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Product Details of [ 86-73-7 ]

CAS No. :86-73-7 MDL No. :MFCD00001111
Formula : C13H10 Boiling Point : -
Linear Structure Formula :- InChI Key :NIHNNTQXNPWCJQ-UHFFFAOYSA-N
M.W : 166.22 Pubchem ID :6853
Synonyms :
Chemical Name :9H-Fluorene

Calculated chemistry of [ 86-73-7 ]

Physicochemical Properties

Num. heavy atoms : 13
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 : 54.89
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.35 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.32
Log Po/w (XLOGP3) : 4.18
Log Po/w (WLOGP) : 3.26
Log Po/w (MLOGP) : 4.67
Log Po/w (SILICOS-IT) : 4.04
Consensus Log Po/w : 3.69

Druglikeness

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

Water Solubility

Log S (ESOL) : -4.19
Solubility : 0.0108 mg/ml ; 0.000065 mol/l
Class : Moderately soluble
Log S (Ali) : -3.89
Solubility : 0.0215 mg/ml ; 0.000129 mol/l
Class : Soluble
Log S (SILICOS-IT) : -5.18
Solubility : 0.0011 mg/ml ; 0.00000664 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 2.0

Safety of [ 86-73-7 ]

Signal Word:Danger Class:9
Precautionary Statements:P403+P233-P501-P281 UN#:3077
Hazard Statements:H360-H410 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 86-73-7 ]

* 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 [ 86-73-7 ]
  • Downstream synthetic route of [ 86-73-7 ]

[ 86-73-7 ] Synthesis Path-Upstream   1~59

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Reference: [1] Justus Liebigs Annalen der Chemie, 1919, vol. 418, p. 291
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  • [ 108-90-7 ]
  • [ 25603-67-2 ]
Reference: [1] Organic and Biomolecular Chemistry, 2014, vol. 12, # 42, p. 8488 - 8498
  • 3
  • [ 86-73-7 ]
  • [ 67665-47-8 ]
Reference: [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6696 - 6700[2] Angew. Chem., 2018, vol. 130, p. 6806 - 6810,5
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  • [ 1016-05-3 ]
  • [ 159-66-0 ]
Reference: [1] Organic Letters, 2016, vol. 18, # 3, p. 384 - 387
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  • [ 159-66-0 ]
Reference: [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6696 - 6700[2] Angew. Chem., 2018, vol. 130, p. 6806 - 6810,5
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  • [ 153-78-6 ]
Reference: [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 1749 - 1757
[2] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2018, vol. 189, p. 22 - 31
[3] Journal of Nanoscience and Nanotechnology, 2018, vol. 18, # 11, p. 7873 - 7881
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YieldReaction ConditionsOperation in experiment
95% With N-Bromosuccinimide In 1,2-propylene cyclic carbonate at 60℃; for 1 h; EXAMPLE 6
2-Bromofluorene
To a solution of fluorene (16.6 g, 0.1 mol), in propylene carbonate (125 ML), at 60° C., N-bromosuccinimide (17.8 g, 0.1 mol) was added in one portion, and the mixture was allowed to cool over a period of 1 hour..
The solids separated on dilution with water (2 L), were collected, dissolved in toluene (250 ML), and the toluene solution was washed with water..
The solids left after concentration were recrystallized from ethanol-water, 23.3 g (95percent yield), m.p. 95.6-101.3° C. Mass Spec. (m/z):322, 324, 326 (M+ dibromo), 244, 246 (M+).
91.35%
Stage #1: at 65℃; for 1.5 h;
Stage #2: at 25℃; for 4 h;
Step (1): adding 30 g of fluorene (0.18 mol), 42.5 g of 40percent by weight of hydrobromic acid, 32 g of triphenylphosphine dibromide, and 3.10 g of benzoyl peroxide in a 500 ml three-necked flask, stirring and heating to Reflow reaction at 65 ° C for 1.5 h; Step (2): After the end of step (1), the three-necked flask is cooled to 25 ° C, 125.0 g of dibromohydantoin is added, and the mixture is stirred for 4 h; Step (3): Step (2) After the reaction is completed, it is cooled to room temperature, the reaction solution is allowed to stand, and the aqueous solution is separated from the organic phase to obtain an aqueous phase and an organic phase, and the aqueous phase is extracted with dichloromethane. Times,The organic phase obtained by the extraction is combined and added to the organic phase obtained by static separation, and the organic phase is washed three times, dried with anhydrous sodium sulfate, and filtered.Concentration, the concentrated product was recrystallized from ethanol, and dried in vacuo to give white crystals. The yield of 2-bromofluorene obtained after drying was 91.35percent, and the purity of the gas chromatograph was 99.65percent.
90% With sodium bromate; hydrogen bromide; trimethylbenzylammonium bromide In dichloromethane; water at 20 - 30℃; for 2 h; 1) take a volume of 100ML two one flask,Through one of the flask's neck, 5 g of fluorene was added,0.34 g of benzyltrimethylammonium bromide,0.9 g sodium bromate;
2) In the flask fitted with a thermometer and constant pressure dropping funnel,Through a constant pressure dropping funnel to the flask by adding another bottle through the flask to the flask was added 34.5mL of water,23 mL dichloromethane;
3) Under normal pressure,The liquid in the flask was stirred and mixed,And the solid dissolved,The reaction temperature was controlled at 30 .
4) To the flask in Step 3 through a constant pressure dropping funnel dropping 40percent by weight of hydrobromic acid 8.8mL,After the addition is completed,Continue stirring at room temperature for 2h,The reaction formula is:
7) The reaction solution in step 4 was allowed to stand,The stationary phase was separated from the aqueous phase and the organic phase,Get the aqueous and organic phases;
6) The aqueous phase obtained in step 5 was extracted once with dichloromethane,It is then combined with the organic phase obtained in step 4,And the combined organic phases washed three times;
7) The organic phase obtained in Step 6 was dried over anhydrous sodium sulfate, filtered, concentrated,And the concentrated product,By recrystallization from ethanol,Dry in vacuo.
After drying,The yield of 2-bromofluorene obtained was 60percentWherein the content of 2-bromofluorene in the substance after drying in step 7 is detected by HPLC,The purity of 90percent, product appearance: white solid powder.
89.8% With iron(III) chloride; N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 24 h; Darkness In 250 mL round bottom flask, fluorene (9.96 g, 60 mmol) and FeCl3 (1.46 g, 9 mmol) dissolved in 80 mL DMF, then a solution of N-bromosuccimide (NBS) (11.74 g, 66 mmol ) in 50 mL of DMF was added dropwise to the flask in dark. The reaction mixture was stirred for 24 h at room temperature. Then the mixture was washed with 5 percent of dilute hydrochloric acid, extracted with CHCl3 (30 mL × 3) and dried over anhydrous magnesium sulfate. After removal of solvent in the rotary evaporator, the residue was collected and purified via recrystallization with ethanol/water (v:v = 95:5) and methanol successively as solvent to afford white crystal (13.2 g, 89.8 percent).
85% at 40 - 50℃; for 10 h; In a 500-ml four-necked flask, 30 g of fluorene and 200 ml of propylene carbonate were added, and the temperature was raised to 40-50° C. while stirring. 33 g of NBS was added in batches. After the addition, the reaction was performed at 40-50° C. for 10 h. The GC was used to detect the basic reaction of the raw materials. Add 200ml water to stir at 20-25°C for 3h, filter and blow at 50°C for 10h.2-Bromofluorene was obtained and crystallized from ethanol to obtain 37 g of the product in a yield of 85percent and GC of 90percent.
84% 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 (17.6g, 0 . 1mol)/ 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, then filtering, chlorofrom recrystallization, the white solid obtained 19.3g, yield 84percent
84% With bromine; iron In chloroform at 5℃; for 16 h; In a 250 mL three-necked flask,Fluorene (16.6 g, 0.1 mol), iron powder (88 mg, 1.57 mmol), Chloroform 100 mL. After cooling in an ice-water bath, 35 mL of a mixed solution of bromine (17.6 g, 0.1 mol) and chloroform was added dropwise.The temperature inside the bottle does not exceed 5 ° C. After 16 hours, the reaction was stopped, filtered and recrystallized from chloroform to give 19.3 g of a white solid in 84percent yield.
84% With bromine; iron In chloroform at 5 - 20℃; for 6 h; Cooling with ice In the 2501 ^ three bottles,Adding fluorene (16.68, 0.1111001),Iron powder (8811 ^, 1.5711111111),Trichloromethane lOOmL.Ice water bath cooled to 5 ° C,Slowly add 35 mL of liquid bromine (17.6 g, 0. lmol) / chloroform mixed solution.The temperature inside the reaction bottle is not more than 5 ° C.After dripping,Let the temperature rise automatically,And then reacted at room temperature for 6 hours,Add saturated aqueous sodium bisulfite solution to wash until orange red disappears.Separate the lower layer of white solid,Filter,The filtrate and organic phase are combined,Washed twice,Remove the layered iron powder and residue,The organic layer was dried over anhydrous MgS04,Then filter,Chloroform recrystallization,Obtained 19.3 g of a white solid,Yield 84
84% With bromine; iron In chloroform at 5℃; Cooling with ice In a 250 mL three-necked flask, fluorene (16.6 g, 0.1 mol), Iron powder (88 mg, 1.57 mmol) and trichloromethane100mL;Ice water bath cooling,Drop bromine(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 19.3g, yield 84percent. 1H NMR, 13CNMR, MS and elements The results show that the obtained compound is the target product. The chemical reaction equation is as follows:
80% With iron(III) chloride; N-Bromosuccinimide In N,N-dimethyl-formamide for 24 h; Inert atmosphere; Darkness 2 - bromofluorene Va at room temperature, drying good 250 ml three-mouth flask, tube, three-way for a good connection, into the magneton, adding fluorene 5g (30mmol),, FeCl30 . 26g (4.4mmol) vacuum-argon, repeated 3 times. Adding anhydrous DMF 50 ml, stirring. Taking 9g NBS (50mmol) with 50 ml anhydrous DMF into solution, constant voltage used in funnel dropwise added in the dark. Stirring the reaction 24h. The resulting HCl solution (0.1M, 10 ml) processing, and NaHCO3(84 mg) in and FeCl3, Extraction and steaming and, n-hexane recrystallization, to obtain white solid 5.88g, yield 80percent.
73% With N-Bromosuccinimide In 1,2-propylene cyclic carbonate at 60℃; for 1 h; Inert atmosphere 9H-fluotcne (60g, 036mo1) was added to the one-neck flask and an argon atmosphere was established in a vacuum. Propylene carbonate (SOOmI) was added and stirred at 60C until 9H-Fluoiene was dissolved. NBS (64g, 036mo1) was added and the mixture was stirred at WC for 1 hour. Upon completion of the reaction, a solid produced by filtration with distilled water was dissolved with PA and the mixture was extracted with distilled water. The organic layer was dried with MgSO, and the solvent was removed using a rotary evaporator. Pure Compound D (64g, 7390) was obtained by recrystallization using ethanol.
71% With N-Bromosuccinimide; thioacetamide In acetonitrile at 20℃; for 19 h; General procedure: Reaction conditions: Thiourea (5.1 molpercent, 2 mg, 0.026 mmol) was added to an acetonitrile solution (10 mL) containing NBS (1.15 equiv, 104.4 mg, 0.587 mmol). Anisole (56.3 mg, 0.51 mmol) was added immediately to the resulting stirred solution and allowed to stir at room temperature for 10 min. The reaction was quenched by the addition of 10percent aqueous solution of Na2S2O3 (10 mL) and extracted with ethyl acetate (70 mL). The organic solution was then washed with additional 10percent Na2S2O3 (2 * 10 mL), followed by deionized water (3 * 15 mL) and brine (2 * 10 mL). The organic solution was then dried over anhydrous Na2SO4 and the solvent was evaporated in vacuo. The major product of each reaction was isolated by centrifugal thin-layer chromatography using a 2 mm thick silica gel 60GF254 coated plate (5percent CH2Cl2/hexanes). The products reported herein are known compounds and were characterised by GC-MS, IR, 1H and 13C NMR. Their spectroscopic data are in agreement with those reported in the literature.

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Reference: [1] Patent: US6555682, 2003, B1,
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YieldReaction ConditionsOperation in experiment
41 %Chromat. With N-Bromosuccinimide In acetonitrile at 20℃; for 19 h; General procedure: Reaction conditions: Thiourea (5.1 molpercent, 2 mg, 0.026 mmol) was added to an acetonitrile solution (10 mL) containing NBS (1.15 equiv, 104.4 mg, 0.587 mmol). Anisole (56.3 mg, 0.51 mmol) was added immediately to the resulting stirred solution and allowed to stir at room temperature for 10 min. The reaction was quenched by the addition of 10percent aqueous solution of Na2S2O3 (10 mL) and extracted with ethyl acetate (70 mL). The organic solution was then washed with additional 10percent Na2S2O3 (2 * 10 mL), followed by deionized water (3 * 15 mL) and brine (2 * 10 mL). The organic solution was then dried over anhydrous Na2SO4 and the solvent was evaporated in vacuo. The major product of each reaction was isolated by centrifugal thin-layer chromatography using a 2 mm thick silica gel 60GF254 coated plate (5percent CH2Cl2/hexanes). The products reported herein are known compounds and were characterised by GC-MS, IR, 1H and 13C NMR. Their spectroscopic data are in agreement with those reported in the literature.
Reference: [1] Tetrahedron, 2017, vol. 73, # 46, p. 6564 - 6572
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YieldReaction ConditionsOperation in experiment
96% With N-Bromosuccinimide; 1,1-bis(tert-butylperoxy)cyclohexane; nitric acid In dichloromethane at 20℃; for 1 h; Schlenk technique; Inert atmosphere The inventors selected the radical bromination of fluorene 27 by N- bromosuccinimide (NBS) at room temperature as a benchmark reaction to evaluate their inventive initiator system (Scheme 4). NBS (1.1 equiv.) (0075) Scheme 5: Room temperature Wohl-Ziegler bromination of fluorene. All reactions were performed according to the following procedure: In an oven- dried Schlenk flask fluorene 27 (83 mg, 0.5 mmol, 1 eq) and N-bromosuccinimide (98 mg, 0.55 mmol, 1 .1 eq) were dissolved in dichloromethane (5 ml). The desired peroxide (0.025 mmol, 5 mol percent) was introduced and the resulting mixture was degassed by the freeze-pump-thaw method (3 cycles). After warming to room temperature, the acid catalyst was added under a stream of argon and after the desired reaction time, the reaction mixture was quenched with NEt3 (250 μΙ_), CH2Br2 (0.5 mmol) was added as a standard for analytical purposes only and an aliquot taken for direct H NMR analysis. Yield was determined by integrating a reference peak of 28 (5.9 ppm, s, 1 H; determined from an authentic sample) relative to the peak of CH2Br2. The results of the reactions are detailed in (Table 1). The bromination proceeded efficiently using a commercial solution of peroxyketal 1 (Trigonox® 22, 50percent weight in mineral oil) in combination with different Bronsted acids. Control experiments confirmed the requirement for both acid and peroxide, no conversion being observed after 24 hours if either one of these components was omitted. A clear trend following the pKa value of the acid catalyst can be seen : stronger acids give faster conversion. Sulfuric and para-toluene sulfonic acid have similar behaviour with 72percent and 67percent of 28 after one hour, respectively (entries 1 and 2). Methane sulfonic acid gave a slightly lower yield (45percent; entry 3) while acids weaker than trifluoroacetic acid (22percent, entry 5) or trichloroacetic acid (1 8percent, entry 6) failed to give any conversion (entry 7). Nitric acid is more efficient than its pKa value would suggest (96percent; entry 4). Eventually, all reactions gave high yields when allowed to reach full conversion (80-95percent yield of 28 after 24 to 72 hours), showing that the acid catalyst only influences the initiation rate. Scandium (II I) triflate, a Lewis acid, was also found to be competent (69percent; entry 8). Different commercial peroxyketal solutions were evaluated using methane sulfonic acid as a standard catalyst of medium reactivity. 2 (Trigonox® D; 50percent weight) proved to be less efficient than 1 (45percent, entry 3), giving 1 0percent of product 28 after one hour and 76percent after 48 hours (entry 1 1 ). 3 (Trigonox® 301 ; 41 percent weight) showed low conversion after two days of reaction (8percent, entry 15). 4 (Luperox® DHD-9, 32percent weight) was found to be slightly more reactive than 3, giving 12percent product after 48 hours (entry 16). Based on the observation of this strong influence of the peroxyketal structure on its reactivity, the inventors evaluated a series of structurally different peroxides. The effect of the group X of Formula (I) is shown by compounds 11a and 11 b. 11 b proved to be less reactive than 1 (21 percent, entry 9) while 11a was more efficient, giving 47percent of 28 after one hour (entry 10). Aromatic substituents around the peroxide moiety can have significant effects: 5 is more effective than 2 (20percent, entry 12 compared to entry 1 1 ), while 6 was much less efficient (33percent after 48 h, entry 13) 9 was found to be slightly more reactive than 1 (50percent, entry 17) while 10 was the most efficient of the structures evaluated, giving 74percent of 28 after one hour of reaction (entry 18).
88% With tribromo-isocyanuric acid In ethyl acetate for 6 h; Reflux; Green chemistry General procedure: a solution of the arene (2.0 mmol) and TBCA (0.25 g, 0.68 mmol) in EtOAc (20 mL) was refluxed for 6 h with stirring. At the end of the reaction, the precipitated cyanuric acid was then separated by filtration and the filtrate was evaporated to dryness under reduced pressure. The residue was passed through a short chromatographic column (SiO2, eluted with 15:1 hexane–ethyl acetate) to give the purified products.
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[3] Patent: WO2017/108761, 2017, A1, . Location in patent: Page/Page column 15-18
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[9] Journal of Organic Chemistry, 1949, vol. 14, p. 470,472
[10] Journal of the American Chemical Society, 1947, vol. 69, p. 234
[11] Chemische Berichte, 1948, vol. 81, p. 368,371
[12] Journal of Organic Chemistry, 1949, vol. 14, p. 470,472
[13] Journal of the American Chemical Society, 1947, vol. 69, p. 234
[14] Chemische Berichte, 1948, vol. 81, p. 368,371
[15] Journal of Organic Chemistry, 1949, vol. 14, p. 470,472
[16] Journal of the American Chemical Society, 1947, vol. 69, p. 234
[17] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1948, vol. 226, p. 87
[18] Journal of the American Chemical Society, 1948, vol. 70, p. 895
[19] Justus Liebigs Annalen der Chemie, 1944, vol. 555, p. 133,137,144
[20] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1948, vol. 226, p. 87
[21] Journal of the American Chemical Society, 1948, vol. 70, p. 895
[22] Justus Liebigs Annalen der Chemie, 1944, vol. 555, p. 133,137,144
[23] Chemische Berichte, 1948, vol. 81, p. 368,371
[24] Journal of Organic Chemistry, 1949, vol. 14, p. 470,472
[25] Journal of the American Chemical Society, 1947, vol. 69, p. 234
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  • 18
  • [ 86-73-7 ]
  • [ 1133-80-8 ]
  • [ 1940-57-4 ]
YieldReaction ConditionsOperation in experiment
41 %Chromat. With N-Bromosuccinimide In acetonitrile at 20℃; for 19 h; General procedure: Reaction conditions: Thiourea (5.1 molpercent, 2 mg, 0.026 mmol) was added to an acetonitrile solution (10 mL) containing NBS (1.15 equiv, 104.4 mg, 0.587 mmol). Anisole (56.3 mg, 0.51 mmol) was added immediately to the resulting stirred solution and allowed to stir at room temperature for 10 min. The reaction was quenched by the addition of 10percent aqueous solution of Na2S2O3 (10 mL) and extracted with ethyl acetate (70 mL). The organic solution was then washed with additional 10percent Na2S2O3 (2 * 10 mL), followed by deionized water (3 * 15 mL) and brine (2 * 10 mL). The organic solution was then dried over anhydrous Na2SO4 and the solvent was evaporated in vacuo. The major product of each reaction was isolated by centrifugal thin-layer chromatography using a 2 mm thick silica gel 60GF254 coated plate (5percent CH2Cl2/hexanes). The products reported herein are known compounds and were characterised by GC-MS, IR, 1H and 13C NMR. Their spectroscopic data are in agreement with those reported in the literature.
Reference: [1] Tetrahedron, 2017, vol. 73, # 46, p. 6564 - 6572
  • 19
  • [ 86-73-7 ]
  • [ 127822-14-4 ]
  • [ 1940-57-4 ]
Reference: [1] Chemische Berichte, 1948, vol. 81, p. 368,371
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  • [ 86-73-7 ]
  • [ 77-48-5 ]
  • [ 1940-57-4 ]
Reference: [1] Anales de la Asociacion Quimica Argentina (1921-2001), 1949, vol. 37, p. 263,266[2] Anales de la Asociacion Quimica Argentina (1921-2001), 1950, vol. 38, p. 5,10
  • 21
  • [ 86-73-7 ]
  • [ 58402-65-6 ]
  • [ 1940-57-4 ]
Reference: [1] Anales de la Asociacion Quimica Argentina (1921-2001), 1949, vol. 37, p. 263,266[2] Anales de la Asociacion Quimica Argentina (1921-2001), 1950, vol. 38, p. 5,10
  • 22
  • [ 56-23-5 ]
  • [ 128-08-5 ]
  • [ 86-73-7 ]
  • [ 1940-57-4 ]
Reference: [1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1948, vol. 226, p. 87
[2] Journal of the American Chemical Society, 1948, vol. 70, p. 895
[3] Justus Liebigs Annalen der Chemie, 1944, vol. 555, p. 133,137,144
  • 23
  • [ 75-15-0 ]
  • [ 86-73-7 ]
  • [ 7726-95-6 ]
  • [ 1940-57-4 ]
Reference: [1] Chemische Berichte, 1948, vol. 81, p. 368,371
[2] Journal of the American Chemical Society, 1947, vol. 69, p. 234
  • 24
  • [ 56-23-5 ]
  • [ 86-73-7 ]
  • [ 7726-95-6 ]
  • [ 1940-57-4 ]
Reference: [1] Chemische Berichte, 1948, vol. 81, p. 368,371
[2] Journal of the American Chemical Society, 1947, vol. 69, p. 234
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  • [ 86-73-7 ]
  • [ 67-66-3 ]
  • [ 7726-95-6 ]
  • [ 1940-57-4 ]
Reference: [1] Chemische Berichte, 1948, vol. 81, p. 368,371
[2] Journal of the American Chemical Society, 1947, vol. 69, p. 234
  • 26
  • [ 128-08-5 ]
  • [ 86-73-7 ]
  • [ 7726-95-6 ]
  • [ 71-43-2 ]
  • [ 1940-57-4 ]
Reference: [1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1948, vol. 226, p. 87
[2] Journal of the American Chemical Society, 1948, vol. 70, p. 895
[3] Justus Liebigs Annalen der Chemie, 1944, vol. 555, p. 133,137,144
  • 27
  • [ 56-23-5 ]
  • [ 86-73-7 ]
  • [ 127822-14-4 ]
  • [ 1940-57-4 ]
Reference: [1] Chemische Berichte, 1948, vol. 81, p. 368,371
  • 28
  • [ 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
70%
Stage #1: With sodium methylate In dimethyl sulfoxide; toluene at 13 - 16℃; for 0.75 h;
Stage #2: With hydrogenchloride In water; dimethyl sulfoxide; toluene
Dimethylsulfoxide (DMSO) (300 ml), toluene (300 ml) and paraformaldehyde (PF) (40 gram) were charged into a round bottom flask, mixed and cooled to a temperature of 13-15 °C. Subsequently, sodium methoxide 30 percent solution (26 gram) was added to this mixture.Gradually fluorene in powder form (100 gram, 0.6 mole) was added to above reaction mixture over a period of 15 minutes, while the temperature was maintained at 14-16 °C. It was observed that most of the paraformaldehyde dissolves instantly upon addition of the fluorene. The resulting mixture was stirred for 30 minutes while the temperature was maintained at 14-16 °C. The resulting mixture was a clear pale yellowsolution.Subsequently, concentrated HCI (8-10 ml) was added to the obtained solution until al neutral pH (pH 6-7) was reached in order to stop the reaction. To the reaction mass gradually water (1000 ml) is added and reaction mass is cooled to 10 °C for 3 hours.The solid product was obtained by filtration. The solid product was filtered and washed with chilled toluene (two times 25 ml). The solid product was kept under vacuum till the toluene was completely removed from the product. The wet weight of the solid product was 120 gram. The product is then dried at 60-70 °C and weighed again. The dry weight was 90-95 gram. The yield was 70percent. The purity of the product as determined by HPLC was >98 percent. The melting point was 139-144 00.
69% With sodium methylate In dimethyl sulfoxide at 13 - 16℃; for 0.75 h; Dimethylsulfoxide (DMSO) (400 ml) and paraformaldehyde (PF) (40 gram) werecharged into a round bottom flask, mixed and cooled to a temperature of 13-15 00.Subsequently, sodium methoxide 30 percent solution (26 gram) was added to this mixture.Gradually fluorene in powder form (100 gram) was added to above reaction mixture over a period of 15 minutes, while the temperature was maintained at 14-16 00 It was observed that most of the paraformaldehyde dissolves instantly upon addition of the fluorene. The resulting mixture was stirred for 30 minutes while the temperaturewas maintained at 14-16 00 The resulting mixture was a clear pale yellow solution.Subsequently, concentrated HCI (8-10 ml) was added to the obtained solution until al neutral pH (pH 6-7) was reached in order to stop the reaction. The following work up was carried out for the reaction mixture: a large 3-5 liter round bottom flask wascharged with water (1200 ml). The reaction mixture was slowed added to the water under stirring. The resulting mixture was stirred for 30 minutes at room temperature. The solid crude reaction product was obtained by filtration.To the crude product toluene (350 ml) was added. The mixture was heated to80-90 00 The heating was stopped and the mixture was allowed to return to roomtemperature. Then the mixture was further cooled to 10 00 and maintained at that temperature for 2 hours. The solid product was filtered and washed with chilled toluene (two times 25 ml). The solid product was kept under vacuum till the toluene was completely removed from the product. The wet weight of the solid product was150 gram. The product is then dried at 60-70 00 and weighed again. The dry weight was 85-93 gram. The yield was 69percent. The purity of the product as determined by HPLC was >98 percent. The melting point was 139-144 00
30% With sodium methylate In dimethyl sulfoxide at 13 - 16℃; for 0.25 h; Dimethylsulfoxide (DMSO) (300 ml) and paraformaldehyde (PF) (25 gram) were charged into a round bottom flask, mixed and cooled to a temperature of 13-15 °C. Subsequently, sodium methoxide 30 percent solution (3.5 gram) was added to this mixture. A solution of fluorene (50 gram) in DMSO (300 ml) was added to above reaction mixture over a period of 1 -2 minutes, while the temperature was maintained at 14- 16 °C. The resulting mixture was stirred for 15 minutes while the temperature was maintained at 14-16 °C. The resulting mixture was a clear pale yellow solution. Subsequently, concentrated HCI (5-10 ml) was added to the obtained solution until al neutral pH (pH 6-7) was reached in order to stop the reaction. The following work up was carried out for the reaction mixture: a large 3-5 liter round bottom flask was charged with water (1200 ml). The reaction mixture was slowed added to the water under stirring. The resulting mixture was stirred for 15-30 minutes at room temperature. The crude reaction product was obtained by extraction with ethyl acetate. The organic phase is dried and distilled under vacuum. The residue was crystallized in 200 ml toluene to get the product as off white crystals. The dry weight was 25 gram. The yield was 30percent. The purity of the product as determined by HPLC was >98 percent.
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YieldReaction ConditionsOperation in experiment
84.8% With sodium chlorate; sulfuric acid; iodine; sodium thiosulfate In methanol; water; acetic acid Example 1
Synthesis of 2-iodofluorene
In a 300-mi four-necked flask were charged 90 ml of glacial acetic acid and 90 ml of water, followed by the addition of 41.6 g (0.25 mole) of fluorene, 12.7 g (0.10 mole) of iodine, 1.93 g (0.018 mole) of sodium chlorate and 4.5 ml of concentrated sulfuric acid under vigorous stirring.
The resulting mixture was refluxed under heat at 85 to 90° C. for 30 minutes and then at 95 to 100° C. for 30 minutes.
After completion of the reaction, the reaction mixture was extracted with 55 ml of toluene.
The organic layer was then washed with a 5percent aqueous solution of sodium thiosulfate.
After the organic layer was washed further with 50 ml of a 20percent saline solution, 216 ml of methanol was added.
The resulting mixture was crystallized for 2 hours at an internal temperature of 25 to 30° C. and the resulting crystals were collected by filtration.
The crude crystals thus obtained were washed with 76 ml of methanol and then dried, whereby 24.8 g (yield: 84.8percent) of the target compound was obtained as white crystals.
As a result of HPLC analysis (column: YMC-A-312, detection UV: 254 nm, flow rate: 1.0 ml/min, eluent: methanol/water=9/1 (by volume), buffer:
triethylamine and acetic acid, each 0.1percent), the compound was found to be composed of 1.3percent of fluorene, 98.4percent of 2-iodofluorene and 0.02percent of 2, 7-diiodofluorene.
72% With iodine; potassium carbonate; periodic acid In sulfuric acid; water; acetic acid at 65℃; for 4 h; 2-1: Synthesis of 2-iodofluorene: Fluorene (30.0 g, 180 mmol) was dissolved in a boiling solvent (acetic acid: water: sulfuric acid / 100:20:3(v/v/v))to prepare a first mixed solution, and then periodic acid dehydrate (8.0 g, 45 mmol) and iodine (23.0 g, 91.0 mmol) wereadded to the first mixed solution to prepare a second mixed solution. Then, the second mixed solution was stirred at65h for 4 hours to obtain a precipitate. The precipitate was filtered and then washed with a 2N aqueous sodium carbonatesolution and water to obtain crystals. The crystals were recrystallized by hexane. The yield ofthe product was 72percent.1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 3.81(2H, s, -CH2), 7.31(2H, m, Ar-H), 7.44(2H, m, Ar-H), 7.66(1H, d, Ar-H),7.73(1H, d, Ar-H), 7.85(1H, s, Ar-H)
65% With iodic acid In water Fluorene (5.0 g, 0.30 mol) was treated with iodic acid. Themixture was poured into water, and the product was filtered off,washed with water, and dried (8.1 g). A portion (1.02 g) waschromatographed on silica gel in cyclohexane, giving almost colourless 2-iodofluorene (0.73 g, 65percent), m.p. 127-128 [14].
60% With iodine; acetic acid; periodic acid In water at 80℃; for 4 h; Inert atmosphere 2-Iodofluorene was synthesized by iodination of fluorene (1 g, 6.02 mmol) with iodine (0.8 g, 3.2 mmol) in the presence of ortho-periodinic acid (H5IO6) (20 g, 0.88 mmol) in 80percent acetic acid aqueous solution (20 mL) at 80 °C for 4 h under nitrogen atmosphere.After cooling, the solvent was removed by decantation, and a brown solid was obtained. This was dissolved in toluene and washed with 5percent NaHSO3aqueous solution to remove the remaining iodine. Then, the resulting solid was purified by alumina column chromatography using toluene as an eluent, to obtain 8(the chemical structure in Scheme 2).Yield: 1.05 g (60percent).1H NMR (CDCl3, 400 MHz) δH7.89 (s,1H), 7.76 (d, J= 8.4 Hz, 2H), 7.70 (d, J= 8.4 Hz, 2H), 7.73(d, J= 8.4 Hz, 2H), 7.38-7.35 (m, 2H), 3.87 (s, 2H), MS(GC-mass): m/z292.0 [M+]; C13H9I (292.1).

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YieldReaction ConditionsOperation in experiment
87% With aluminum (III) chloride In nitromethane at 20℃; for 20 h; 1-neck 1L flask into a fluorene (18g, 0.108mol) and 2,5-dichloro-2,5-dimethylhexane (2.0eq, 40g),To this was added a stirred 300ml nitromethane.To AlCl3 (1.33eq, 19.2g) it was slowly added to the reaction solution at room temperature. After reacting for 20 hours at room temperature, 350ml disappointed slowly dropped in cold water to form a purple precipitate. Back into the filtered precipitate was dissolved in ethanol 250ml boiling impurities filtered, after cooling, this was repeated tasks such as hexane 150ml. Vacuum drying of the white solid were obtained Yield 36.7g, 87percent.
87% With aluminum (III) chloride In nitromethane at 20℃; for 20 h; Inert atmosphere 1-neck 1L flask fluorene (18g, 0.108mol) and 2,5-dichloro-2,5-dimethylhexane (2.0eq, 40g), this was stirred by introducing a nitrogen atmosphere 300ml. To AlCl3 (1.33eq, 19.2g) it was slowly added to the reaction solution at room temperature. After reacting for 20 hours at room temperature, 350ml disappointed slowly dropped in cold water to form a purple precipitate. Back into the filtered precipitate was dissolved in ethanol 250ml boiling impurities filtered, after cooling, this was repeated tasks such as hexane 150ml. Vacuum drying of the white solid were obtained Yield 36.7g, 87percent.
Reference: [1] Journal of the American Chemical Society, 2004, vol. 126, # 51, p. 16716 - 16717
[2] Patent: KR2016/9266, 2016, A, . Location in patent: Paragraph 0147; 0148; 0149; 0150; 0151
[3] Patent: KR2016/9263, 2016, A, . Location in patent: Paragraph 0175; 0176; 0177; 0178; 0179
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YieldReaction ConditionsOperation in experiment
53%
Stage #1: With aluminum (III) chloride In dichloromethane at -8 - 20℃; for 22.1667 h;
Stage #2: With sodium hydrogencarbonate In water
(i)
Synthesis of octamethyloctahydrodibenzofluorene
Into a 500 ml three-necked flask thoroughly purged with nitrogen, equipped with a three-way cock, a dropping funnel and a magnetic stirrer, were introduced fluorene 9.72 g (58.6 mmol) and 2,5-dimethyl-2,5-hexanediol 19.61 g (134 mmol) at room temperature.
Dehydrated dichloromethane 85 ml was further added, and the contents were stirred by the magnetic stirrer and cooled to -8°C in an ice bath.
Ground anhydrous aluminum chloride 38.9 g (292 mmol) was added to the mixture over a period of 70 minutes, and stirring was conducted for 2 hours at 0°C and further for 19 hours at room temperature outside the ice bath.
Then the resulting solution was quenched by being poured into ice water 150 ml.
Soluble matters were extracted with diethyl ether 500 ml, and an organic phase was neutralized with a saturated aqueous solution of sodium hydrogencarbonate and then washed with water.
The fractionated organic phase was dried over anhydrous magnesium sulfate.
After the magnesium sulfate was filtered off, the solvent of the filtrate was distilled away under reduced pressure.
The residue was washed six times with n-hexane 10 ml through a Kiriyama funnel and dried under reduced pressure to give white powder (12.0 g, 53 percent yield).
1H NMR spectrum (270 MHz, CDCl3): δ/ppm 1.3 (s, 12H), 1.4 (s, 12H), 1.7 (s, 8H), 3.8 (s, 2H), 7.4 (s, 2H), 7.6 (s, 2H) FD-MS spectrum: M/z 386 (M+)
Reference: [1] Patent: EP1548018, 2005, A1, . Location in patent: Page/Page column 28
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Reference: [1] Bulletin de la Societe Chimique de France, 1980, vol. 2, # 7-8, p. 334 - 344
  • 50
  • [ 75-21-8 ]
  • [ 86-73-7 ]
  • [ 203070-78-4 ]
YieldReaction ConditionsOperation in experiment
40.1%
Stage #1: With sodium hydride In N,N-dimethyl-formamide at 0 - 10℃; for 1.25 h; Inert atmosphere
Stage #2: at 15℃; for 5 h;
The raw material fluorene (100 g) was added to N, N-dimethylformamide (750 ml), and the mixture was nitrogen-protected and stirred until the solid was completely dissolved.But to 0 ° C, sodium hydride (60g, 3 to 4 times, 15 minutes plus), to maintain the temperature between 0 ~ 5 (a large number of gas release). After the addition was complete, the temperature in the reaction flask was kept at 0 to 10 ° C, stirred for one hour, then cooled to 0 ° C, and ethylene oxide (60 ml)Diluted with N, N-dimethylformamide (50ml) added to the reaction bottle (one minute added), plus finished, slowly rose to 15 ,The reaction was warmed for 5 hours (at 1). The reaction mixture was slowly poured into 800 g of ice water and quenched with EA (ethyl acetate)(800 ml x 3). The organic phases were combined and the organic phase was washed once with saturated brine (800 ml) and dried over sodium sulfate. InAfter the desiccant was removed by filtration, the solvent was spun to a half volume (water bath temperature around 45C), 10 g of activated charcoal was added,After half an hour, the activated charcoal was filtered off and the solvent was again dried (bath temperature was about 45 ° C) to obtain 170 g of crude product. The crude product was 510 mlThe toluene was heated to 100 ° C and then cooled to room temperature (10-15 ° C). After 2 hours of incubation, the reaction mixture was filtered and the filter cake was washed with toluene (100 ml× 2) and dried (60 ° C, -0.09 MPa) to obtain 63 g of an off-white powder. The product was heated to 100 ° C with 210 ml of tolueneAfter cooling to room temperature (10-15 & lt; 0 & gt; C) for 2 hours and filtering, the filter cake was washed with toluene (100 ml x 1), dried (60 &-0.09 MPa) to give white crystal 61g (median 2). Molar yield = 40.1percent, HPLC = 99.7percent.Further, after the addition of ethylene oxide, the reaction temperature must be maintained at 10 to 15 ° C and not more than 20 ° C.
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Reference: [1] Patent: US2015/259321, 2015, A1,
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