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CAS No. : | 457-68-1 | MDL No. : | MFCD00000360 |
Formula : | C13H10F2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DXQVFHQUHOFROC-UHFFFAOYSA-N |
M.W : | 204.22 | Pubchem ID : | 96094 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.08 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 55.81 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.31 cm/s |
Log Po/w (iLOGP) : | 2.67 |
Log Po/w (XLOGP3) : | 3.15 |
Log Po/w (WLOGP) : | 4.4 |
Log Po/w (MLOGP) : | 4.95 |
Log Po/w (SILICOS-IT) : | 4.7 |
Consensus Log Po/w : | 3.97 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.55 |
Solubility : | 0.0575 mg/ml ; 0.000281 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.82 |
Solubility : | 0.309 mg/ml ; 0.00151 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.88 |
Solubility : | 0.000267 mg/ml ; 0.00000131 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.48 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With formaldehyd; ethanol; sulfuric acid | ||
With tetrachloromethane; formaldehyd; hydrogen fluoride anschliessendes Behandeln mit ZnCl2; | ||
Multi-step reaction with 2 steps 2: water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfur tetrafluoride; hydrogen fluoride at 180℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nitric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With chloro-trimethyl-silane; sodium iodide In acetonitrile at 20℃; for 4h; | |
97% | With 1,2-benzenedisulfonimide; isopropanol at 80℃; for 8h; | |
86% | With boron trifluoride diethyl ether complex; water monomer In dibutyl ether at 140℃; for 2h; Inert atmosphere; |
84% | With boron trifluoride diethyl ether complex In water monomer for 2h; Inert atmosphere; Reflux; | |
70% | Stage #1: 4,4'-difluorobenzhydryl alcohol With n-butyllithium In dichloromethane at 0℃; Stage #2: With (dichloro)hydroborane In dichloromethane at 0 - 20℃; | |
62% | With hydrogen In methanol for 90h; Ambient temperature; | |
With black phosphorus; water monomer; iodine Reagens 4: Essigsaeure; | ||
100 %Spectr. | With triethylsilane In dichloromethane for 1h; Reflux; | Deoxygenation of benzylic alcohols with Sn-Mont / Et3SiH General procedure: In a round-bottomed flask was placed 30 mg ofSn-Mont, 1 mmol of 1a, 2 mmol of Et3SiH and 5mL of CH2Cl2. The mixture was refluxed for 1 h. Then, Sn-Montwas filtered off, and the filtrate was concentrated and analyzed by NMR usingmesitylene as the internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With carbon disulfide; aluminium trichloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Cyclohepta-1,3,5-triene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With pyridine hydrogenfluoride; sodium nitrite 1.) O deg C, 20 min, 2.) 100 deg C, 1 h; | |
75% | Stage #1: 4,4'-diamino diphenyl methane With tetrafluoroboric acid; sodium nitrite In water at 0 - 20℃; for 0.333333h; Stage #2: With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate In water at 90℃; for 1.5h; | 1 Example 1; Conversion of 4,4'-methylenedianiline to bis(4-fluorophenyl)methane 4,4'-Methylenedianiline (1mmol) was dissolved in HBF4 (25% by weight, 2ml) at 0°C. Sodium nitrite (2.1mmol) (0.145g) dissolved in distilled water (0.5ml) was added dropwise to the 4,4'-methylenedianiline. A white precipitate formed and the resultant mixture was stirred for 20 minutes at 20°C to allow completion of the diazotisation step.1-Butyl-3-methyl-imidazolium hexafluorophosphates [bmim][PF6] (2g) (7mmol) was then added to the reaction mixture which resulted in the immediate dissolution of the precipitate and separation of the mixture into a yellow hydrophobic ionic liquid layer and a clear aqueous layer.The clear aqueous layer was removed by decantation. The remaining hydrophobic ionic liquid layer was flushed and dried using dry nitrogen (N2) and the sample vessel sealed from contact with the atmosphere. The hydrophobic ionic liquid layer was then heated at 90°C for 90 minutes during which time the ionic liquid turned pink and vigorous effervescence was visible. After cooling, the ionic liquid was extracted with diethyl ether (5 x 5mls) and the ethereal extracts reduced in vacua to give a yellow oil.The resultant yellow oil was confirmed by 1H-NMR to be 82% bis (4-fluorophenyl) methane. The overall yield of bis (4-fluorophenyl)methane was calculated to be 75%, based on the initial weight of 4,4'-methylenedianiline. |
With pyridine; hydrogen fluoride; sodium nitrite 1.) room temperature, 2.) 0 deg C, 3.) 100 deg C; Yield given. Multistep reaction; |
Stage #1: 4,4'-diamino diphenyl methane With hydrogenchloride; tetrafluoroboric acid; sodium nitrite In water at 8 - 10℃; for 0.5h; Stage #2: With boron trifluoride for 0.5h; Reflux; | (1), 4, 4'-Diaminodiphenyl methane, a 42% aqueous solution of Fluoroboric acid and aqueously concentrated hydrochloric acid, a quantitative solvent put into the reactor, under ice salt bath with stirring cooled at 8 ° C after that added the drops of Sodium nitrite aqueous solution, temperature control below 10 ° C, add drops and the reaction is continued with stirring for 0.5h, after that filtered, washed with solvent, Filter dry, dried at room temperature and obtain Boron fluoride diazonium salt; (2), the Boron fluoride diazonium salt which is obtained in step 1, the catalyst and the solvent are added into a beaker which is equipped with a distillation apparatus and a BF3 gas absorption unit, under stirring slowly warmed, keep this temperature and does not exceed to 97 ° C, until there is no more decomposition of gas so far, after that warmed to reflux temperature, carry on reaction for 30min, the solvent has been evaporated, and then vacuum distillation, obtained 4,4'-difluorodiphenyl methane; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Fluorbenzol, Paraformaldehyd, wfr. ZnCl2, HCl-Gas, 8 h, 60grad; neben 4-Fluor-benzylamid; | ||
...presented by the following formula (4) which can respectively correspond to the formula (1) can be obtained. (D) Fluorine substituted aromatic compound represented by the formula (4) corresponding to the hydroxy compound wherein X1 is a substituent of the group (a) in the formula(1): ... 4-methylsulfonyl-4'-fluorobenzophenone, 4-phenylsulfonyl-4'-fluorobenzophenone, 2,2'-difluorodiphenylmethane, 2,3'-difluorodiphenylmethane, 2,4'-difluorodiphenylmethane, 3,3'-difluorodiphenylmethane, 3,4'-difluorodiphenylmethane, 4,4'-difluorodiphenylmethane, 4-methyl-4'-fluorodiphenylmethane, 4-methoxy-4'-fluorodiphenylmethane, 4-phenyl-4'-fluorodiphenylmethane, 4-nitro-4'-fluorodiphenylmethane, 4-cyano-4'-fluorodiphenylmethane, 4-chloro-4'-fluorodiphenylmethane, ... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With pyridine; tert.-butylhydroperoxide In decane; acetonitrile at 80℃; for 24h; | |
99% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; C12H8Cl3FeN2O4Zr4; oxygen; sodium nitrite In acetonitrile at 60℃; for 24h; | |
97% | With oxygen; sodium t-butanolate In dimethyl sulfoxide at 50℃; for 5h; Sealed tube; | 2) General procedure for autoxidative oxygenation General procedure: To a predried 5 mL round-bottom flask diarylmethane 1 (0.4 mmol), dry DMSO (1 mL), andt-BuONa (0.8 mmol) were subsequently added as soon as possible. The reaction system wassealed by a rubber septum with a needle connected to an O2 balloon, and then stirred at 50 oC for5 h. During this period, the reaction system suffered complex color changes. Then the reactionmixture was allowed to cool at room temperature, and diluted with 1 mol/L HCl to pH = 6-7,washed with ethyl acetate (20 mL × 3), dried over anhydrous Na2SO4, and filtered to get clearorganic solution. The solvent was removed reduced pressure by a rotary evaporator, and theresulting residue was subjected to column chromatography on silica gel using co-solvent (ethylacetate / petroleum ether = 1/20, v/v) as eluent to give the corresponding diarylketones. |
96% | With pyridine; tert.-butylhydroperoxide; air; K(1+)*AuCl4(1-)*0.5H2O=K[AuCl4]*0.5H2O In decane at 90℃; for 24h; | |
93% | With pyridine; tert.-butylhydroperoxide; iron(III) chloride at 82℃; for 24h; | |
93% | With pyridine; tert.-butylhydroperoxide In acetonitrile at 80℃; for 24h; | 3 General procedure for the oxidation of benzylic methylenes A mixture of 4,4-diuorodiphenylmethane (178.4 L,1.0 mmol) and P4VPDVB2.5-40%-Fe(III) catalyst (2.0 mol%), pyridine (8.0 L,0.1 mmol), TBHP (5.0-6.0 M in decane, 545.0 L, 3.0 mmol) and 1.0 mL acetonitrile was dissolved in a 25 mL single-necked flask fitted with a reflux condenser. The mixture was heated at 80°C for 24 h under air atmosphere in an oil bath. Then the mixture was cooled to 25°C and centrifuged to get a catalyst and supernatant solution. Then the solution was analyzed by Agilent 7890/5975C-GC/MSD using nitrobenzene as an internal standard. A calibration curve for each reactant and product has been built, which is included in the ESI†. The in situ 1H NMR monitoring of the reaction conversion and yield was performed in the DMSO-d6 solvent, the crude sample of entry 11 in Table 3 was filtered for direct 1H NMR analysis (see ESI†). Furthermore, the products of entries 1 and 7 in Table 2 were isolated through column chromatography and the isolated yields were provided. |
93% | With tert.-butylhydroperoxide; C24H18N6O3*Cu(1+)*I(1-) In water at 20℃; for 4h; | |
91% | Stage #1: 4,4'-difluorodiphenylmethane With tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Inert atmosphere; Stage #2: With dimethyl sulfoxide In dichloromethane at -78℃; for 0.0833333h; Inert atmosphere; Stage #3: With triethylamine In dichloromethane at 35℃; for 1h; Inert atmosphere; | |
90% | With N-Bromosuccinimide; water In chloroform for 3h; Reflux; | Generalprocedure for synthesis of diaryllketones (3a-x) General procedure: In around-bottom flask, diarylmethanes (1.0 mmol), NBS (889.9 mg, 5.0 mmol) andwater (0 or 5.0 mmol) were dissolved in CHCl3 (4.0 mL). After refluxing for 3 h in the air, the reaction mixture was quenched withNa2S2O3·5H2O, cooled to roomtemperature, washed with 5mL CH2Cl2, dried with MgSO4,and filtered to get clear organic solution. The solvent was removed reduced pressure by a rotary evaporator, and the resulting residue was subjected to column chromatography on silica gel using co-solvent(ethyl acetate / petroleum ether, v/v) as eluent to give the corresponding diaryllketones. |
88% | With tert.-butylhydroperoxide; copper(II) acetate monohydrate In water at 80℃; for 8h; | |
84% | With N-hydroxyphthalimide; oxygen In acetonitrile at 80℃; for 12h; | |
80% | With tert.-butylhydroperoxide In acetonitrile at 70℃; | |
67% | With oxygen In 1,2-dichloro-benzene at 130℃; for 6h; Schlenk technique; | |
48% | With cercosporin; oxygen; potassium bromide In methanol at 20℃; Irradiation; Schlenk technique; Green chemistry; chemoselective reaction; | |
30% | With sodium hypochlorite; tetra(n-butyl)ammonium hydrogensulfate; sodium bromide In hexane at 25℃; for 8h; | |
89 % Chromat. | With N-hydroxyphthalimide; oxygen; benzaldehyde In acetic acid at 30℃; for 7h; | |
99 %Chromat. | With pyridine; tert.-butylhydroperoxide; nickel cobalt oxide In acetonitrile at 90℃; for 24h; | |
With N-hydroxyphthalimide; oxygen In acetonitrile at 60℃; for 24h; | ||
With nitric acid for 6h; Reflux; | according to the present invention the preparation method of 4, 4'-difluorobenzophenone, it includes the following preparation steps the above obtained 4, 4'-difluorodiphenyl methane is put into a flask, add quantitative 24% dilute nitric acid and catalyst, warmed to reflux temperature, after that added the drops of measured amount 55% of nitric acid, add about 4h and then finished, after adding the drops carry on reaction for 2h, cool at room temperature to precipitate the crystals, filter, the filtrate is reused, the filter material is re-crystallized from 70% ethanol, dry and then obtained white flake 4,4'-difluorobenzophenone crystals. | |
93 %Spectr. | With oxygen In dodecane at 120℃; for 10.5h; | 2.3. Catalytic aerobic oxidation of alkylarenes General procedure: The oxidation was carried out in a carousel reaction tube to which diphenylmethane (1.0 mmol), Ni2Mn-LDH (0.2 g), dodecane (2 mL) and chlorobenzene (0.5 mmol, used as the internal standard reference) were added. The mixture was then magnetically stirred at 120 under oxygen atmosphere (1 atm). The reaction was sampled periodically andanalyzed through a gas chromatograph (Shimadzu GC-2010AF). Afterthe reaction, the catalyst was separated via filtration, washed with ethyl acetate, dried at 120 for 4 h and introduced into a new reaction torecycle the catalyst. The conversion of the diphenylmethane and the selectivity of benzophenone were calculated using the internal standardmethod according to the GC analysis with no allowance for the background.The turnover frequency (TOF) value was calculated based onthe mol of diphenylmethane converted per hour per mol of Mn on thesurfaces of catalysts. The catalytic oxidations of other substrates wereconducted with similar procedure, and the conversion and selectivitywere calculated using the normalization method. Some of the productswere isolated using flash chromatography analyzed through a NMR spectrometer. |
41 %Chromat. | With tert.-butylhydroperoxide; 2Cu(2+)*C33H17NO8(4-)*H2O*3C3H7NO In acetonitrile at 65℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | for 0.0333333h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 1.28 g 2: 0.27 g 3: 1.29 g 4: 0.85 g | With nitric acid In acetic anhydride at -50℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | at 20℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: thiophene In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: 1,2,3-trimethoxybenzene In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: 1-methoxy-2-methyl-1-trimethylsiloxy-1-propene In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: diethylzinc In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: In dichloromethane at -78℃; Electrolysis; | |
27% | With pyridine; [bis(acetoxy)iodo]benzene; N-fluorobis(benzenesulfon)imide at 100℃; for 15h; Sealed tube; Green chemistry; | 1. General procedure for the synthesis of dibenzylic product: General procedure: Alkane 2 (30 mmol), IBDA (2 mmol), Py (1 mmol), and NFSI (1 mmol) were added in a sealed tube with a Teflon lined cap. The mixture was placed in an oil bath at 100 °C for 15 h. After cooling to room temperature, the reaction mixture was quenched with water and extracted with EtOAc (40 mL). The combined organic layer was dried with anhydrous Na2SO4 and the solvent was removed under vacuum. The crude product was purified over a column of silica gel (eluant: hexane/ethyl acetate = 30:1) to afford the desired product 2a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; | ||
With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrochemical reaction; | ||
With tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; |
With tetrabutylammonium tetrafluoroborate In dichloromethane-d2 at -78℃; Electrolysis; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: allyl-trimethyl-silane In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: Bu4NBF4; CF3SO3H / CH2Cl2 / -78 °C / Electrolysis 1.2: 81 percent / CH2Cl2 / -78 °C / Electrolysis 2.1: Bu4NBF4; CF3SO3H / CH2Cl2 / -78 °C / Electrolysis 2.2: 55 percent / CH2Cl2 / 0.33 h / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: Bu4NBF4; CF3SO3H / CH2Cl2 / -10 °C / Electrolysis 1.2: 83 percent Spectr. / CH2Cl2 / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 86 percent / triethylamine / ethane-1,2-diol / 0.25 h / Heating 2: 80 percent / 1.5 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 43 percent / 1.) Mg / diethyl ether / 18 h / Heating 2: 62 percent / hydrogen / 5 percent Pd/C (70 percent perchloric acid) / methanol / 90 h / 1520 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With gallium trifluoromethanesulfonate; dimethylmonochlorosilane In dichloromethane at 20℃; for 1.5h; | |
87% | With phosphonic Acid; iodine In benzene at 80℃; for 22h; Sealed tube; Inert atmosphere; | 4.2. Typical procedure for preparation of targeted molecules General procedure: Under N2, a mixture of aromatic ketone 1 (0.6 mmol), H3PO3 (147.6 mg, 1.8 mmol), I2 (76.2 mg, 0.3 mmol) and benzene (1.2 mL) was stirred in a 25 mL closed sealed tube in oil bath at 80°C for indicated time. After the mixture was cooled down to the room temperature, the mixture was quenched by Na2S2O3 aqueous solution and was extracted with EtOAc three times. Then the combined the organic layer was dried over MgSO4 and filtrated. The filtrate was concentrated and the residue was further purified by column chromatography on silica gel to give the product 2. |
69% | With triethylsilane; C19H26B(1+)*C24BF20(1-) In dichloromethane at 20℃; for 0.166667h; |
Multi-step reaction with 2 steps 1: zinc-powder; ethanolic NaOH / 45 - 70 °C 2: phosphorus; iodine; H2O / Reagens 4: Essigsaeure | ||
Multi-step reaction with 2 steps 1.1: boron trifluoride diethyl ether complex / dichloromethane / 20 °C / Inert atmosphere 2.1: sodium iodide; chloro-trimethyl-silane / dichloromethane / 20 °C / Inert atmosphere; Green chemistry 2.2: 20 °C / Inert atmosphere; Green chemistry | ||
Multi-step reaction with 2 steps 1: Sodium sulfate [anhydrous]; boron trifluoride diethyl ether complex / chloroform / 0 - 20 °C / Inert atmosphere 2: N,N,N',N'-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a;2',1'-c][1,4]diazepine-2,12-diamine / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With di-tert-butyl peroxide; iron(II) chloride at 80℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; tetrabutylammomium bromide; palladium dichloride In water at 100℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With di-tert-butyl peroxide; iron(II) chloride at 100℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 33 %Chromat. 2: 10 %Chromat. | With iron(III) chloride In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11% | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: Diphenylmethane In dichloromethane at -78℃; for 0.333333h; Stage #3: With triethylamine In dichloromethane at -78 - 20℃; for 0.333333h; | 4.2. Preparation of the first generation dendritic organosilicon compounds General procedure: 4.2.1. The electrochemical method. The anodic oxidation was carried out in an H-type divided cell (4G glass filter) equipped with a carbon felt anode (Nippon Carbon JF-20-P7, ca. 160 mg, dried at 250 °C/1 mmHg for 2.5 h before use) and a platinum plate cathode (20 mm×10 mm). In the anodic chamber were placed a solution of 4,4'-difluorodiphenylmethane (75.1 mg, 0.368 mmol) and 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL). In the cathodic chamber were placed trifluoromethanesulfonic acid (64 μL, 0.72 mmol) and 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL). The constant current electrolysis (12.0 mA) was carried out at -78 °C with magnetic stirring until 3.0 F/mol of electricity was consumed. Then (diphenylmethyl)trimethylsilane (36.2 mg, 0.151 mmol) was added to the anodic chamber at -78 °C and the mixture was stirred for 20 min. The resulting mixture was treated with triethylamine (0.3 mL) at -78 °C. After stirring at room temperature for 10 min, the solvent was removed under reduced pressure and the residue was quickly filtered through a short column (2×3 cm) of silica gel to remove Bu4NBF4 by using hexane/AcOEt=1/1 as an eluent. Removal of the solvent of the combined filtrate under reduced pressure and the crude product thus-obtained was purified with flash chromatography to obtain 3b as a colorless crystal in 79% yield (NMR yield). Bis(4-bis(4-fluorophenyl)methylphenyl)methyl-trimethylsilane (3b). Mp 125 °C. 1H NMR (400 MHz, CDCl3) δ 7.20-7.18 (m, 4H), 7.07-7.04 (m, 8H), 7.00-6.96 (m, 12H), 5.48 (s, 2H), 3.50 (s, 1H), 0.05 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 161.2 (d, J=236.5 Hz), 140.8, 140.0, 139.5 (d, J=2.8 Hz), 130.6 (d, J=7.9 Hz), 128.9, 128.5, 115.0 (d, J=21.1 Hz), 54.9, 45.4, -1.5. HRMS (FAB) m/z calcd for C42H36F4Si: 644.2522, found 644.2523. IR (cm-1): 2955, 1601, 1504, 1223, 1157. X-ray data for 3b: C42H36F4Si, M=644.80, triclinic, space group P-1 (No. 2), a=10.9102(4) Å, b=11.5590(4) Å, c=14.7982(5) Å, β=77.4670(10), V=1744.86(11) Å3, Z=2, Dc=1.227 g/cm3, μ=1.17 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate / dichloromethane / -78 °C / Electrolysis 1.2: 0.33 h / -78 °C 1.3: 0.33 h / -78 - 20 °C 2.1: trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate / dichloromethane-d2 / -78 °C / Electrolysis |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate / dichloromethane / -78 °C / Electrolysis 1.2: 0.33 h / -78 °C 1.3: 0.33 h / -78 - 20 °C 2.1: trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate / dichloromethane / -78 °C / Electrolysis 2.2: 1 h / -78 °C 2.3: 0.17 h / -78 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79 %Spectr. | Stage #1: 4,4'-difluorodiphenylmethane With trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In dichloromethane at -78℃; Electrolysis; Stage #2: trimethylsilyldiphenylmethane In dichloromethane at -78℃; for 0.333333h; Stage #3: With triethylamine In dichloromethane at -78 - 20℃; for 0.333333h; | 4.2. Preparation of the first generation dendritic organosilicon compounds General procedure: 4.2.1. The electrochemical method. The anodic oxidation was carried out in an H-type divided cell (4G glass filter) equipped with a carbon felt anode (Nippon Carbon JF-20-P7, ca. 160 mg, dried at 250 °C/1 mmHg for 2.5 h before use) and a platinum plate cathode (20 mm×10 mm). In the anodic chamber were placed a solution of 4,4'-difluorodiphenylmethane (75.1 mg, 0.368 mmol) and 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL). In the cathodic chamber were placed trifluoromethanesulfonic acid (64 μL, 0.72 mmol) and 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL). The constant current electrolysis (12.0 mA) was carried out at -78 °C with magnetic stirring until 3.0 F/mol of electricity was consumed. Then (diphenylmethyl)trimethylsilane (36.2 mg, 0.151 mmol) was added to the anodic chamber at -78 °C and the mixture was stirred for 20 min. The resulting mixture was treated with triethylamine (0.3 mL) at -78 °C. After stirring at room temperature for 10 min, the solvent was removed under reduced pressure and the residue was quickly filtered through a short column (2×3 cm) of silica gel to remove Bu4NBF4 by using hexane/AcOEt=1/1 as an eluent. Removal of the solvent of the combined filtrate under reduced pressure and the crude product thus-obtained was purified with flash chromatography to obtain 3b as a colorless crystal in 79% yield (NMR yield). Bis(4-bis(4-fluorophenyl)methylphenyl)methyl-trimethylsilane (3b). Mp 125 °C. 1H NMR (400 MHz, CDCl3) δ 7.20-7.18 (m, 4H), 7.07-7.04 (m, 8H), 7.00-6.96 (m, 12H), 5.48 (s, 2H), 3.50 (s, 1H), 0.05 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 161.2 (d, J=236.5 Hz), 140.8, 140.0, 139.5 (d, J=2.8 Hz), 130.6 (d, J=7.9 Hz), 128.9, 128.5, 115.0 (d, J=21.1 Hz), 54.9, 45.4, -1.5. HRMS (FAB) m/z calcd for C42H36F4Si: 644.2522, found 644.2523. IR (cm-1): 2955, 1601, 1504, 1223, 1157. X-ray data for 3b: C42H36F4Si, M=644.80, triclinic, space group P-1 (No. 2), a=10.9102(4) Å, b=11.5590(4) Å, c=14.7982(5) Å, β=77.4670(10), V=1744.86(11) Å3, Z=2, Dc=1.227 g/cm3, μ=1.17 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrabutylammonium tetrafluoroborate / dichloromethane-d2 / -78 °C / Electrolysis; Inert atmosphere 2: dichloromethane-d2 / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: 1-Bromo-4-fluorobenzene; 4,4,5,5-tetramethyl-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]-1,3,2-dioxaborolane With bis(tri-t-butylphosphine)palladium(0); potassium hydroxide In 1,4-dioxane; water at 20℃; for 12h; Inert atmosphere; Stage #2: With potassium hydroxide In 1,4-dioxane; water at 60℃; for 6.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With N-iodo-succinimide In dichloromethane at 20℃; for 16h; Irradiation; | |
73% | With N-Bromosuccinimide; dichloro(2,2′-bipyridine)gold(III) chloride In acetonitrile at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With N-Bromosuccinimide; dichloro(2,2′-bipyridine)gold(III) chloride In acetonitrile at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-tert-butyl peroxide; iron(II) chloride at 80℃; for 8h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: iron(II) chloride; di-tert-butyl peroxide / 8 h / 80 °C / Inert atmosphere; Schlenk technique 2: iron(III) chloride hexahydrate / 1,2-dichloro-ethane / 12 h / 20 - 100 °C / Schlenk technique; Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: carbon disulfide; 4,4'-difluorodiphenylmethane With potassium carbonate In N,N-dimethyl-formamide at 0 - 20℃; for 0.5h; Stage #2: ethyl iodide In N,N-dimethyl-formamide at 20℃; for 8.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 0.5 h / 0 - 20 °C 1.2: 8.25 h / 20 °C 2.1: sulfuric acid / dichloromethane / 10 h / 0 - 20 °C 3.1: [bis(acetoxy)iodo]benzene; potassium fluoride / acetonitrile / 0.5 h / 20 °C / Sealed tube; Glovebox |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 0.5 h / 0 - 20 °C 1.2: 8.25 h / 20 °C 2.1: sulfuric acid / dichloromethane / 10 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With palladium diacetate; caesium carbonate; triphenylphosphine In water; N,N-dimethyl-formamide at 153℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With ferric(III) bromide; di-tert-butyl peroxide In neat (no solvent) at 90℃; for 48h; Schlenk technique; Molecular sieve; | |
79% | With tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With NHC-Pd(II)-Im; sodium hydroxide In tetrahydrofuran at 100℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With NHC-Pd(II)-Im; lithium tert-butoxide In water at 80℃; for 12h; Inert atmosphere; Schlenk technique; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With manganese(III) triacetate dihydrate; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 90℃; for 12h; Schlenk technique; Inert atmosphere; | |
86% | With manganese(II) acetate dihydrate; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 90℃; for 12h; Inert atmosphere; | 12 Synthesis of N-(bis(4-fluorophenyl)methyl)acetamide To the reactor was added 0.2 mmol of bis (4-fluorophenyl) methane,0.04 mmol manganese acetate dihydrate, 0.4 mmol DDQ,0.15 mL of acetonitrile, 0.15 mL of TFA, 0.35 mL of DCE,Heated to 90 ° C under nitrogen, stirring for 12 h, stopping the reaction,Cooled to room temperature, potassium carbonate was added to neutral, extracted with ethyl acetate,Dried, and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain the desired product,Yield 86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With manganese(III) triacetate dihydrate; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 90℃; for 12h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 40 %Spectr. 2: 4 %Spectr. | With trifluorormethanesulfonic acid In chloroform-d1 at 20℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate In acetonitrile at 20℃; for 15h; Sealed tube; Inert atmosphere; Irradiation; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; | |
65% | With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; | 46 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 2,2-bis(4-fluorophenyl)-1,3-dithiane With chloro-trimethyl-silane; sodium iodide In dichloromethane at 20℃; Inert atmosphere; Green chemistry; Stage #2: With water In dichloromethane at 20℃; Inert atmosphere; Green chemistry; | |
31.4 mg | With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 4,4'-difluorodiphenylmethane With Benzophenone imine; copper(l) iodide; 1,10-Phenanthroline; di-tert-butyl peroxide In chlorobenzene at 90℃; for 48h; Inert atmosphere; Sealed tube; Stage #2: With hydrogenchloride In methanol; water; chlorobenzene at 40℃; for 15h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 10% Pt/activated carbon; water-d2 In isopropyl alcohol at 20℃; for 24h; Sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 2,3-dicyano-5,6-dichloro-p-benzoquinone; iron(II) chloride In 1,2-dichloro-ethane at 90℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 34% 2: 9% | Stage #1: bis(methanesulfonyl)peroxide; 4,4'-difluorodiphenylmethane With trimethylsilyl acetate; copper (I) acetate In dichloromethane at 23℃; for 12h; Inert atmosphere; Stage #2: With sodium methylate In methanol at 23℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sodium bromide In dichloromethane at 40℃; for 4h; Inert atmosphere; chemoselective reaction; | Representative experimental procedure for the benzylic C-H acetoxylation by the PIDA/NaBr system General procedure: In a flame-dried two-necked round-bottomed flask, under nitrogen, phenyliodine(III) diacetate (PIDA, 193 mg, 0.6 mmol) and finely powdered sodium bromide (103 mg, 1.0 mmol) were subsequently added to a stirred solution of arylalkane 1 (0.50 mmol) and acetic acid (0.57 mL, ca. 10 mmol) in dry dichloromethane (5 mL). Then the mixture was vigorously stirred at 40 °C with or without zinc acetate (92 mg, 0.5 mmol). After checking the reaction completion by TLC, saturated aqueous sodium carbonate was added to the mixture and the resulting solution was stirred for an additional 5 min. The organic layer was separated, washed again with saturated aqueous sodium carbonate, then with dilute aqueous sodium thiosulfate, and was dried over anhydrous sodium sulfate. After removal of the solvents, the residue was subjected to column chromatography on silica gel (eluents: n-hexane/ethyl acetate) to give the benzylacetate 2 in the indicated yield; the physical and spectral data ofthe reported compounds (2a-d, g-j) matched those of the authentic samples (see Supporting Information File 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen fluoride; FH2(1+)*F6Sb(1-) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: hydrogen fluoride 3: hydrogen fluoride; FH2(1+)*F6Sb(1-) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: hydrogen fluoride; CCl3(1+)*ClF5Sb(1-) 3: water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With trimethylsilylazide; copper diacetate; (S,S)-4,4'-bis(phenylmethyl)-2,2',5,5'-tetrahydro-2,2'-bioxazole; N-fluorobis(benzenesulfon)imide In nitromethane at 30℃; for 48h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: dichloromethane With bis(1,5-cyclooctadiene)nickel (0); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine at 20℃; for 0.5h; Inert atmosphere; Schlenk technique; Sealed tube; Stage #2: 4-fluoro-1-iodobenzene at 20℃; for 20h; Irradiation; Inert atmosphere; Schlenk technique; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; sodium hydrogencarbonate In acetonitrile at 20℃; Schlenk technique; Inert atmosphere; Molecular sieve; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 4,4'-difluorodiphenylmethane With Benzophenone imine; tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; Stage #2: With hydrogenchloride In methanol at 50℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrabutylammonium perchlorate In acetonitrile; <i>tert</i>-butyl alcohol at 30℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With diisopropyl hydrogenphosphonate; 1,1,1,3',3',3'-hexafluoro-propanol; tetrabutylammomium bromide; N-fluorobis(benzenesulfon)imide; copper(ll) bromide In dichloromethane at 50℃; for 16h; Inert atmosphere; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tetra-n-butylammonium perchlorate In 1,2-dichloro-ethane at 20℃; for 4h; Inert atmosphere; Electrochemical reaction; chemoselective reaction; |