83 mmol (2.75 times) of liquid bromine was dissolved in 30 mL of dry chloroform solution,The above mixed solution was added dropwise to the reaction flask at 0 ° C in a constant pressure dropping funnel and stirred overnight in the dark, and the saturated Na2S2O3 solution was added to the reaction solution to neutralize the excess liquid bromine,Quenching reaction,Dispensing,After the organic layer was washed several times with water,In the organic phase by adding anhydrous MgSO4 dry for half an hour,Filtered to remove anhydrous magnesium sulfate,Vacuum spin to remove the solvent,Recrystallization from ethanol,Afforded the white solid 2,7-dibromo-9H-fluorene 2a in yield
95% With bromine In chloroform at 0℃; In 250 mL round-bottomed flask, 5 g fluorene dissolved in 50 mL dry chloroform, to 4.18 mL (2.74 times) of liquid bromine was dissolved in 30 mL chloroform solution was dried, pressure-equalizing dropping funnel at 0 ° C and was added dropwise to the above mixed reaction flask.Was stirred overnight protected from light, saturated Na2S2O3Was added to the reaction mixture and the excess liquid bromine in the quench the reaction, liquid separation, the organic layer was washed several times with water, the organic phase was added anhydrous MgSO4Dried for half an hour, filtered to remove anhydrous magnesium sulfate, the solvent was removed by rotary evaporation in vacuo and recrystallized from ethanol to give a white solid 2a, in 95percent yield.
95% With bromine In chloroform at 0℃; Darkness In a 250 mL round bottom flask,Dissolve 5 g of fluorene in 50 mL of dry chloroform,4.18 mL (2.74 times) of liquid bromine was dissolved in 30 mL of dry chloroform solution,The above mixture was added dropwise to the reaction flask at 0 ° C in a constant pressure dropping funnel.Under dark conditions, stirring overnight,Saturated Na2S2O3 solution was added to the reaction solution and excess liquid bromine,Quench the reaction, liquid separation,After washing the organic layer several times with water,Add anhydrous MgSO4 to the organic phase for half an hour,Filtered to remove anhydrous magnesium sulfate,The solvent was removed by rotary evaporation in vacuo,Recrystallization in ethanol,A white solid 2a was obtained,Yield 95percent.
92% With bromine In chloroform at 0 - 20℃; Darkness To a solution of fluorene (14.7g, 88.44mmol) in dry chloroform (150mL) at 0°C was added with a solution of Br2 in chloroform (80mL). The reaction was stirred overnight at room temperature in darkness. After quenched with saturated aqueous Na2S2O3, the reaction mixture was separated and the organic phase was washed with water, dried with MgSO4 and concentrated in vacuo. The crude product was recrystallized in ethanol to give the title product as a white solid (26.3g, 92percent). 1H NMR (500MHz, CDCl3): δ (ppm) 7.68 (s, 2H), 7.61 (d, J=8.1Hz, 2H), 7.52 (d, J=8.1Hz, 2H), 3.87 (s, 2H).
91.8% With bromine; iron In chloroform at 0℃; for 4 h; Darkness Fluorene (8.31 g, 50.0 mmol, 1.00 eq) was dissolved in chloroform (83 mL, 0.6 M) and iron powder (279 mg, 5.00 mmol, 0.10 eq) was added. The solution was cooled in a water/ice bath to 0 °C. Bromine (5.38 mL, 105.0 mmol, 2.10 eq) in chloroform (42 mL) was added through a dropping funnel over one hour in the dark to the vigorously stirred mixture. After complete addition the mixture was stirred for an additional three hours at 0 °C. Saturated Na2S2O3 solution (100 mL) was slowly added at the same temperature and stirring was continued for 30 minutes. Chloroform (100 mL) was added, the organic phases were separated and the aqueous layer was extracted with chloroform (3 x 50 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and the solvent was evaporated in vacuo. The crude product was purified by a silicagel column chromatography (Petroleum ether) to produce compound 2 as white solid in 91.8percent yield (15.27g). 1H-NMR (300 MHz, CDCl3), δ (ppm): 7.64-7.62 (d, J = 7.2 Hz, 2H, ArH), 7.58-7.52 (t, J = 9.0 Hz, 2H, ArH), 7.49-7.46 (d, J = 8.1 Hz, 2H, ArH), 3.84-3.78 (d, J = 15.6 Hz, 2H, fluorene-9H). Elemental analysis calcd (percent) for C13H8Br2 (324.02): C, 48.19; H, 2.49; found: C, 48.37; H, 2.66.
88% With bromine In dichloromethane at 0℃; for 6 h; After inserting the round flask 9H- fluorene (10g, 60.11mmol) in, placed methylene chloride (MC) in 200mL solvent. From 0 slowly injected bromine (6.78mL, 2.2eq). Gave the HBr gas was discharged out of the room temperature Thereafter, the mixture was stirred for 6 hours. After completion of the reaction with aqueous NaOH solution, and extracted with MC and the organic layer with brine to remove the remaining water over anhydrous magnesium sulfate and, after evaporation of the solvent was recrystallized from methanol and the MC 2,7-dibromo-9Hfluorene of a white solid ( to give a compound e-1) (yield: 88percent).
83% With bromine; iron In chloroform at 5 - 20℃; for 6 h; In a 250 ml three-mouth bottle, by adding fluorene (16.6g, 0 . 1mol), iron powder (88 mg, 1 . 57mmol), chcl 100 ml. Ice water bath cooling, instillment bromine (35.2g, 0 . 22mol)/ chcl mixed solution 35 ml. When the temperature is not exceeded in the bottle drops 5 °C. After dropping, so that automatic temperature rise, then reaction under the room temperature condition for 6 hours, saturated sodium bisulfite solution to washing to salmoneous dematerialised. The separated white solid, filtered, and the filtrate combined organic phase, water washing 2 times, remove the sub-layer of iron powder and residue, organic layer with anhydrous MgSO4drying, filtering, to evaporate the solvent to obtain white solid, the resulting solid with direct filtering to obtain solid combine and obtain the crude product. The crude product is recrystallized in chloroform after purification, to obtain white crystal 26.9g, yield 83percent.
83% With bromine; iron In chloroform at 5℃; Cooling with ice In a 250 mL three-necked flask, fluorene (24.5 g, 0.1 mol) was added,Iron powder (88mg, 1.57mmol)And methyl chloride 100mL; ice bath cooling,(17.6g, 0.1mol) / chloroform mixed solution 35mL, drop the bottle when the temperature does not exceed 5 ; reaction is completed, filtration, chloroform recrystallization, white solid 20.3g, yield 83percent.
83% With iron In chloroform at 5℃; In a 250 mL three-necked flask, fluorene (24.5 g, 0.1 mol) was added,Iron powder (88 mg, 1.57 mmol) and chloroform (100 mL)Ice water bath cooling,(17.6 g, 0.1 mol) in chloroform (35 mL) was added dropwise, and the temperature in the bottle was not more than 5 ° C.The reaction was completed, filtered and recrystallized from chloroform to give 20.3 g of a white solid,Yield 83percent.1HNMR, 13CNMR, MS and elemental analysis showed that the resulting compound was the target product.
83% With bromine; iron In chloroform at 5℃; In a 250 mL three-necked flask, a solution of fluorene (24.5 g, 0.1 mol), iron powder (88 mg, 1.57 mmol) and methyl chloride 100 mL; Ice water bath cooling, a solution of 35 mL of a mixed solution of bromine (17.6 g, 0.1 mol) / trichloromethane was added dropwise, Drop the bottle when the temperature does not exceed 5 ; The reaction was completed, filtered and recrystallized from chloroform to give 20.3 g of a white solid in 83percent yield.
83% With bromine; iron In chloroform at 5℃; Cooling with ice Fluorene (16.6 g, 0.1 mol) and iron powder (88 mg, 1.57 mmol) were dissolved in 100 mL of chloroform. In an ice bath, 35 mL of chloroform-diluted liquid bromine (35.2 g, 0.22 mol) was slowly added dropwise. When the bottle temperature does not exceed 5 . The reaction was completed, filtered and recrystallized from chloroform to give a beige solid powder (26.9 g, 83percent).
83% With bromine; iron In chloroform at 5℃; Cooling with ice In a 250mL three-vial bottle,Add hydrazine (24.5g, 0.1mol), iron powder (88mg, 1.57mmol) and chloroform (100mL);Ice water bath cooling,Bromine (17.6g, 0.1mol) / chloroform mixed solution was added dropwise 35mL, when the bottle temperature does not exceed 5 °C;After the reaction was completed, filtration and recrystallization from chloroform gave 20.3 g of a white solid with a yield of 83percent.
82% With iron(III) chloride; bromine In chloroform at 0 - 20℃; Darkness Br2 (6.4 mL, 123 mmol) in chloroform (80 mL) was added to a solution of fluorene (10 g, 60 mmol) and Iron(III) chloride anhydrous (150 mg, 0.92 mmol) in chloroform (150 mL) at 0 °C for 3 hours with stirring. The reaction was performed in dark environment and at the room temperature. After quenched with saturated aqueous Na2S2O3, the reaction mixture was separated and the organic phase was washed with water, dried with MgSO4 and concentrated in vacuum line. The crude product was recrystallized in ethanol to give compound 1 as white solid (16.03 g, 82percent). 1H NMR (500 MHz, CDCl3): δ (ppm) 7.61 (d, J = 1.5 Hz, 2H), 7.54-7.52 (d, J = 8.1 Hz, 2H), 7.47-7.45 (dd, J1= 8.1 Hz, J2=1.5 Hz, 2H), 3.79 (s, 2H). 13C NMR (125 MHz, CDCl3): δ (ppm) 144.92, 139.81, 130.27, 128.43, 121.31, 121.07, 36.68. Anal. Calcd for C13H8Br2: C, 48.09; H, 2.39. Found: C, 48.19; H,2.49.
80% With bromine; iron In chloroform at 20℃; for 12 h; Cooling with ice; Darkness In the 1000mL three bottles,A solution of fluorene (60 g, 301 mmol)Iron powder (0.84 g, 15 mmol) and chloroform (400 mL)Ice bath to 5 ° C,Under dark conditions,A solution of liquid bromine (35 mL, 753 mmol) and 115 mL of chloroform was slowly added dropwise to the reaction solution,Drop finished,And stirred at room temperature (stirring speed: 800 rpm) for 12 hours.The reaction was quenched by adding 200 mL of saturated aqueous sodium bisulfite solution to the reaction flask.The reaction mixture was subjected to suction filtration,The residue was washed with saturated aqueous sodium bisulfite solution,Water and ethanol washed three times,After drying the residue,Recrystallization from CHC13 for purification,To obtain 77.8 g of white crystals,Yield: 80percent.
80% With bromine; iron In chloroform at 5 - 20℃; for 12 h; Darkness In a 1000 mL three-necked flask,A solution of fluorene (60 g, 301 mmol)Iron powder (0.84 g, 15 mmol) and chloroform (400 mL)Ice bath (5 ) in the dark,A solution of bromine (35 mL, 753 mmol)And 115 mL of chloroform were slowly added dropwise to the reaction solution,Plus,The reaction was vigorously stirred at room temperature for 12 hours.A reaction solution was prepared by adding 200 mL of a saturated aqueous solution of sodium bisulfite to the reaction flask.The reaction mixture was suction-filtered, and the residue was washed three times with saturated aqueous sodium bisulfite solution, water and ethanol, dried by filtration and recrystallized from CHCl3 to obtain 77.8 g of white crystals and 80percent yield.
79% With bromine In chloroform at 0 - 20℃; for 4.5 h; The raw material fluorene (5.000 g, 30.0 mmol) was dissolved in 30 ml in a three-neck bottle.Trichloromethane, the three bottles are placed in an ice water bath and cooled to below 0 C.Pipette bromine (3.6 ml, 70.0 mmol) in 5 mlThe chloroform was placed in a constant pressure funnel, and liquid bromine was slowly added dropwise with stirring.After 30 minutes, the addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 4 h.A white solid precipitated. Stop the reaction after 24 h,The mixture was filtered under reduced pressure to give a white solid.The white crystal 2,7-dibromoindole (W) was obtained.Yield: 7.210 g (79percent).
78.5% With bromine; iron In chloroform at 0℃; for 2 h; Small molecule derivative (Compound 5) Synthesis of fluorene (see Figure 1):Fluorene 50mL round bottom flask was added the 2 g, 20 mL of chloroform, iron 10.6mg, iceBath cooled to below 0 , and liquid bromine was slowly added dropwise 4.12g 10mL chloroform mixture, a solutionAfter reacted for 2 hours. Aqueous sodium bisulfite to remove excess bromine. MinuteThe chloroform layer was isolated, concentrated, and the solid was filtered, purified by recrystallization with chloroform to give white crystalsBody 2,7-dibromo fluorene (compound 1) 2.95g, Yield: 78.5percent.
72.2% With bromine In chloroform at 0℃; for 10 h; Darkness Dissolve fluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.Stop the reaction and pour the mixed solution into aqueous Na2S2O3 solution.Extract with dichloromethane (15 mL × 3), combine the organic layers with deionized water (25 mL × 3) and saturated brine (20 mL), dry the organic layer over anhydrous magnesium sulfate, and remove the solvent using a rotary evaporator.The crude product is recrystallized from absolute ethanol solution.A white solid of 2,7-dibromo-fluorene (7.04 g, 72.2percent) was obtained;2,7-Dibromo-fluorene (6.40 g, 19.75 mmol) and tetrabutylammonium bromide (0.10 g, 0.31 mmol) obtained from the previous reactionDissolve 1-bromododecane (10 mL, 41.65 mmol) in 60 mL of toluene and 25 mL of 50 wtpercent NaOH aqueous solution, and argon at 80 °C for 24 hours under reflux.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated by a chromatography column (petroleum ether:dichloromethane=4:1) to give didodecyl-fluoreneas a pale yellow solid (11.30 g, 86.6percent). );Finally, the resulting 2,7-dibromo-9,9-didodecyl-fluorene (2.00 g, 3.03 mmol) was reacted in the previous step.Dissolve in 60 mL of dichloromethane, add 10 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (4.98 g, 9.08 mmol) was added in portions to the above mixed solution and the reaction was stirred for 1 hour.Stop the reaction by adding 50 mL of deionized water and extract with dichloromethane (15 mL x 3).The organic phase was washed with deionized water (25 mL×3) and saturated brine (20 mL), respectively.Dry the organic layer by adding anhydrous magnesium sulfate,The solvent was removed using a rotary evaporator and the crude product was separated on a chromatography column (petroleum ether: dichloromethane = 4:1).The orange-yellow product 2,7-dibromo-9,9-didoceyl-1,6-dinitrofluorene (1.7 g, 74.56percent) was obtained.
65% With bromine; iron In chloroform for 2 h; Darkness (1) Synthesis of Intermediate 1 (2,7-dibromofluorene)
Under ice cooling, in a 100mL three-neck flask fluorene (2.49g, 15mmol) and 20mL of chloroform, mechanical stirrer, 6.0g of iron powder was added until the solid dissolved, and then slowly added dropwise bromine (4.75g, 30mmol), after dark reaction 2h, stirring was stopped. The reaction mixture was poured into water, washed with saturated sodium sulfite until the red color disappears, liquid separation, the aqueous layer was extracted with chloroform (30mL × 3), the organic layers combined, dried over anhydrous magnesium sulfate, and solvent was removed through rotary evaporation under reduced pressure, the crude product by column chromatography on silica gel, eluent petroleum ether to give white crystals, yield 65percent.

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YieldReaction ConditionsOperation in experiment
99% With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide for 5 h; Sonication (1) 2,7-dibromofluorene (9.72 g, 30 mmol), tetra-n-butylammonium bromide (0.08 g, 0.25 mmol), methyl iodide (12.8 g, 90 mmol) NaOH solution 10mL, DMSO 120mL, added to 250mL single-necked flask, ultrasonic reaction 5h (100W), after the reaction was poured into 500mL of water, stirred for 30min after suction filtration, washed with water and dried to give a pale yellow solid 10.5g, yield 99 percent.
99% With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 5 h; Sonication Step 2: At room temperature, 2,7-dibromofluorene (9.72 g, 30 mmol) and tetra-n-butylammonium bromide were added to the reactor. (0.08g, 0.25mmol), methyl iodide (12.77g, 90mmol), 10percent NaOH solution, 10mL, DMSO 120 mL, ultrasonic reaction for 5 h, then add 500 mL of water to stop the reaction, stirring, suction filtration, washing with water, and drying to obtain Intermediate 1-2 (10.46 g, 99percent).
98% With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 5℃; In a stream of argon, 32 g (0.1 mol) of 2,7-dibromofluorene, 27 g (0.24 mol) of t-butoxypotassium, and 500 mL of DMSO were added to a 3-L three-necked flask, and the reaction system was cooled to 5°C. Subsequently, 34 g (0.24 mol) of methyl iodide were slowly dropped to the resultant, and then the whole was stirred overnight. After the completion of the reaction, water was added to the resultant, and an organic layer was extracted with ethyl acetate and washed with a saturated salt solution. After the washed product had been dried with magnesium sulfate, the solvent was removed by distillation with a rotary evaporator, whereby a coarse reaction product was obtained. The product waspurified by meansof column chromatography (silica gel (hexane solvent) : ethyl acetate = 95 : 5), whereby 34 g of Intermediate 6 (white crystal, 98percent yield) as a target were obtained.
98% With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 5℃; Inert atmosphere Synthesis Example 4; (4-1) Synthesis of Intermediate 7 Into a 3 liter three-necked flask, 32 g (0.1 mole) of 2,7-dibromofluorene, 27 g (0.24 moles) of t-butoxypotassium and 500 ml of DMSO were placed under the stream of argon, and the reaction system was cooled at 5° C. After 34 g (0.24 moles) of methyl iodide was slowly added dropwise, the resultant mixture was stirred for one night. After the reaction was completed, water was added, and the organic layer was separated by extraction with ethyl acetate, washed with a saturated aqueous solution of sodium chloride and dried with magnesium sulfate. The solvent was removed by distillation using a rotary evaporator, and a crude reaction product was obtained. The crude reaction product was purified in accordance with the column chromatography (silica gel; hexane:ethyl acetate=95:5), and 34 g of Intermediate 7 of the object compound was obtained (white crystals; the yield: 98percent).
94%
Stage #2: for 0.5 h;
2, 7-dibromofluorene (2.0 g, 6.2mmol), dimethyl sulfoxide (0.2 ml), benzyltriethylammonium chloride (0. 07 g, 0.3 mmol), and a 50 wtpercent aqueous solution of NaOH (2 g) were added to a flask. Next, iodomethane (2.2 g, 15 mmol) was dropped to the mixture, and the whole was stirred for 30 minutes. Water (100 mL) and toluene (100 mL) were added to the reaction liquid in such a manner that an organic layer would be separated. The organic layer was washed with a saturated brine, and was then dried with anhydrous magnesium sulfate. The resultant was concentrated under reduced pressure by using a rotary evaporator, and then the residue was purified by means of silica gel column chromatography, whereby Intermediate 4-1 was obtained (amount 2.0 g, yield 94 percent).
93.5%
Stage #1: With sodium t-butanolate In tetrahydrofuran at 0 - 20℃; Inert atmosphere
Stage #2: for 2 h;
These compounds were obtained following an essentially similar procedure. An illustrative example is provided for 8: 2-bromofluorene (4.90 g, 0.02 mol) was dissolved in anhydrous THF (100 mL) in a three-necked round-bottom flask fitted with a magnetic stirrer, a condenser and a N2 purge. t-BuONa (in THF, 8.64 g, 0.09 mol) was added dropwise at 0 °C and under N2 gas. The reaction mixture was stirred for 1.5 h at room temperature. Iodomethane (3.12 mL, 0.05 mol) was added dropwise and then the reaction was continued for another 2 h the reaction mixture was filtered and the filtrate was evaporated under reduced pressure. The residue was purified by silica gel chromatography with petroleum ether as the eluent to afford a white liquid (8) (5.21 g, 95.1percent).
84% With potassium hydroxide In dimethyl sulfoxide at 20℃; for 32 h; 2,7-Dibromofluorene (13.2 g, 40 mmol), potassium hydroxide (10 g, 179 mmol) were stirred in dimethylsulfoxide (80 mL). Iodomethane (12.5 g, 88 mmol) in dimethylsulfoxide (80 mL) was added dropwise for 8 h. The reaction was stirred at room temperature for 24 h and then poured into 500 mL water. The product was extracted with dichloromethane and the combined organic layers were evaporated to dryness. The crude product was recrystallized in ethanol to give compound 2 as yellow solid (12.11 g, 84percent). 1H NMR (500 MHz, CDCl3): δ (ppm) 7.53 (d, J = 1.2 Hz, 2H), 7.51 (d, J =8.3 Hz, 2H), 7.45-7.43 (dd, J1= 8.3 Hz, J2=1.2 Hz, 2H), 1.45 (s, 6H). 13C NMR (125 MHz, CDCl3): δ (ppm) 155.22, 137.13, 130.33, 126.21, 121.43, 121.32, 47.36, 26.82. Anal. Calcd for C15H12Br2: C, 51.01; H, 3.68. Found: C, 51.17; H,3.44.

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  • 17
  • [ 112-29-8 ]
  • [ 16433-88-8 ]
  • [ 175922-78-8 ]
YieldReaction ConditionsOperation in experiment
92.7% With potassium hydroxide; potassium iodide In dimethyl sulfoxide at 0 - 20℃; for 4 h; EXAMPLE 1
2,7-Dibromo-9,9-didecyifluorene
A mixture of 2,7-dibromofluorene (64.8 g, 0.20 mol potassium iodide (3.0 g, 0.018 mol), finely powdered KOH (56.0 g, 1 mol), and DMSO (150 ML) was mechanically stirred under nitrogen in a three-necked round-bottom flask..
The flask was cooled in an ice water bath before adding four batches of the bromoalkyl (90 ML. 95.94 g, 0.434 mol)..
After each addition, the internal temperature rose sharply..
Once the last aliquot was completed, the reaction was stirred for 4 hours at room temperature before water (200 ML) was added..
The solid was filtered off and dried in a desiccator equipped with P2O5 under vacuum for 16 hours..
The crude product was recrystallized from ethanol to produce 2,7-dibromo-9,9-didecylfluorene as white crystals (m.p. 40-41° C.) in 92.7percent yield..
Mass Spec. m/z 602,604,606 (M+), 461,463,465 (M-C10H21), 382,384 (461-Br). Anal. Calcd for C33H48Br2: C, 65.56percent; H, 8.00percent; Br, 26.44percent. Found: C, 64.99percent; H, 8.21percent; Br, 27.25percent.
92% With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 4 h; 2.2.1
2,7-dibromo-9,9-didecylfluorene (1)
1-bromodecane (4.42 g, 20.0 mmol) was added by syringe to a mixture of 2,7-dibromofluorene (2.59 g, 8 mmol), tetrabutyl ammonium bromide (0.02 g, 0.064 mmol) and 2.50 mL of 50percent aqueous sodium hydroxide in dimethyl sulfoxide (50.0 mL).
After stirring at room temperature for 4 h, the mixture was poured into water and extracted three times with dichloromethane.
The solvent was removed under reduced pressure and the precipitate was purified by column chromatography on silica gel (eluent: petroleum ether) to afford 2,7-dibromo-9,9-didecylfluorene as a white powder (4.45 g, Yield 92percent).
1H NMR (500 MHz, CDCl3, δ): 7.51 (d, 2H, J = 8.70 Hz, Ar-H), 7.45 (m, 4H, Ar-H), 1.91 (m, 4H, CH2), 1.13 (m, 28H, CH2), 0.85 (t, 6H, J = 6.95 Hz, CH3), 0.58 (m, 4H, CH2). FT-IR (cm-1, KBr): ν = 2950, 2836 (s; CH), 1638, 1551 (w; Ar). Anal. Calcd. for C33H48Br2: C 65.56, H 8.00; Found: C 64.72, H 7.62.
90.7%
Stage #1: With potassium <i>tert</i>-butylate In tetrahydrofuranInert atmosphere
Stage #2: for 5.5 h; Cooling with liquid nitrogen
To a 2 L three-necked round bottom flask equipped with mechanical stir, nitrogen inlet and outlet, 81.00 g (0.250 mol) 25 2,7-dibromo-9H-fluorence and 500 mL 11 THF were charged. After the 2,7-dibromofluorence was dissolved, 58.9 g (0.525 mol) 26 potassium t-butoxide was added in three batch. The mixture was turned from colorless to dark red immediately, 116.1 g (0.525 mol) of 27 1-bromodecane in 150 mL THF was added drop wise within 3.5 hrs. After addition completed, the mixture was stirred under nitrogen for 2 hrs. Potassium salts was removed through filtration. The filtrate was concentrated under vacuum to give yellow viscous oil. The final product was purified by silica gel chromatography using hexanes as eluent. 137.1 g 28 product was obtained as waxy crystals, 90.7percent isolated yield, m.p. 37.8-39.0° C.
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  • 18
  • [ 111-25-1 ]
  • [ 16433-88-8 ]
  • [ 189367-54-2 ]
YieldReaction ConditionsOperation in experiment
86%
Stage #1: With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide for 0.5 h;
Stage #2: at 20℃; for 3 h;
2,7-dibromo fluorene 1.5g, triethyl benzyl ammonium chloride 0.009g, 30mL dimethylSulfoxides discharge suspended in three flask, was added dropwise 1.5 mL of 50wtpercent aqueous sodium hydroxide,The reaction for half an hour, and then dropping 1.59g1- bromine hexane. The mixture was stirred at room temperature for 3 hours,Extracted with ether. The organic phase was washed with brine, dried over anhydrous magnesium sulfate. The solvent was distilled off, noRecrystallization from aqueous ethanol orange needle crystals of 2,7-dibromo-9,9-dihexylfluorene (fluorenyl Compound 2)1.96g, Yield: 86percent
84.36% With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 80℃; for 24 h; Inert atmosphere Dissolve hfluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.The reaction was stopped and the mixed solution was poured into an aqueous Na2S2O3 solution and extracted with dichloromethane (15 mL x 3).The combined organic layers were washed with deionized water (25 mL x 3) and saturated brine (20 mL), respectively.After that, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was recrystallized from an absolute ethanol solution to give 2,7-dibromo-fluorene (7.04 g, 72.2percent) as a white solid;Then, 2,7-dibromo-fluorene (6.40 g, 19.75 mmol) obtained from the previous reaction was dissolved with tetrabutylammonium bromide (0.10 g, 0.31 mmol) and 1-bromohexane (7.30 mL, 44.24 mmol). In 60mL of tolueneAnd 25mL of 50percent water by mass of NaOH solution, and argon is kept at 80°C and stirred under reflux for 24 hours.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated on a chromatography column (petroleum ether:dichloromethane = 4:1) to give 2,7-dibromo-9,9-dihexyl-fluorene (8.20 g, 84.36percent) as a pale yellow solid;Finally, the resulting 2,7-dibromo-9,9-dihexyl-fluorene (1.00 g, 2.03 mmol) was reacted in the previous step.Dissolve in 30 mL of dichloromethane, add 5 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (3.34 g, 6.09 mmol) was added portionwise to the above mixed solution, and the reaction was stirred for 1 hour.Stop the reaction and add 30 mL of deionized water and extract with dichloromethane (15 mL × 3).The organic phase was washed with deionized water (15 mL x 3) and saturated brine (20 mL), respectively.The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by a chromatography column (petroleum ether: dichloromethane=2:1) to give an orange-yellow product.2,7-dibromo-9,9-dihexyl-1,6-dinitro-fluorene (0.62 g, 52.54percent),
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  • 19
  • [ 544-10-5 ]
  • [ 16433-88-8 ]
  • [ 189367-54-2 ]
YieldReaction ConditionsOperation in experiment
77.1 %Chromat. With sodium hydroxide; Aliquat 336 In water; toluene at 55 - 75℃; for 33.5 h; A mixture of 16.2 g (0.05 moles) dibromofluorene, 13.7 g (0.113 moles) chlorohexane, 0.9 g (0.002 moles) tricaprylmethylammonium chloride (commercially known as Aliquat 336) and 15 ml of toluene was heated to 55° C. under nitrogen. To this was shot added 60.1 g (0.76 moles) 50percent NaOH. No exotherm was detected. The system was heated at 55° C. for 3 hours, 65° C. for 19.5 hours, then 75° C. for 11 hours. At this point, a GC analysis indicated 98+percent conversion. The system was cooled to 60° C. The solids (NaCl) remained suspended in the top organic phase. The aqueous phase was separated and the organic phase was extracted with 1.x.18 ml water, keeping the system at about 60° C. This seemed to be enough water to dissolve all of the solids. The organic phase remained the top phase. The aqueous phase was separated and the organic phase extracted with 19 ml 3.5percent HCl. The organic phase now became the bottom phase and changed color from dark to green and then orange. The organic phase was separated off and product precipitated with of 30.6 g of acetonitrile. It was cooled to 10° C. and filtered. The cake was rinsed with 1.x.10 ml of acetonitrile and air-dried to 19.3 g of a pale yellow solid. By area percent GC it was 98.3percent 2,7-dibromo-9,9-di-n-hexylfluorene, a 77.1percent yield.
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YieldReaction ConditionsOperation in experiment
86.6% With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 80℃; for 24 h; Inert atmosphere Dissolve fluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.Stop the reaction and pour the mixed solution into aqueous Na2S2O3 solution.Extract with dichloromethane (15 mL × 3), combine the organic layers with deionized water (25 mL × 3) and saturated brine (20 mL), dry the organic layer over anhydrous magnesium sulfate, and remove the solvent using a rotary evaporator.The crude product is recrystallized from absolute ethanol solution.A white solid of 2,7-dibromo-fluorene (7.04 g, 72.2percent) was obtained;2,7-Dibromo-fluorene (6.40 g, 19.75 mmol) and tetrabutylammonium bromide (0.10 g, 0.31 mmol) obtained from the previous reactionDissolve 1-bromododecane (10 mL, 41.65 mmol) in 60 mL of toluene and 25 mL of 50 wtpercent NaOH aqueous solution, and argon at 80 °C for 24 hours under reflux.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated by a chromatography column (petroleum ether:dichloromethane=4:1) to give 2,7-dibromo-9,9-didodecyl-fluoreneas a pale yellow solid (11.30 g, 86.6percent). );Finally, the resulting 2,7-dibromo-9,9-didodecyl-fluorene (2.00 g, 3.03 mmol) was reacted in the previous step.Dissolve in 60 mL of dichloromethane, add 10 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (4.98 g, 9.08 mmol) was added in portions to the above mixed solution and the reaction was stirred for 1 hour.Stop the reaction by adding 50 mL of deionized water and extract with dichloromethane (15 mL x 3).The organic phase was washed with deionized water (25 mL×3) and saturated brine (20 mL), respectively.Dry the organic layer by adding anhydrous magnesium sulfate,The solvent was removed using a rotary evaporator and the crude product was separated on a chromatography column (petroleum ether: dichloromethane = 4:1).The orange-yellow product 2,7-dibromo-9,9-didoceyl-1,6-dinitrofluorene (1.7 g, 74.56percent) was obtained.
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