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CAS No. : | 602-09-5 | MDL No. : | MFCD00004068 |
Formula : | C20H14O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PPTXVXKCQZKFBN-UHFFFAOYSA-N |
M.W : | 286.32 | Pubchem ID : | 11762 |
Synonyms : |
|
Num. heavy atoms : | 22 |
Num. arom. heavy atoms : | 20 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 90.94 |
TPSA : | 40.46 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.26 cm/s |
Log Po/w (iLOGP) : | 2.98 |
Log Po/w (XLOGP3) : | 5.34 |
Log Po/w (WLOGP) : | 5.07 |
Log Po/w (MLOGP) : | 4.02 |
Log Po/w (SILICOS-IT) : | 4.6 |
Consensus Log Po/w : | 4.4 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -5.59 |
Solubility : | 0.000743 mg/ml ; 0.00000259 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -5.94 |
Solubility : | 0.000327 mg/ml ; 0.00000114 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -7.11 |
Solubility : | 0.0000222 mg/ml ; 0.0000000776 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.97 |
Signal Word: | Danger | Class: | 6.1 |
Precautionary Statements: | P301+P310+P330-P302+P352-P305+P351+P338 | UN#: | 2811 |
Hazard Statements: | H301-H315-H319 | Packing Group: | Ⅲ |
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 |
---|---|---|
90% | Stage #1: With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide for 0.833333 h; Cooling with ice Stage #2: at 0℃; for 1.33333 h; |
NaH (1.92 g, 80 mmol) was added to DMF (30 mL) in an ice bath. BINOL (1,1’-bi-2-naphthol) (10 g , 34 mmol) in THF (50 ml) was dropped to this solution for 20 min. After 30 min, chloromethyl methyl ether (6.4 g, 80 mmol) was dropped to this solution for 20 min. The reaction was monitored by TLC. After 1 h stirring, 3 was isolated from the organic layer by extraction of the reaction mixture with chloroform and water. The product 3 was further purified by silica gel column chromatography with a petroleum ether/ethyl acetate (5/1)mixture. Yield: 90percent.1H NMR (400 MHz, CDCl3) δ 7.95-7.93 (d, J = 9.6Hz, 2H), 7.87-7.85 (d, J = 8.4 Hz, 2H), 7.58-7.56 (d, J = 9.6 Hz, 2H),7.35-7.31 (m, 2H), 7.23-7.14 (m, 4H), 5.08-4.96 (q, J = 6.8 Hz, 4H), 3.13 (s,6H). |
90% | Stage #1: With sodium hydride In tetrahydrofuran; mineral oil for 0.833333 h; Cooling with ice Stage #2: for 1 h; |
The reaction was carried out in an ice bath. Tetrahydrofuran (30 mL) was added to a solution of sodium hydride (1.92 g, 80 mmol)Three-necked flask. A solution of 1,1'-binaphthol (compound (1)) (10 g, 34 mmol) in tetrahydrofuran (50 mL) was dissolvedThe solution was slowly added dropwise to the reaction solution over a period of 20 minutes. After completion of the addition, the reaction was continued for 30 minutes, and then chloromethyl ether (6.4 g, 80 mmol) was slowly added dropwise to the reaction solution. The reaction was continued for about one hour and monitored by thin layer chromatography. After the reaction was complete, the reaction was quenched with water (20 mL). The organic material was extracted with dichloromethane and water and the solvent was removed. The compound (2) was isolated by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (5: 1) as the eluent. Yield: 90percent. |
71% | Stage #1: With sodium hydride In tetrahydrofuran at 0℃; for 0.25 h; Inert atmosphere Stage #2: at 20℃; for 4 h; |
under nitrogen protection,2.5 g of binaphthol was dissolved in 100 ml of tetrahydrofuran,The solution was cooled to 0 ° C,Then slowly add 0.88 g of sodium hydride and stir for 15 minutes.Take 1.65 ml of 98percent chloromethyl ether slowly,The mixture was warmed to room temperature for 4 hours and quenched with water.Extracted with ethyl acetate, dried over anhydrous sodium sulfate,The column was purified by silica gel column to give 2.3 g of product as a 71percent yield. |
63% | Stage #1: With sodium hydride In tetrahydrofuran for 1 h; Stage #2: for 12 h; |
To 18.3 g of sodium hydride was added 50 g (0.175 mol) of 2,2'-dihydroxy-1,1'-dinaphthyl and stirred under nitrogen in 1.0 L of dry tetrahydrofuran (THF). After 1 hour, 116 g of chloromethyl methyl ether was added to the heavy precipitate and the resulting mixture was stirred for about 12 hours and then filtered through a pad of celite. The filtrate was shaken with 500 ml of water and 1 L of methylene chloride. An aqueous layer formed and was extracted two times more with methylene chloride. The combined organic layers were washed with water saturated with potassium bicarbonate. The organic layer was dried and filtered through a squat column of alumina and the column filtrate was evaporated until crystals appeared. The crude product was purified on a silica gel column by elution with a methylene chloride/hexane solution. About 53.5 g (63percent) of 2,2'-bis(methoxymethoxy)-1,1'-dinaphthyl, m.p 93-94° C., 0.11 mol was collected. [00053] Next, 171 ml of 1.6 N butyllithium in hexane was added to a mixture of 41 g of the above bisacetal in 1 L of tetrahydrofuran and stirred under nitrogen at 0° C. for 45 minutes. The reaction mixture was then allowed to warm to 25° C. and 25.8 ml of dimethyl sulfate was added to the suspension and the mixture was stirred for 12 hours. About 30 ml of water saturated with sodium carbonate was added and the solvent was evaporated under reduced pressure at 50° C. [00054] The residue, in 300 ml of methylene chloride, was washed twice with water. An additional 300 ml of methylene chloride, 300 ml of methanol, and 25 ml of concentrated hydrochloric acid was added to the organic solution. The solution was stirred for 3 hours, and the solvent was evaporated. The yellow product was recrystallized from methylene chloride-hexane and was purified on a silica gel column (methylene chloride, hexane 1:1) to give 29.5 g (86percent) of (R)-3-3'-dimethyl-2,2'-dihydroxy-1,1'-dinaphthyl, m.p. 204-206° C.; 1HNMR:2.2(s.6H), 7.1(d.2H), 7.3(m.2H), 7.4(m.2H), 7.8(m.4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With carbon dioxide; zinc In water at 20℃; for 48h; | |
With copper at 230℃; | ||
With copper |
Multi-step reaction with 5 steps 1: sodium hydride / N,N-dimethyl-formamide 2: sulfuryl dichloride / dichloromethane 3: potassium carbonate / N,N-dimethyl-formamide 4: 1,10-Phenanthroline; potassium <i>tert</i>-butylate / pyridine / 4 h / 120 °C / Microwave irradiation; Inert atmosphere 5: hydrogenchloride / ethanol; water / 3 h / 50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium hydroxide In toluene at 70℃; | 19.b b) Preparation of 2,2'-dimethoxy-1,1'-binaphthyl; 52 g NaOH with the concentration of 30% is formulated at room temperature. Under stirring, 143 g 2,2'-dihydroxy-1,1'-binaphthyl prepared according to the above method, 5.2 g tetrabutylammonium hydrogen sulfate and 500 ml methylbenzene are heated up to 70° C. while being dropwise added with 164 g dimethyl sulfate in order to perform stirring reaction, which is followed by TLC tracing, and upon the disappearance of monoether spots, the reaction continues for a while. The reaction product is cooled and filtered, the filter cake is washed sequentially with 400 ml methylbenzene and 400 ml NaOH solution with the concentration of 5%, then washed with water to be neutral and finally dried to obtain the 2,2'-dimethoxy-1,1'-binaphthyl. The HPLC analysis result shows that the conversion rate of the 2,2'-dihydroxy-1,1'-binaphthyl is more than 99%, the purity of the 2,2'-dimethoxy-1,1'-binaphthyl is more than 98% and the yield of the 2,2'-dimethoxy-1,1'-binaphthyl is more than 95%. Methylbenzene layers are merged to separate out the methylbenzene for recycling. |
92% | With sodium hydride In tetrahydrofuran for 2h; Heating; | |
92% | With potassium carbonate at 60℃; for 2h; |
78% | With sodium hydroxide In ethanol for 3h; Heating; | |
70% | With sodium hydroxide In water at 70 - 80℃; for 1h; | |
With alkali | ||
With sodium hydroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With C24H13Cu2F9N4O7; oxygen In isopropyl alcohol at 90℃; for 24h; | |
99.3% | With manganese (IV) dioxide In acetonitrile at 25℃; | 2.2 The Synthesis of1,1′-bi-2-naphthols General procedure: For the synthesis of 1,1′-bi-2-naphthols, 0.1g MnO2powderwas added into 40mL of 25mm 2-naphthols acetonitrile ortoluene solution. Due to the toxicity of toluene solvent andsame synthetic effect (see Fig. S2), our investigations weremainly conducted in 2-naphthols acetonitrile solution. Thesynthesis reaction was performed at atmospheric pressureand room temperature, and the MnO2powder was continuouslystirred. For the sake of comparison, the 2-naphtholssolution/MnO2 powder reaction system was put in dark andvisible-light irradiation condition, respectively. In addition,2-naphthol solution/P25(TiO2) powder reaction system and2-naphthol solution/BiVO4 powder reaction system weresimilarly treated. As the reaction time increased, the 2-naphtholacetonitrile solution gradually changed from colorlessinto brown. To detect the formation of 1,1′-bi-2-naphthols,the resultant solution was analyzed by liquid chromatography(LC-16, Shimadzu) and liquid chromatography-massspectrometry (LCMS-8040, Shimadzu), respectively. Thedetection wavelength of liquid chromatography was 280nm,and the volume ratio of mobile phase was 70% methanol-H2O. Before the detection of 1H and 13C NMR spectroscopy(JEOL Eclipse 400), the 1,1′-bi-2-naphthols product waspurified by SiO2gel thin plate using ethyl acetate/hexane(4:6) as an unfolding agent. In addition, for the 2-naphthol/-MnO2 powder system, the dissolved Mn in the reaction solutionafter 12h was detected by inductively coupled plasmamass spectrometry (ICP-MS, Thermo ICAP6300). |
98.6% | With 2,6-dimethylpyridine; sodium perchlorate In acetonitrile electrolysis; |
98.5% | With phosphomolybdic acid; silica gel In Petroleum ether for 6h; Ambient temperature; | |
98% | With air; silica gel; iron(III) chloride In xylene at 138℃; for 2.5h; | |
98% | With C34H24Cl4Cu2FeN10O4(1-)*C8H20N(1+); oxygen; sodium hydroxide In methanol at 25℃; for 6h; | |
98% | Stage #1: β-naphthol With di-tert-butyl peroxide In chlorobenzene for 0.0833333h; Microwave irradiation; Stage #2: at 200℃; for 0.166667h; | Representative Phenoxy Radical, Microwave Heating Procedure General procedure: To a 0.2-5 mL microwave reaction vial equipped with a stirbar, 2-tert-butyl-4-chloro-5-methylphenol (590 mg, 1.5 mmol, 1.0 equiv) was dissolved in chlorobenzene (1.5 mL). Di-tert-butyl peroxide (287 L, 1.58 mmol, 1.05 equiv) was then added. The vial was capped and placed in the microwave reactor. After thoroughly mixing for 5 minutes to ensure that the peroxide was thoroughly distributed throughout the reaction mixture, the reaction was heated to 200 C for 10 minutes. Upon cooling, the reaction was directly purified by flash chromatography on silica gel to afford the desired product in 98% isolated yield. |
98% | With C26H26N2O8V2*CH4O In tetrachloromethane at 20℃; for 144h; | 2.4 Representative procedure for oxidative coupling of 2-naphthol catalyzed by complex 1 Liquid phase catalytic coupling of 2-naphthol was carried out in a 25mL round bottom flask equipped with a magnetic stirrer. In a typical experiment, catalyst (63mg, 0.01mmol) was added to a flask containing the anhydrous solvent (5mL). The solution was stirred for 10 minutes under desired atmosphere and then treated with a solution of 2-naphthol (2-naphthol was dissolved in the same solvent used in the reaction). Temperature was kept stable during the reaction and controlled by a thermometer and the course of the reaction was monitored by TLC (24h). After checking by TLC, the reaction mixture was concentrated under reduced pressure and the product was isolated by column chromatography (ethyl acetate:petroleum ether=1:3) to give the coupling product, BINOL. M.p. 205-207°C. Anal. Calc. for C20H14O2 (MW=286.33): C, 83.90; H, 4.39. Found: C, 83.88; H, 4.36%. FT-IR (KBr, cm-1): 34.85 (m), 34.03 (m), 3051 (w), 2923 (w), 2851 (w), 1617 (s), 1590 (s), 1508 (m), 1470 (m), 1461 (m), 1435 (w), 1404 (w), 1382 (vs), 1347 (w), 1322 (m), 1273 (m), 1252 (m), 1217 (s), 1175 (s), 1146 (s), 1125 (m), 1023 (w), 979 (w), 960 (w), 930 (w), 864 (w), 826 (vs), 784 (w), 774 (w), 751 (vs), 723 (w), 675 (w), 665 (w), 624 (w), 585 (w), 573 (m), 533 (w), 489 (w). 1H NMR (250.13MHz, CDCl3, 25°C, TMS): δ=7.97 (d, J=9.0Hz, 2H), 7.53 (d, J=7.75Hz, 2H), 7.40-7.25 (m, 6H), 7.15 (d, J=8Hz, 2H), 5.03ppm (s, 2H, OH). 13C NMR (62.90MHz, CDCl3): δ=152.73 (C-OH), 133.4, 131.4, 129.44, 128.4, 127.5, 124.2, 124.0, 117.7, 110.8ppm. UV-Vis (in CH3OH, c=2.5×10-5M, λmax [nm] with ε [M-1cm-1]): 228 (51300), 278 (4440), 335 (3400). |
97% | With air; copper(II) sulfate In chlorobenzene at 140℃; for 8h; other arenes, other solvents, various reactants ratio, air absence; | |
97% | With air In chlorobenzene at 140℃; for 8h; | |
97% | With air; copper(II) sulfate In chlorobenzene at 140℃; for 8h; | |
97% | With iron(III) chloride for 0.0833333h; microwave irradiation; | |
97% | With oxygen In toluene at 20℃; for 12h; Irradiation; Green chemistry; | |
96% | With air In dichloromethane at 0℃; for 20h; variation of oxidant atmosphere; coupling of further naphthol derivatives; | |
96% | With air In dichloromethane at 0℃; for 20h; | |
96% | With oxygen In dichloromethane | |
96% | With air; CuCl(OH)-TMEDA at 50℃; for 4h; | |
96% | With silica gel; iron(III) chloride for 0.0166667h; microwave irradiation; | |
96.3% | With iron(III) chloride hexahydrate In water at 50℃; for 1h; | |
95% | With iron(III) chloride at 50℃; for 2h; other temp., reagent or irradiation with ultrasound; oxidative coupling reactions of other phenols in the solid state; | |
95% | With iron(III) chloride at 50℃; for 2h; other fenols; other reagent; var. reaction time and temp.; | |
95% | With iron(III) chloride at 50℃; for 2h; solid state; | |
95% | With iron(III) chloride at 50℃; for 2h; | |
95% | With ethylamine; copper dichloride In methanol for 20h; Ambient temperature; | |
95% | With iron(III) chloride In water at 50℃; for 1h; | |
95% | With air; Cu-exchange montmorillonite In chlorobenzene at 140℃; for 6h; | |
95% | With Cu(II) oxymetasilicate for 0.05h; microwave irradiation; | |
95% | With potassium <i>tert</i>-butylate In tetrahydrofuran for 0.49h; Inert atmosphere; | |
93% | With air; copper(l) chloride In methanol for 10h; Heating; | |
92% | With CuCl(OH)-TMEDA; oxygen In dichloromethane for 1h; Ambient temperature; | |
92% | With oxygen In dichloromethane at 20℃; for 24h; | |
92% | With ammonium cerium(IV) nitrate In methanol at 20℃; for 0.166667h; | |
92% | With oxygen In chlorobenzene for 12h; Heating; | |
92% | With iron(III) chloride hexahydrate In water at 50℃; for 1h; | |
91% | With iron(III) chloride In water for 3h; Reflux; | 4.2. 1,1'-Binaphthalene-2,2'-diol or BINOL (8)9 To a suspension of 2-naphthol (7) (3.00 g, 20.81 mmol) in H2O (100 mL) was added anhydrous FeCl3 (5.00 g, 30.83 mmol) and the mixture was then refluxed for 3 h. Subsequently, the crude product was extracted from reaction mixture with ethyl acetate. The combined organic layer was washed with water and brine, dried over anhydrous Na2SO4 and evaporated to dryness. Finally, column chromatography (Silica gel; 8:2 hexane/ethyl acetate as an eluent) was followed to provide 1,1'-binaphthalene-2,2'-diol (8) (2.71 g,91%) as a white solid, mp 210-212 C (lit. mp 216-218 C);9bvmax(neat) 3484, 3399, 1617, 1595, 1509, 1470, 1461, 1380, 1321,1209, 1168, 1141, 1124, 825, 814, 750, 664 cm1; dH (500 MHz,CDCl3) 7.16 (2H, d, J 8.4 Hz, Ar), 7.30e7.33 (2H, m, Ar), 7.36e7.39(4H, m, Ar), 7.89 (2H, d, J 8.1 Hz, Ar), 7.97 (2H, d, J 9.0 Hz, Ar); dC(125 MHz, CDCl3) 110.9, 117.8, 124.0, 124.2, 127.5, 128.4, 129.5, 131.4,133.4, 152.7; HRMS (ESI): MNa, found: 309.0887. C20H14O2Na requires 309.0886. |
90% | With air; Cu(OH)Cl*1,2-di(pyrrolidin-1-yl)ethane In dichloromethane at 20℃; for 18h; | |
90% | With iron(III) chloride hexahydrate In neat (no solvent, solid phase) at 50℃; | |
90% | With sodium hydroxide In toluene at 100℃; for 12h; | |
89% | With oxygen; iron oxide In toluene at 20℃; for 2h; Irradiation; | 3.2.5. Photocatalytic oxidation of 2-naphthol to BINOL with molecularoxygen (O2) Initially, the reaction was performed with the optimized parametersobtained for photocatalytic BA oxidation for both the oxidants. Underthis condition, BINOL was obtained with very unsatisfactory yield. Fromour own investigation and various other literature reports suggesttoluene as a suitable solvent for such oxidative coupling reaction [24,68]. Accordingly, the reaction was carried out by using toluene as thesolvent under the photocatalytic conditions with O2 and H2O2 separately.At first, we dissolved 2 mmol of 2-naphthol in 20 mL of toluene inpresence of 25 mg of Fe2O3-HNT catalyst, and the whole reactionmixture was saturated with O2 at the flow rate of 60 mL/ min. Consequently,the photoirradiation time was set for 30 min and after this interval,it was observed that BINOL was selectively obtained with 32%yield. As we know that there was a major influence of the photoirradiationtime in the reaction progress, so varying the photoirradiationtime-lapse from 30 to 120 min an increase% yield of BINOL wasobserved up to 64% and after 120 min the formation of BINOL gotsaturated. Therefore, 120 min of photoirradiation was considered as theoptimum time for this transformation (Fig. S13a). The time interval inthis oxidative coupling reaction was found to be effectively low incomparison with various other non-photocatalytic conditions [69]. Likethe BA oxidation reaction, we varied the rate of flow of O2 partialpressure to get a better% yield. It was noticed that maximum 87% yieldof BINOL was formed when the O2 flow rate was 100 mL/ min under thisapplied condition (Fig. S13b). Declination in the % selectivity of BINOLwas observed when O2 flow rate was increased beyond 100 mL/ min(Fig. S13c). After getting the optimum time interval as well as the idealrate of O2 partial pressure, amount of the catalyst was varied. Initially, the reaction proceeded in presence of 25 mg of the synthesized catalystwith the same condition cited above. By varying the amount of thecatalyst from 5 to 30 mg there was an increase in the% yield up to 89%and after increasing the same BINOL formation got saturated. Hence, 30mg of Fe2O3-HNT was considered to be the effective amount of thecatalyst for this photocatalytic transformation (Fig. S13d). |
88% | With ferric chloride Inert atmosphere; | |
87% | With iron(III) chloride; sodium chloride In solid for 3h; | |
87% | With tetrasodium cobalt(II) 4,4',4'',4'''-tetrasulphophthalocyanine; oxygen In water at 100℃; for 15h; Schlenk technique; | |
87% | With 3-Methylbenzo<b>thiophene sulfoxide; trifluoroacetic anhydride In dichloromethane at -40 - 20℃; for 2.25h; Inert atmosphere; | |
86% | With Ru-Co-Fe-CO3 hydrotalcite-like compound; air at 50℃; for 24h; Neat (no solvent); | |
86% | With iron(III) chloride hexahydrate In water at 20 - 50℃; for 3h; Inert atmosphere; | |
86% | With bis(acetylacetonato)manganese(II) In chloroform at 50℃; | |
86% | With (Ra,S,S)-(C10H9(VO2(OH))(CHNCH(C(CH3)3)COO))2; rac-[4,4′-biphenanthrene]-3,3′-diol In 1,2-dichloro-ethane at 10℃; for 24h; | |
86% | With Fe2Co(O)[(OOCC6H4NO2)6]NO3*2H2O supported on zeolite Y In methanol at 45℃; for 18h; | |
86% | With iron(II) triflate; tert.-butylhydroperoxide; (S)-1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine oxide) In nonane; nitromethane at 0℃; | |
85% | With iron(III) chloride at 25 - 50℃; | |
84% | With iron(III) chloride In water for 3h; Reflux; | |
83% | With nitrosonium tetrafluoroborate; trifluoroacetic acid In dichloromethane at -15℃; for 1h; Sealed tube; | |
82% | With p-methoxy-phenylazide; iron(II) chloride In 1,2-dichloro-ethane at 80℃; for 10h; Inert atmosphere; | |
81% | With iron(III) chloride hexahydrate In water at 50℃; for 1h; | |
81% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; copper(l) chloride In butan-1-ol at 50 - 70℃; for 3.5h; | 1-2; 1-4 Example 2 Add 40g of 2-naphthol to a 500ml four-necked flask equipped with heating and stirring devices, thermometers, and reflux condenser devices.200g n-butanol, 0.823g solid catalyst CuCl, 1.265g ligand DBU,Then heat to above 56°C to dissolve 2-naphthol, and oxidize with air with a flow rate of 300ml/min.React for 3.5 hours at 50-70°C, add water to the reaction mixture,Stir and raise the temperature to 80°C, wash with water to separate the liquids, remove the waste water layer to obtain the organic layer.Cool down to 25°C, crystallize, filter, and dry to obtain a crude product of off-white binaphthol. The filtrate is distilled under reduced pressure.Recovery of n-butanol solvent for recycling.After the crude binaphthol is recrystallized, it is dried to obtain 32.40 g of binaphthol product with a yield of 81.0%. |
81.8% | With 1,10-Phenanthroline; copper(l) chloride In butan-1-ol at 50 - 70℃; for 24h; | 1-2; 1-4 Example 2 A method for efficiently preparing 1,1′-bin-2-naphthol with a solid ligand-assisted catalyst is equipped with a heating and stirring device, a thermometer,Add 40g of 2-naphthol and 200g of n-butanol to the 500ml four-necked flask of the reflux condenser device.The catalyst solid CuCl 0.823g, the ligand o-phenanthroline 1.498g, and then heated to 56°C above 2-naphthol to dissolve,Add air with a flow rate of 300ml/min for oxidation, react at 50-70°C for 4.5 hours, add water to the reaction mixture,Stir and raise the temperature to 80°C, wash with water to separate the liquids, remove the waste water layer to obtain the organic layer, and cool to 25°C,Crystallized, filtered and dried to obtain crude 1,1'-bi-2-naphthol, the filtrate was distilled under reduced pressure, and the n-butanol solvent was recovered for recycling.The crude 1,1'-bi-2-naphthol product is recrystallized and dried to obtain 32.72g of 1,1'-bi-2-naphthol product with a yield of 81.8%. |
80% | With dipotassium peroxodisulfate In trifluoroacetic acid at 20℃; for 16h; Sealed tube; Schlenk technique; regioselective reaction; | |
79% | With iron(III) chloride In water for 0.5h; Heating; | |
78% | With perchloric acid; ammonium vanadate In water; acetone for 20h; Ambient temperature; | |
78.3% | With aluminum oxide; iron(III) chloride In dichloromethane at 90℃; for 0.5h; | |
77% | With iron(III) chloride In water at 100℃; for 0.5h; | |
75% | With FeCl In water for 0.5h; Heating; | |
75% | With phosphate buffer; dihydrogen peroxide In acetonitrile at 20℃; horseradish peroxidase; | |
74% | With air; 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene for 21h; Irradiation; | |
74% | With oxygen In toluene at 90℃; for 24h; | |
73% | With manganese(IV) oxide; trifluoroacetic acid In dichloromethane at 20℃; for 8h; | |
72% | With oxygen In toluene at 60℃; for 11h; | |
71% | With iron(III) chloride In water Reflux; | |
70% | With copper acetylacetonate for 0.0333333h; microwave irradiation; | |
68% | With air; trifluorormethanesulfonic acid; sodium nitrite In dichloromethane; acetonitrile at -78℃; for 1h; | |
63% | With iron(III) chloride hexahydrate In acetonitrile at 60℃; for 5h; | |
60% | With iron(III) chloride In tetrahydrofuran for 3h; Heating; | |
60% | With titanium tetrachloride In nitromethane at 40℃; for 4.5h; | |
58% | With iron(III) chloride for 504h; | |
58% | With sodium hypochlorite; water; sodium hydroxide at 20℃; for 2h; | |
55.9% | With iron(III) chloride at 60℃; | |
53% | With dicarbonyl(chloro)(η5-pentaphenylcyclopentadienyl)ruthenium(II); potassium <i>tert</i>-butylate In toluene at 20℃; for 6h; | |
52% | With iron(III) chloride hexahydrate In methanol; water at 90 - 100℃; for 0.0833333h; Flow reactor; Green chemistry; | |
41% | With tetraethylammonium methyl sulfate In hexafluoropropan-2-ol at 50℃; Electrolysis; | |
40% | With di-tert-butyl peroxide In 1,2-dichloro-ethane for 12h; Inert atmosphere; Irradiation; regioselective reaction; | |
39% | With iron(III) chloride; Methylated β-cyclodextrin In dichloromethane; water at 60℃; for 2h; | |
35% | With dihydrogen peroxide; horseradish peroxidase In 1,4-dioxane at 20℃; | |
21% | With oxygen In dichloromethane at 30℃; for 24h; | |
21% | With heptafluorobutyric Acid at 100℃; Ionic liquid; Electrochemical reaction; | |
18% | With potassium phosphate; palladium diacetate In 1,4-dioxane at 130℃; for 16h; Inert atmosphere; Glovebox; Sealed tube; | |
15% | With oxygen; manganese(II) acetate In toluene at -10℃; for 24h; | |
13% | With tert.-butylhydroperoxide; C26H30Cl4CoN4O2(1+)*Cl(1-); potassium hydroxide In decane; toluene at 25℃; for 4h; Inert atmosphere; Schlenk technique; | Oxidative coupling of 2-naphthol (general procedure). General procedure: A 5.5 M solution of tert butyl hydroperoxide in decane (0.03 mL, 3•10-4mol) was added to a Schlenk flask (charged with a mixture of 2-naphthol (14 mg,125 mmol), catalyst (1.01 10-5 mol), and freshly ground solid KOH (3 mg, 5•10-5 mol) in toluene (1.25 mL) under a flow of argon at room temperature. The reaction mixture was vigorously stirred for 4 h. The product was isolated by preparative chromatography on silica gel adsorbent and petroleum ether-ethyl acetate (5 : 1) as eluent. Yield 74%, white solid. 1H NMR, δ 7.98 (d, 2 H, J = 8.9 Hz); 7.90 (d, 2 H, J = 7.9 Hz);7.43-7.35 (m, 4 H); 7.34-7.28 (m, 2 H); 7.17 (t, 2 H, J = 9.7 Hz); 5.03 (s, 2 H, OH). |
With copper(II) nitrate; ethylamine In methanol Ambient temperature; further amines and copper salts, variation of substrate/reagent ratio,; | ||
With iron(III) chloride In water at 50℃; for 1h; other Fe salts; var. temp. and time; | ||
With oxygen; calcium oxide at 300℃; | ||
With hydrogenchloride; iron(III) chloride | ||
With sodium acetate; iron(III) chloride at 85℃; | ||
With iron(III) oxide; water | ||
With iron(III) oxide at 260℃; | ||
With copper(II) oxide at 260℃; | ||
With manganese(IV) oxide at 260℃; | ||
With vanadia at 300℃; | ||
With iron(III) chloride | ||
With iron(III) chloride | ||
With copper diacetate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate In acetone for 20h; Inert atmosphere; Reflux; | Preparation of ( ±)-2,2′-dimethoxy-1,1′-binaphthalene [( ±)-6, in Scheme 2] A 100-mL, one-necked, round-bottomed flask equipped witha stir bar was charged with potassium carbonate (K2CO3)(2.42 g, 17.5 mmol, 3.5 equiv), methyl iodide (MeI)(1.25 mL, 20 mmol, 4 equiv), ( ±)-BINOL (1.43 g, 5 mmol,1 equiv) and anhydrous acetone (40 mL). With stirring, thereaction mixture was heated for 20 h under reflux conditions,and then cooled down to room temperature. The reactionmixtures were diluted with deionized water and washed withEtOAc. The combined organic phase was washed with brine,dried over Na2SO4,filtered and concentrated in vacuo toafford 1.49 g (95%) corresponding product as a pale yellowsolid. |
92% | With potassium carbonate In acetone | |
89% | With potassium carbonate In acetone for 3h; Reflux; | 4.4. General procedure A: synthesis of compounds 9-12 and 19 General procedure: To a mixture of BINOL (8) or dibromobinaphthol 18 (1.75 mmol) and alkyldihalide (1.75 mmol) or methyliodide (17.5 mmol) in acetone (50 mL) was added K2CO3 (17.5 mmol). The reaction was then refluxed until BINOL was completely consumed (monitored byTLC). After that the reaction mixture was filtered by reduced pressure, the filtrate was evaporated to dryness to yield the crude product which was then purified by column chromatography (Silicagel; 19:1 hexane/ethyl acetate as an eluent) to provide BINOL derivatives. 4.4.1. Dinaphtho[2,1-d:1',2'-f][1,3]dioxepine (9). |
84% | With potassium carbonate In N,N-dimethyl-formamide at 50℃; | |
83% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; | |
80% | With NaCO3 | |
With potassium hydroxide | ||
With potassium carbonate In N,N-dimethyl-formamide at 50℃; | ||
With sodium chloride In tetrahydrofuran; hexane; water monomer; mineral oil; benzene | R.1 R-2,2'-Dimethoxy-1,1'-binaphthyl REFERENCE EXAMPLE 1 R-2,2'-Dimethoxy-1,1'-binaphthyl A solution of 465 mg of R-2,2'-dihydroxy-1,1'-binaphthyl in 10 ml of tetrahydrofuran was added to a suspension of 1.35 g of potassium hydride in mineral oil (content 22.5% w/w) with cooling in an ice-bath and the mixture was stirred at room temperature for one hour. To the solution obtained was added a solution of 2.00 ml of methyl iodide in 4 ml of tetrahydrofuran, and the mixture was stirred at ambient temperature for 16 hours. The reaction mixture was poured into 100 ml of a mixture of benzene and water (1:1), and separated into an aqueous layer and an organic layer. The aqueous layer was extracted with benzene, and the extract was combined with the organic layer, washed with a saturated aqueous solution of sodium chloride, dried over sodium sulphate and concentrated under reduced pressure. The residue was purified by recrystallisation from a mixture of benzene and hexane to give 461 mg of the title compound as white crystals having the following physical characteristics: melting point: 225°-226° C.; [α]D21 =+72.0° (c=0.286, tetrahydrofuran). | |
With potassium carbonate In acetone Reflux; | ||
With potassium carbonate | ||
14.9 g | Stage #1: 1,1'-bi-2-naphthol With anhydrous sodium carbonate In acetone for 0.166667h; Stage #2: iodomethane In acetone at 60℃; for 24h; | 1-6 Example 1 Adding a single configuration of BINOL to the reactor(14.32g, 50mmol), anhydrous acetone and sodium carbonate (23.3g, 168.6mmol),After stirring for 10 minutes, methyl iodide (12.2 mL, 196 mmol) was added, and stirring was continued at 60 ° C for 24 hours.After completion of the reaction, the solvent was removed, suction filtration, washing with water, and drying were performed to obtain 14.9 g of 2,2'-dimethoxy-1,1'-binaphtyl. |
With potassium carbonate; Cs2CO3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In various solvent(s) for 5h; Heating; | |
94% | With HY zeolite In 1,2-dichloro-benzene at 180℃; for 4h; | |
94% | In toluene Reflux; Acidic conditions; |
93% | With trifluorormethanesulfonic acid; trifluoromethylsulfonic anhydride In benzene for 5h; Ambient temperature; | |
92% | With HY zeolite In 1,2-dichloro-benzene at 180℃; | |
91% | With Nafion-NR50 ion-exchange resin In o-xylene for 16h; Heating; | |
90% | With 1,2-dichloro-benzene for 5h; Reflux; | |
90% | With Zeolith CBV780 In 1,2-dichloro-benzene for 18h; Reflux; | 8 A 300mL eggplant-shaped flask, the raw material 1,1'-bi-2-naphthol (5.4g, 19mmol), Zeolyst Co. weighed Zeolith the CBV780 (2.5g), was suspended was added o- dichlorobenzene (30mL). After the suspension was heated to reflux 18 hours, heating was filtered, washed with toluene column. After concentrating the filtrate to approximately o- dichlorobenzene are others, was precipitated by adding methanol. The resultant solid was filtered to give the intermediate 7 as a white powder (4.6g, 18mmol, 90%). It was identified as the desired compound by FDMS (field desorption mass analysis). |
84% | With toluene-4-sulfonic acid In toluene at 140℃; for 48h; | |
74% | With HY Zeolite (HS-320) In 1,2-dichloro-benzene for 144h; Reflux; | |
70% | With toluene-4-sulfonic acid In toluene at 100℃; for 12h; | 1 Synthesis of Intermediate I-1 5.73 g (20 mmol) of (1,1′-binaphthalene)-2,2′-diol and 4.10 g (20 mmol) of p-TsOH were dissolved in 150 mL of toluene, and then stirred at about 100° C. for about 12 hours. The resulting product was cooled down to room temperature, and an aqueous potassium carbonate solution was added thereto, followed by extraction three times with 60 mL of ethyl acetate. An organic layer was collected from the resulting product and dried using magnesium sulfate. After evaporating the solvent from the resulting product, the residue was separated and purified using silica gel column chromatography to obtain 3.76 g (Yield: 70%) of Intermediate I-1. This compound was identified using liquid chromatography-mass spectrometry (LC-MS). (0315) C20H12O: M+1 268.3 |
70% | With toluene-4-sulfonic acid In toluene at 100℃; for 12h; | 1 Synthesis of intermediate I-1 A solution of 5.73 g (20 mmol) of (1,1'-binaphthyl) -2,2'-diol and 4.10 g (20 mmol) of p-TsOH were dissolved in 150 mL of toluene,The solution was stirred at 100 & lt; 0 & gt; C for 12 hours.The reaction solution was cooled to room temperature,Adding a potassium carbonate solution thereto,The organic layer was extracted three times by using 60 mL of ethyl acetate.The organic layer thus collected was dried with magnesium sulfate,The residue obtained after the solvent was evaporated from the silica gel column chromatography was used to separate and purify the residue,To obtain 3.76 g of intermediate I-1 (yield: 70%).The compounds thus produced were determined by using liquid chromatography-mass spectrometry (LC-MS). |
With zinc | ||
With zinc(II) chloride at 270℃; | ||
With phosphorus pentaoxide | ||
With trichlorophosphate | ||
With vanadia | ||
With calcium oxide at 350℃; | ||
With potassium hydrogensulfate at 200℃; for 3h; | ||
With zeolite In 1,2-dichloro-benzene at 180℃; for 5h; | ||
With trifluorormethanesulfonic acid In toluene for 48h; Inert atmosphere; Reflux; | Dinaphtho[2, l-h: l ',2 '-d]furan [ 1 , 1 ,-Binaphthalene]-2,2'-diol (30.0 g, 0. 1 05 mo I, 1 .0 eq. ) was placed in a flask and flushed with argon. Anhydrous toluene (300 m L ) was added, followed by trifluoromethanesulfonic acid (1 1.7 ml., 0.2 1 0 mo I, 2.0 eq. ). After further degassing, the mixture was re fluxed for 48 hours. After cool ing, the organic layer was extracted with water (500 m l. ), dried over gSO i, and reduced under vacuum until precipitation. Hexane (300 ml.) was then added, and the resulting suspension was stirred for 2h before being filtered off. This solid was dissolved in DC I, and filtered over silica (elution with hexane / DCM 2 : 1 ). The volume of the fraction obtained was reduced to ca. 50 m l., and the resulting crystals were filtered off, yielding the title compound. | |
With toluene-4-sulfonic acid In toluene at 140℃; for 36h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer In methanol at 40℃; for 24h; Inert atmosphere; regioselective reaction; | |
94% | With hydrogen | |
93% | With 10% Rh/C; hydrogen In isopropyl alcohol at 60℃; for 10h; |
76% | With palladium on activated carbon In ethanol at 100℃; for 1h; Autoclave; | |
75.8% | With hydrogen In ethanol; ethyl acetate at 165℃; for 4h; | |
With methanol; nickel at 110 - 130℃; Hydrogenation; | ||
With ethanol; nickel at 110 - 130℃; Hydrogenation; | ||
With nickel; isopropyl alcohol at 110 - 130℃; Hydrogenation; | ||
With potassium hydroxide; nickel at 110 - 130℃; Hydrogenation; | ||
With sodium hydroxide; nickel at 110 - 130℃; Hydrogenation; | ||
With hydrogen In acetic acid | ||
With palladium on activated charcoal; hydrogen Inert atmosphere; Schlenk technique; | ||
With palladium/alumina; hydrogen In ethanol at 20 - 130℃; for 5h; Autoclave; | 1 [Example 1] A 500 mL autoclave equipped with a magnetic stirrer was charged with 45.0 g (0.16 mol) of 1,1′-bi-2-naphthol, 33.00 g of 5% Pd / Al 2 O and 105 g of ethanol, and with stirring, a hydrogen pressure of 5 MPa. ,The reaction was carried out at a reaction temperature of 130 ° C. for 5 hours.After the reaction mixture was cooled to room temperature, the catalyst was filtered off.The obtained filtrate was gradually heated from room temperature at normal pressure to distill off ethanol, and then purified on a silica gel column (developing solvent: hexane / diethyl ether = 2/1).Purity 99.6 GC area%5,5 ', 6,6', 7,7 ', 8,8'-octahydro-2,2'-dihydroxy-1,1'-binaphthyl was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With nitric acid In acetic acid at 20℃; for 1h; Cooling with ice; | 2.2. Synthesis of monomer binaphthyl diamine In a round-bottom flask, 1,10 -binaphthol (3.49 mmol) were dissolvedin acetic acid (15 mL). After kept in the ice-water bath for 15 min, nitricacid (98%, 0.62 mL) was dropped into the solution slowly under a strongmagnetic stirring. Then, the ice water bath was removed and the solutionwas stirred at room temperature for 1 h. While, the clear mixture became white, turned to black and finally was green. The mixture was poured into ice-water (500 mL) and stirred for 10 min. The powder (compound 1) was collected from the ice-water using the vacuum filtration and was washed with cold ethanol till its color became grayish yellow. The yield of compound 1 is 78%. Mp > 300 C. 1H NMR(DMSO-d6, 400 MHz, δ, ppm): 10.34 (s, 2H), 8.96 (d, J 1.5 Hz, 2H),8.28 (dd, J 1.5, 7.2 Hz, 2H), 7.97 (d, J 7.2 Hz, 2H), 7.53 (d,J 9.0 Hz, 2H), 7.09 (d, J 9.0 Hz, 2H); 13C NMR (DMSO-d6, 75 MHz):δ 157.1, 142.4, 137.0, 132.1, 126.3, 125.5, 125.2, 120.6, 119.6, 115.0 |
73.6% | With nitric acid; acetic acid In dichloromethane at 20℃; for 16h; | |
61% | With tert.-butylnitrite In tetrahydrofuran at 20℃; for 18h; |
With nitric acid; acetic acid | ||
With nitric acid; acetic acid In dichloromethane at 20℃; | 1 (1) 6,6'-Dinitro(1,1'-binaphthyl-2,2')diol Add 22.88 g (80 mmol) of binaphthol to 100 mL of acetic acid and 100 mL of CH 2 Cl 2 solution, and add 6.8 mL (160.4 mmol) of fuming HNO3 in an ice bath, and stir at room temperature overnight.TLC detects the formation of new substances and pours the product into ice water for filtration.The solid was washed with CH 2 Cl 2 and methanol.TLC is detected as a point, vacuum dried,The product a6,6'-dinitro(1,1'-binaphthyl-2,2') diol was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With ammonium hydroxide; ammonium bisulfite; at 220℃; for 16h;Autoclave; | General procedure: Racemic 2,2'-dihydroxy-1,1'-binaphthyl (rac-BINOL, 1.6 g, 5.6 mmol), half the amount of ammonium sulfite monohydrate (AR, as described in Table 2 as aminating agent 9.0 g, 67 mmol) and aqueous ammonia (12 mL, 174 mmol) were placed in an autoclave. The mixture in the autoclave was stirred at the reaction temperature described in Table 2 for half the reaction time described in Table 2 and the mixture was cooled to 25 C. To the cooled reaction mixture, the remaining half amount of AR (9.0 g, 67 mmol) and aqueous ammonia (12 mL, 174 mmol) described in Table 2 were added, and the reaction described in Table 2 was performed again.The mixture was stirred at the temperature for the remaining reaction time described in Table 2.The reaction mixture was cooled to 25 C., and the resulting solid was washed with water and filtered. The filtrate was recrystallized with benzene to separate rac-NOBIN and DBC.The reaction yield was calculated from chiral HPLC, and the isolated yield recrystallized from benzene was calculated and described in Table 2. |
27% | With ammonium hydroxide; ammonium sulfite monohydrate; In water; at 200℃; under 13501.4 - 33753.4 Torr; for 120h;Autoclave; | 7H-Dibenzo[c,g]carbazole (12c): 30 g (0.105 mol) of 1,1'-binaphthalene-2,2'-diol (BINOL), 30 g (0.224 mol) of (NH4)2SO3·H2O and 90 ml of 26 % NH4OH was heated at 200C in a 160 ml autoclave (Parr Instrument) for 5 days (after 48 h the pressure dropped from 45 to 18 bar). Upon cooling down, the crude matter was washed with boiling water, dissolved in a 1:1 mixture of EtOH:HCl (conc.), extracted with hot toluene (3x200 ml) and concentrated under vacuum. Residual starting material was removed by extraction with 2M NaOH solution (3x200 ml). Organic layers were combined, dried over Na2SO4, filtered, concentrated and chromatographed on a SiO2 column (50 % DCM in hexanes). Yield: 7.7 g (27 %) of dark-yellow crystalline solid. M.p. 154-156C. 1H NMR (CDCl3, 300 MHz): delta 9.22 (d, J=8.5, 2H), 8.79 (br, s, 1H), 8.05 (dd, J=8.1, 1.3, 2H), 7.89 (d, J=8.7, 2H), 7.74-7.65 (m, 4H), 7.53 (ddd, J=8.0, 6.9, 1.0, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1-methyl-1H-imidazole; potassium carbonate; copper(l) chloride In m-xylene at 120℃; for 20h; | |
78% | With 1-methyl-1H-imidazole; potassium carbonate; copper(l) chloride In m-xylene at 120℃; for 24h; | |
64% | With copper(l) iodide; Trimethylacetic acid In dimethyl sulfoxide at 140℃; for 8h; |
With manganese(IV) oxide; nitrobenzene | ||
With potassium hexacyanoferrate(III) | ||
With copper(II) oxide at 300℃; | ||
With potassium carbonate; nitrobenzene | ||
With copper diacetate In sodium hydroxide | ||
With potassium carbonate; nitrobenzene | ||
With manganese(IV) oxide; nitrobenzene | ||
With copper(II) oxide at 300℃; | ||
With 1-methyl-1H-imidazole; potassium carbonate; copper(l) chloride In m-xylene at 120℃; for 20h; | Then, 1,1'-binaphthol (1.0047g, 3.5mmol), K2CO3 (0.9696g, 7mmol), CuCl (0.1054g, 1.05mmol) were added to the round bottom flask, and 20mL of meta-xylene was added at room temperature. Heat and stir thoroughly to dissolve. After the solution becomes transparent, slowly add methyl imidazole (157 μL, 2.0 mmol), continue heating to increase the temperature to 120° C., react for 20 hours, and monitor the reaction by TLC during the reaction. After the reaction, the solvent was spin-dried to obtain a yellow solid. Using CHCl3 as the eluent, the solid was separated by column chromatography, and the obtained solid was recrystallized from toluene to obtain the yellow powdery solid PXX. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With pyridine; dmap In dichloromethane; toluene for 6h; Ambient temperature; | |
89% | With pyridine; dmap In dichloromethane; toluene at 0 - 20℃; for 6h; | 2 Synthesis of 1-(2-hydroxynapthalen-1-yl)napthalen-2-yl acetate (±)-(2): (C22H16O3) Dimethyl amino pyridine (17.1 mg, 0.139 mmol) and acetic anhydride (392 mg, 3.84 mmol) at 0 °C were added to a solution of 1,1'-binaphthyl-2,2'-diol (1.00 g, 3.49 mmol) in a mixture of toluene (15 mL), CH2Cl2 (10 mL) and pyridine (3 mL). The mixture was stirred at room temperature for 6 h and the solvent was removed in vacuo. The residue was dissolved in ether (25 mL), successively washed with 2 N HCl (20 mL), sat. NaHCO3 (20 mL) and brine (20 mL) and then dried (anhydrous Na2SO4). Evaporation and silica gel column chromatography (EtOAc: Hexane; 2:98) gave 1-(2-hydroxynapthalen-1-yl)napthalen-2-yl acetate (+-)-2 (1.02 g, 89%). Colorless crystals; mp 125-127 °C; IR (KBr) cm-1: 1230, 1740, 3460. 1H NMR, δ: 1.86 (s, 3H, CH3CO), 5.22 (s, 1H, OH), 7.03 (d, J = 8.2 Hz, ArH), 7.23-7.26 (m, 2H, ArH), 7.31-7.35 (m, 3H, ArH), 7.40 (d, J = 8.5 Hz, ArH), 7.50 (t, J = 7.5 Hz, 1H, ArH), 7.85 (d, J = 8.0 Hz, ArH), 7.91 (d, J = 8.5 Hz, 1H, ArH), 7.97 (d, J = 8.5 Hz, 1H, ArH), 8.07 (d, J = 9.0 Hz, 1H, ArH). 13C NMR, δ 20.1, 114.1, 118.3, 121.8, 123.2, 123.6, 124.6, 125.8, 126.4, 126.7, 127.5, 128.1, 128.4, 129.1, 130.4, 130.8, 132.3, 133.5, 133.6, 148.1, 151.8, 170.4. ESI-MS (m/z): 328. Anal. Calc. for C22H16O3: C, 80.47; H, 4.91. Found C, 80.52; H, 4.96. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | NaH (1.92 g, 80 mmol) was added to DMF (30 mL) in an ice bath. BINOL (1,1?-bi-2-naphthol) (10 g , 34 mmol) in THF (50 ml) was dropped to this solution for 20 min. After 30 min, chloromethyl methyl ether (6.4 g, 80 mmol) was dropped to this solution for 20 min. The reaction was monitored by TLC. After 1 h stirring, 3 was isolated from the organic layer by extraction of the reaction mixture with chloroform and water. The product 3 was further purified by silica gel column chromatography with a petroleum ether/ethyl acetate (5/1)mixture. Yield: 90%.1H NMR (400 MHz, CDCl3) delta 7.95-7.93 (d, J = 9.6Hz, 2H), 7.87-7.85 (d, J = 8.4 Hz, 2H), 7.58-7.56 (d, J = 9.6 Hz, 2H),7.35-7.31 (m, 2H), 7.23-7.14 (m, 4H), 5.08-4.96 (q, J = 6.8 Hz, 4H), 3.13 (s,6H). | |
90% | The reaction was carried out in an ice bath. Tetrahydrofuran (30 mL) was added to a solution of sodium hydride (1.92 g, 80 mmol)Three-necked flask. A solution of 1,1'-binaphthol (compound (1)) (10 g, 34 mmol) in tetrahydrofuran (50 mL) was dissolvedThe solution was slowly added dropwise to the reaction solution over a period of 20 minutes. After completion of the addition, the reaction was continued for 30 minutes, and then chloromethyl ether (6.4 g, 80 mmol) was slowly added dropwise to the reaction solution. The reaction was continued for about one hour and monitored by thin layer chromatography. After the reaction was complete, the reaction was quenched with water (20 mL). The organic material was extracted with dichloromethane and water and the solvent was removed. The compound (2) was isolated by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (5: 1) as the eluent. Yield: 90%. | |
88% | (1) Sodium hydride (0.7 g, 17.5 mmol) and 20 ml of anhydrous THF were added to a reaction flask equipped with a stirring apparatus, and stirred. a mixture of BINOL (2 g, 7.0 mmol) and 15 ml of anhydrous THF was added dropwise to the reactor through a constant pressure dropping funnel at 0 C, after completion, in this state for at least 15 minutes;To the reactor, chloromethyl methyl ether (1.33 ml, 17.5 mmol) was added, and after the addition, the temperature was raised to room temperature, stirring was continued, and the reaction was stopped by TLC until the starting point disappeared; then 100 ml of water was added to the reactor. The organic phase was separated with a sep. funnel, and the aqueous phase was extracted three times with ethyl acetate. The organic phase was combined and washed twice with saturated sodium hydrogen carbonate and brine and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and purified by silica gel column chromatography (ethyl ether: ethyl acetate = 20:1, v/v)The compound of formula IIa was obtained in a yield of 88% |
71% | under nitrogen protection,2.5 g of binaphthol was dissolved in 100 ml of tetrahydrofuran,The solution was cooled to 0 C,Then slowly add 0.88 g of sodium hydride and stir for 15 minutes.Take 1.65 ml of 98% chloromethyl ether slowly,The mixture was warmed to room temperature for 4 hours and quenched with water.Extracted with ethyl acetate, dried over anhydrous sodium sulfate,The column was purified by silica gel column to give 2.3 g of product as a 71% yield. | |
63% | To 18.3 g of sodium hydride was added 50 g (0.175 mol) of 2,2'-dihydroxy-1,1'-dinaphthyl and stirred under nitrogen in 1.0 L of dry tetrahydrofuran (THF). After 1 hour, 116 g of chloromethyl methyl ether was added to the heavy precipitate and the resulting mixture was stirred for about 12 hours and then filtered through a pad of celite. The filtrate was shaken with 500 ml of water and 1 L of methylene chloride. An aqueous layer formed and was extracted two times more with methylene chloride. The combined organic layers were washed with water saturated with potassium bicarbonate. The organic layer was dried and filtered through a squat column of alumina and the column filtrate was evaporated until crystals appeared. The crude product was purified on a silica gel column by elution with a methylene chloride/hexane solution. About 53.5 g (63%) of 2,2'-bis(methoxymethoxy)-1,1'-dinaphthyl, m.p 93-94 C., 0.11 mol was collected. [00053] Next, 171 ml of 1.6 N butyllithium in hexane was added to a mixture of 41 g of the above bisacetal in 1 L of tetrahydrofuran and stirred under nitrogen at 0 C. for 45 minutes. The reaction mixture was then allowed to warm to 25 C. and 25.8 ml of dimethyl sulfate was added to the suspension and the mixture was stirred for 12 hours. About 30 ml of water saturated with sodium carbonate was added and the solvent was evaporated under reduced pressure at 50 C. [00054] The residue, in 300 ml of methylene chloride, was washed twice with water. An additional 300 ml of methylene chloride, 300 ml of methanol, and 25 ml of concentrated hydrochloric acid was added to the organic solution. The solution was stirred for 3 hours, and the solvent was evaporated. The yellow product was recrystallized from methylene chloride-hexane and was purified on a silica gel column (methylene chloride, hexane 1:1) to give 29.5 g (86%) of (R)-3-3'-dimethyl-2,2'-dihydroxy-1,1'-dinaphthyl, m.p. 204-206 C.; 1HNMR:2.2(s.6H), 7.1(d.2H), 7.3(m.2H), 7.4(m.2H), 7.8(m.4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 1,1'-bi-2-naphthol With sodium hydride In N,N-dimethyl-formamide at 80℃; for 0.333333h; Stage #2: N,N-Dimethylthiocarbamoyl chloride In N,N-dimethyl-formamide at 100℃; for 16h; | |
62% | With sodium hydride In N,N-dimethyl-formamide at 0 - 85℃; for 1h; Inert atmosphere; | |
With sodium hydride 1) DMF, 0 deg C, 2 h, 2) 85 deg C, 1 h; Yield given. Multistep reaction; |
With sodium hydride 1) DMF, ice-cooled, 2) 85 deg C, 1 h; Yield given. Multistep reaction; | ||
With sodium hydride 1) DMF, 0 deg C, 2 h, 2) DMF, 85 deg C, 1 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium hydroxide In ethanol Reflux; | 3.2 General procedure for the synthesis 1-a,b,c General procedure: Separately, each of the dihydroxy-substituents, catechol (a), 2,3-dihyroxynaphthalene (b), 2,2'-dihydroxy-1,1'-bisnaphthalene (c) (50 mmol), and NaOH (0.12 mol) were dissolved in 20-25 ml ethanol and 2-chloroethanol (0.12 mol) was added to this solution dropwise over 15 min. After refluxing the reaction mixture for 20 h, the resulting solid was separated by filtration. Ethanol was evaporated in vacuo and the resulting oily product was dissolved in 200 ml chloroform. The chloroform solution was washed with 3% NaOH and then with distilled water until the pH reached neutrality. |
65% | With potassium carbonate In acetone for 24h; Reflux; | |
54% | With sodium hydroxide In ethanol at 50 - 78℃; for 48.25h; Inert atmosphere; | 2.3.1 Synthesis of 2,2’-[1,1′-Binaphtalene-2,2’-diyl bis(oxy)]diethanol (1) 1,1′-Binaphthalene-2,2′-diol (10g, 35mmol) was dissolved in 60mL absolute ethanol under a N2 (g) atmosphere and NaOH (35g, 87.5mmol) was added. The mixture was heated at 50°C, and 2-chloroethanol (6mL, 87.4mmol) and 17mL absolute ethanol were added dropwise for 15min. Then it was refluxed for two days under N2 (g) atmosphere. The mixture was controlled with chloroform/ methanol (9.5:0.5) solvent system and then the synthesis was completed. The cream-like mixture was cooled to room temperature, filtered and evaporated to dryness under vacuum and finally a viscous liquid product was obtained. This product was redissolved in chloroform (200mL), and then washed with 10% NaOH and water, respectively. The combined organic extracts were dried with anhydrous MgSO4 and evaporated to dryness. The product was isolated as a cream-like solid following recrystallization of the crude residue from ethanol. Yield: 7g (54%). m.p.: 100-102°C. Anal. Calcd for C24H22O4: C: 77.01; H: 5.88. Found: C: 77.20; H: 5.76%. IR (KBr tablet), νmax/cm-1: 3516-3240 (OH), 3055(Ar-H), 2917 (Alif. C-H), 1619, 1456, 1242 (Ar-O-C),1141-1047 (-OCH2), 972. 1H NMR (CDCl3), (δ:ppm): 8.06-7.87 (m, 4H, ArH), 7.47-7.11 (m, 8H, ArH), 4.19-4.03 (m, 4H, O-CH2), 3.57 (br s, 4H, O-CH2), 2.29 (s, 2H, OH). 13C NMR (CDCl3), (δ:ppm): 155.03, 134.02, 130.12, 129.87, 127.66, 126.92, 124.44, 123.69, 117.84, 111.14, 71.96, 61.46. MS (FAB) (m/z): 374 [M]+. |
17% | With potassium hydroxide In water at 70 - 90℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With pyridine; dmap In dichloromethane; toluene Ambient temperature; | |
88% | With pyridine; dmap In dichloromethane; toluene at 0 - 20℃; | 4 Synthesis of 1-(2-hydroxynapthalen-1-yl)napthalen-2-yl butyrate (±)-(4): (C24H20O3) 1-(2-Hydroxynapthalen-1-yl)napthalen-2-yl butyrate (+-)-4 (3.13 g, 88%) was prepared from 1,1'-binaphthyl-2,2'-diol (2.86 g, 10 mmol) using the same procedure as applied for (+-)-2; mp 136-138 °C, IR (KBr) cm-1: 1170, 1730, 3410; 1H NMR, δ: 0.57 (t, J = 7.4 Hz, 3H, CH3), 1.21 (sex, J = 7.3 Hz, 2H, CH2), 2.04-2.17 (m, 2H, CH2CO), 7.04 (d, J = 8.2 Hz, 1H, ArH), 7.23-7.41 (m, 6H, ArH), 7.51 (t, J = 7.5 Hz, 1H, ArH), 7.84 (d, J = 8.0 Hz, 1H, ArH), 7.90 (d, J = 9.0 Hz, 1H, ArH), 7.97 (d, J = 8.5 Hz, 1H, ArH), 8.07 (1H, d, J = 9.0 Hz, ArH); 13C NMR, δ: 13.1, 18.1, 35.7, 114.2, 118.3, 121.8, 122.8, 123.5, 124.5, 125.7, 126.3, 126.7, 127.5, 127.9, 128.3, 129.0, 130.4, 130.8, 131.3,133.5, 147.2, 152.1, 174.1. ESI-MS (m/z): 356. Anal. Calc. for C24H20O3: C, 80.88; H, 5.66. Found C, 80.89; H, 5.68. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With pyridine In dichloromethane at 0℃; for 6h; | |
99% | With 2,6-dimethylpyridine; dmap In dichloromethane | |
99% | With pyridine In dichloromethane at 20℃; for 6h; |
99% | With triethylamine In dichloromethane for 14h; Reflux; | |
95% | With pyridine In toluene at 0 - 25℃; for 3.5h; | |
95% | With pyridine; dmap In dichloromethane at 20℃; for 8h; | 1.1 The specific operation process of preparation: 20.0 g (69.93 mol) of the starting material SM-0 was dissolved in 300 ml of anhydrous dichloromethane, 27.5 g (0.35 mol) of pyridine and 1.5 g of DMAP were added, 43.4 g (0.15 mol) of a solution of trifluoromethanesulfonic anhydride dissolved in dichloromethane was slowly added dropwise, the reaction was stirred at room temperature for 8 hours, and stirred with 300 ml of water for 30 minutes, the organic phase was collected, concentrated, dried, and purified using silica gel column, concentrated and dried under reduced pressure to obtain 36.5 g of a white solid in a yield of 95% . |
With triethylamine In dichloromethane | ||
In pyridine | ||
With pyridine In dichloromethane at 20℃; for 2h; | ||
With triethylamine In dichloromethane at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.7% | With sodium hydroxide In ethanol; water at 70℃; for 4h; | 25 Example 25; 1.0 g NaOH, 20 ml water and 2.8 g 2,2'-dihydroxy-1,1'-binaphthyl prepared in the step a) of the Example 19 are added to a round bottom flask with the volume of 100 mL, 3.7 g bromopropane, 0.2 g tetrabutylammonium bromide and 10 ml ethanol are dropwise added to the round bottom flask, the temperature of the water bath is 70° C., and after the reaction is performed for 4 hours, the reaction product is poured, while hot, into 50 g crushed ice, followed by separating crystal out. The crystal is filtered and the filter cake is washed with diluted alkali solution and icy water as well as recrystallized with ethanol to obtain white crystal 2,2'-dipropoxy-1,1'-binaphthyl with the yield of 93.7%, the melting point of 87° C. and the content, according to HLPC detection, of 96.4%. |
With sodium ethanolate; potassium iodide In ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.3% | With sodium hydroxide In ethanol; water at 70℃; for 4h; | 26 Example 26; 1.0 g NaOH, 20 ml water and 2.8 g 2,2'-dihydroxy-1,1'-binaphthyl prepared in the step a) of the Example 19 are added to a round bottom flask with the volume of 100 mL and are then stirred to be dissolved, 4.1 g n-butyl bromine, 0.2 g tetrabutylammonium bromide and 10 ml ethanol are dropwise added to the round bottom flask, the temperature of the water bath is maintained at 70° C., and after the reaction is performed for 4 hours, the reaction product is poured, while hot, into 50 g crushed ice, followed by stirring to further separate crystal out. The crystal is filtered the filter cake is washed with alkali solution and icy water to obtain light yellow granular solid. The solid is recrystallized with ethanol to obtain yellow-white crystal 2,2'-dibutoxy-1,1'-binaphthyl with the yield of 92.3%, the melting point of 85° C. and the content, according to HLPC detection, of 96.6%. |
92.7% | With potassium carbonate In N,N-dimethyl acetamide at 90℃; for 22h; | 2.1 Step 1: Preparation of intermediate 172A (±)-BINOL (24.9 g, 86.9 mmol), 1-bromobutane (25.0 g, 182.5 mmol), potassium carbonate (36.0 g, 260.7 mmol) was added to a solution of DMAc (250 mL), and the mixture was stirred at 90 °C. for 10 hours for reaction. Further, potassium carbonate (15.0 g, 108.5 mmol), 1-Bromobutane (11.5 g, 83.9 mmol) was added, the mixture was stirred at the same temperature for 12 hours and reacted. After cooling to room temperature, toluene and ion exchanged water were added, the organic layer was washed twice with ion exchanged water, and the solvent was distilled off under reduced pressure. Methanol was added to the concentrate, the solid content was dispersed, filtered, dried under reduced pressure at 40 ° C., Intermediate 172A (32.1 g, 92.7%) was obtained as a cream colored solid. |
With sodium ethanolate; potassium iodide In ethanol |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate In acetone for 48h; Reflux; | 4.4. General procedure A: synthesis of compounds 9-12 and 19 General procedure: To a mixture of BINOL (8) or dibromobinaphthol 18 (1.75 mmol) and alkyldihalide (1.75 mmol) or methyliodide (17.5 mmol) in acetone (50 mL) was added K2CO3 (17.5 mmol). The reaction was then refluxed until BINOL was completely consumed (monitored byTLC). After that the reaction mixture was filtered by reduced pressure, the filtrate was evaporated to dryness to yield the crude product which was then purified by column chromatography (Silicagel; 19:1 hexane/ethyl acetate as an eluent) to provide BINOL derivatives. 4.4.1. Dinaphtho[2,1-d:1',2'-f][1,3]dioxepine (9). 10 White solid; mp173-175 C (lit. mp 83-84 C); 24 85% yield; vmax(neat) 2958, 2920,2897, 2851, 1587, 1505, 1460, 1326, 1266, 1238, 1138, 1078, 969, 925,816, 747, 662 cm1; δH (300 MHz, CDCl3) 5.61 (2H, s, OCH2O), 7.22(2H, m,Ar), 7.34e7.45 (6H, m, Ar), 7.86 (2H, d, J 8.2 Hz, Ar), 7.90 (2H,d, J 8.7 Hz, Ar); δC (75 MHz, CDCl3) 103.1, 120.9, 125.0, 126.0, 126.1,126.9, 128.4, 130.3, 131.8, 132.1, 151.2; HRMS (ESI): MNa, found: 321.0889. C21H14O2Na requires 321.0886. |
80% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; | |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; |
With potassium carbonate | ||
With potassium carbonate In acetone at 50℃; for 24h; | 1.1; 2.1; 4.1; 5.1 Example 1 (1) 2.8 g of compound I, 2.67 g of diiodomethane and 2.0 g of anhydrous potassium carbonate were mixed and added to 20 ml of acetone,And the mixture was stirred at 50 ° C for 24 hours to give 2,2'-methylenedioxy-1,1'-binaphthalene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With HCl In diethyl ether (N2); stirring the components in Et2O for 18 h, addn. of HCl in Et2O, stirring (6 h); removal of volatiles (vac.), extn. (warm toluene), evapn., recrystn. (toluene); elem. anal.; | |
65% | In diethyl ether for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With pyridine; trichlorophosphate at 20℃; for 1h; | |
95% | Stage #1: 1,1'-bi-2-naphthol With pyridine; trichlorophosphate at 20℃; for 3h; Stage #2: In water for 0.5h; | |
74% | With dmap; tributyl-amine; trichlorophosphate In acetone at 20℃; for 0.0333333h; Flow reactor; | (±)-Binaphthylphosphoric acid (BNP) Reaction mixture was collected for 2 minutes. The mixture was washed with 6M HCl solution and organic phase was collected. Then, 0.2M NaOH solution was added and a precipitation was observed. The precipitation was collected by filtration, dissolved in MeOH and DCM, and washed with 6M HCl solution. Organic phase was dried with Na2SO4 and the solvent was removed in vacuo. Finally, 411 mg of BNP was obtained in 74% yield.1H-NMR (400 MHz; DMSO-d6): δ 8.17 (d, J = 8.9 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H), 7.56-7.50 (m, 4H), 7.37 (td, J = 7.7, 1.3 Hz, 2H), 7.23 (d, J = 8.5 Hz, 2H); 13C NMR (101 MHz; DMSO-d6): δ 147.7, 147.61, 131.6, 131.0, 128.7, 126.9, 126.1, 125.5, 121.3 (d, JC-P = 2.6 Hz), 121.0 (d, JC-P = 2.3 Hz); HRMS (ESI, m/z): calcd for C20H12O4P ([M-H]-) 347.0479, Found 347.0478. |
Multi-step reaction with 2 steps 1: POCl3; pyridine / CH2Cl2 / 3 h / Heating 2: sodium carbonate / H2O / 0.33 h / Heating | ||
Multi-step reaction with 2 steps 1.1: pyridine; trichlorophosphate / 50 - 90 °C 2.1: water / 118 °C 2.2: Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: NaH / tetrahydrofuran / 0 - 20 °C 1.2: 100 percent / tetrahydrofuran / 4.5 h / 20 °C 2.1: n-BuLi / diethyl ether; hexane / 3 h / 20 °C 2.2: 85 percent / dibromotetrachloroethane / diethyl ether; hexane; tetrahydrofuran / 0.25 h / 20 °C 3.1: 85 percent / aq. Na2CO3 / Pd(PPh3)4 / 1,2-dimethoxy-ethane / 10 h / Heating 4.1: 89 percent / Amberlyst 15 resin / tetrahydrofuran; methanol / 15 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With triethylamine; In dichloromethane; at 0 - 20℃; for 12h;Inert atmosphere; | Example 1 BINOL-Camphor Sulfonyl Coupling To a flame-dried 50 mL 3-neck flask was added 0.35 mmol of (S)-camphor sulfonyl chloride. The flask was evacuated and backfilled with N2 three times and submerged in an ice bath. 5 mL of a 0.07 M solution of racemic [1,1'-binaphthalene]-2,2'-diol (BINOL) (0.35 mmol) in anhydrous dichloromethane (DCM) was cooled to 0 C. in an ice bath and added via syringe to the flask under positive N2 pressure. 0.121 mL of anhydrous trimethylamine (TEA) was then added to the reaction flask. The mixture was stirred under N2 and allowed to return to room temperature over 12 hours. The reaction was quenched with 5 mL of H2O, stirred for 15 minutes, and extracted three times with DCM. The organic layer was then washed with brine, and dried over Na2SO4. Liquid was removed under vacuum to yield a yellow waxy solid. A silica column was prepared using 12 g of 400-600 mesh silica, wet packed with hexanes. The crude product was dissolved in 0.5 mL of DCM, and wet loaded onto the column. The product was eluted with 20% ethylacetate in hexanes. Liquid was evaporated under vacuum to yield monosubstituted camphor sulfonyl BINOL (54% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 20h; | 4.3.1. Compound 6. 2,2'-Bis[2-(2-nitrophenoxy)ethoxy]-1,1'-binaphthalene A mixture of 1,1'-binaphthalene-2,2'-diol (3.29 g, 11.5 mmol), 1-(2-bromoethoxy)-2-nitrobenzene (6.58 g, 26 mmol), K2CO3 (5.8 g), and dimethylformamide (30 mL) was stirred and heated at 80 °C for 20 h. The mixture was then diluted with water; the precipitate was separated, washed with water, dried, and next recrystallized from propan-2-ol. Yield 6.71 g (94%) of pale yellow solid, mp 165-167 °C. 1H NMR (CDCl3), δ [ppm]: 4.00-4.10 (4H, m); 4.24-4.36 (4H, m); 6.55 (2H, d, J=8.3 Hz); 6.92 (2H, t, J=7.8 Hz); 7.12 (2H, d, J=8.8 Hz); 7.15 (2H, t, J=7.3 Hz); 7.20 (2H, t, J=7.8 Hz); 7.34 (2H, t, J=7.2 Hz); 7.46 (2H, d, J=8.8 Hz); 7.71 (2H, d, J=7.8 Hz); 7.86 (2H, d, J=8.3 Hz); 7.95 (2H, d, J=9.3 Hz). IR (Nujol): 1604; 1589; 1519; 1327; 1234; 1166; 1145; 1092; 1041; 991; 972; 852; 807; 772; 744; 725 cm-1. HRMS (EI): [M]+=616.18357 calculated for C36H28N2O8 616.18457. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.84% | In methanol; acetonitrile; at 20℃; | To a methanol solution (2 ml) of 1,4-bis(N-imidazolyl)butane (L1) (38 mg, 0.2 mmol) was added Binol (57.3 mg, 0.2 mmol) dissolved in acetonitrile (8 ml). The solution was stirred for half an hour, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days, colorless block crystals were isolated after slow evaporation of the solution in air. The crystals were collected and dried in air to give the title compound [(L1)*(Binol)] (1). Yield: 78 mg, 81.84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; di(tert-butyl)chlorophosphine; 1,5-diphenyl-1,5-cyclooctadiene; caesium carbonate; tricyclohexylphosphine tetrafluoroborate In toluene at 120℃; for 24h; Inert atmosphere; | 1 Example 1: Synthesis of 3,3'-diphenylbinaphthol Raw materials la (56 mg, 0.2 mmol) and 2a (1 mL), cesium carbonate (130 mg, 2.0 eq) were sequentially added to the reaction flask.Double dilute ligand L2-1 (2.6mg, 5mol%),Tricyclohexylphosphine tetrafluoroborate1.8mg, 2.5mol%),[Rh(cod) Cl] 2 (2.5 mg, 2.5 mol%),Di-tert-butylphosphonium chloride (18 mg, 0.1 mmol) and toluene (2 mL) were stirred at 120 ° C for 24 hours under nitrogen atmosphere, cooled to room temperature, diluted with ethyl acetate (5 mL), and dropped into 1 M Dilute hydrochloric acid (2 mL), saturated brine (5 mL), EtOAc (EtOAc)EtOAc. It was 83 mg as a white solid, yield 95%. |
51% | With silver(I) acetate; sodium t-butanolate In 1,4-dioxane at 155℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; at 50.0℃; for 5.0h; | Synthesis of [Ni(binol)(bpy)]CH3OH complex. Toa solution of NiCl26H2O (0.235 g, 1 mmol) in 10 mLof water was added 2,2′- bipyridine (0.154g, 1 mmol)in 10 mL of methanol dropwise with continuous stirring.The reaction was stirred at 100C under refl ux for8 h. To the mixture was added a solution of rac-H2binol(0.286 g, 1 mmol) and NaOH (0.08 g, 2 mmol) in 20 mLof water-alcohol (1 : 1 mixture) dropwise with continuousstirring. The reaction mixture was stirred at 50C for5 h. After cooling the yellow-brown colored solid formedwas fi ltered, fi rst washed with water-methanol (1 : 1 mixture)for several times, and then with ether and dried in avacuum. Analytically calculated for NiC31H24O3N2, %:yield 66, C 70.1, H 4.52, N 5.28. Found, %: C 69.98, H4.55, N 5.21. 13C NMR spectrum, 125 MHz DMSO-d6, δ,ppm: 79.5, 116.4, 119.9, 121.4, 124.1, 124.7, 125.2, 127.3127.7, 128.2, 129.1, 134.1, 136.6, 154.4, 160.8, 162.7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.5% | With potassium carbonate In toluene at 110℃; for 10h; | 1 Example 1 Stirrer, condenser, and a glass reactor equipped with a thermometer, (RS) -1,1'- bi -2-naphthol 180g (0.629mol), ethylene carbonate 127g (1.439mol), was charged with potassium carbonate 9.0g and toluene 180g, 10 at 110 It was stirred time. The mother liquor 110 obtained in toluene 200g and Production Example 1 in the reaction productAfter the addition of 0g, the organic solvent layer kept at 80 , and washed with sodium hydroxide aqueous solution. SubsequentlyThe organic solvent layer, wash water was washed with water until neutral. Dee and the resulting organic solvent layerTo obtain a dehydrated crystallization solution under reflux using a Nsutaku equipment, cold in such a way that 30 after 8 hoursTo precipitate a crystal at 39 by retirement. Thus obtained slurry solution of the above-mentioned conditionsIn After filtration, further wash the crystal with toluene 200g,It was separated into the crystal section and the mother liquor . ThisIt took 10 minutes to filtration and washing operation . Also , it was analyzed to collect part of the resulting crystals , sinteredSolvent content of Akirachu is 15 wt % , the shape of the crystals was plate- shaped crystals . It is separated by filtrationThe mother liquor was 1603g. Then , drying the crystals obtained by the filtration operation (RS) -2,2'- Bis ( 2-hydroxyethoxy ) -1,1'- binaphthalene of white crystals 2Was obtained 11g (89.5% yield , HPLC purity 99.7%, YI value : 4 ) . The obtained crystalsThe physical properties as follows [DSC melting endotherm maximum : 107 , powder X-ray diffraction pattern : polymorph C,Crystal shape : plate-like crystal , aspect ratio : 1.3 (absolute value of the width : 70μm), mode diameter and jointThe ratio of the Anne diameter (Dmode / Dmedian): 1.0]. |
87.19% | With potassium carbonate In N,N-dimethyl acetamide; toluene at 100℃; for 6h; | 1-3; 1-5 Example 2 In a 3000 mL four-necked flask, 343.2 g (1.2 mol) of (±)-1,1'-bi(2-naphthol), 600 g of toluene, 48 g of N,N-dimethylacetamide, 22.8 g of potassium carbonate and 704 g (3 mol) of ethylene carbonate. After 6 hours of reaction at 100 °C, The content of (±) -2,2'-bis- (2-hydroxyethoxy) -1,1'-binaphthalene was less than 0.1% by HPLC analysis, and the reaction was stopped. Toluene was added, washed with water to neutrality, and the solid was precipitated by cooling, and put into a 1000 mL oven with spiral stirring. Toluene was added, washed with water to neutrality, and the solid was precipitated by cooling, and put into a 1000 mL oven with spiral stirring. Grinding the dried under vacuum, drying temperature 85 , drying time of 18 hours, to give (±) -2,2'- two - (2-hydroxyethoxy) -1,1'-binaphthyl 391.73g, yield 87.19%. |
86.7% | With potassium carbonate In toluene Inert atmosphere; Reflux; | 3.3.3.1 3.1 : 2,2'-bis-(2-hydroxyethoxy)-1 ,1 '-binaphthyl (compound VIII, with X = 1 ,2-ethandiyl) 150.0 g (523.88 mmol) of 1 ,1 '-bi-2-naphthol (compound II), 138.37 g (1571 .3 mmol) of ethylene carbonate (3 equiv.) and 21 .75 g (157.13 mmol) of potassium carbonate (30 mol-%) in 1 L toluene were heated under reflux for at least 5 to 6 hours, by maintaining argon atmosphere. During the reaction gas evolves. The reaction is monitored by TLC using TBME as solvent. When TLC indicates complete reaction the slightly yellow reaction mixture is cooled to 70°C and mixed with 100 g of water (Caution: CO2 gas evolution) The reaction mixture is then stirred for further 10-15 min at 70°C to dissolve potassium carbonate. The stirrer is stopped and phases are separated at about 70°C. The organic phase is washed with 100 g of 5% w/w aqueous solution of NaOH at 80- 90°C for at least 1 h (Caution: CO2 gas evolution), followed by washing with water (each 100 mL) at 70°C, until the pH of the washing water is neutral (pH 7). 15 g of charcoal is optionally added to the organic phase and the mixture is stirred at 70°C for 30 min. Then the warm solution is filtered through Celite. The clear and slightly yellowish filtrate is cooled to RT and product crystallizes in the form of thin platelets. The solid is filtered off, washed with toluene and dried. 142-170 g (72.4-86.7 %) of the title compound are obtained as a white, dry solid. |
86.7% | With potassium carbonate In toluene Reflux; Inert atmosphere; | 2.1 2.1 : 2, 2'-bis-(2-hydroxyethoxy)-1 ,1 '-binaphthyl (compound VI’, with Aik’ = 1 ,2-ethandiyl) 150.0 g (523.88 mmol) of 1 , 1 '-bi-2-naphthol (compound VI), 138.37 g (1571.3 mmol) of ethylene carbonate (3 equiv.) and 21.75 g (157.13 mmol) of potassium carbonate (30 mol-%) in 1 L toluene were heated under reflux for at least 5 to 6 hours, by maintaining argon atmosphere. During the reaction gas evolves. The reaction is monitored by TLC using MTBE as solvent. When TLC indicates complete reaction the slightly yellow reaction mixture is cooled to 70°C and mixed with 100 g of water (Caution: C02 gas evolution) The reaction mixture is then stirred for further 10-15 min at 70°C to dissolve potassium carbonate. The stirrer is stopped and phases are separated at about 70°C. The organic phase is washed with 100 g of 5% w/w aqueous solution of NaOH at 80- 90°C for at least 1 h (Caution: C02 gas evolution), followed by washing with water (each 100 mL) at 70°C, until the pH of the washing water is neutral (pH 7). 15 g of charcoal is optionally added to the organic phase and the mixture is stirred at 70°C for 30 min. Then the warm solution is filtered through Celite. The clear and slightly yellowish filtrate is cooled to RT and product crystallizes in the form of thin platelets. The solid is filtered off, washed with toluene and dried. 142-170 g (72.4- 86.7%) of the title compound are obtained as a white, dry solid. |
86.7% | With potassium carbonate In toluene Reflux; Inert atmosphere; | 2.2.1 2.1 : 2, 2'-bis-(2-hydroxyethoxy)-1 ,1 '-binaphthyl (compound VI’, with Aik’ = 1 ,2-ethandiyl) 150.0 g (523.88 mmol) of 1 , 1 '-bi-2-naphthol (compound VI), 138.37 g (1571.3 mmol) of ethylene carbonate (3 equiv.) and 21.75 g (157.13 mmol) of potassium carbonate (30 mol-%) in 1 L toluene were heated under reflux for at least 5 to 6 hours, by maintaining argon atmosphere. During the reaction gas evolves. The reaction is monitored by TLC using MTBE as solvent. When TLC indicates complete reaction the slightly yellow reaction mixture is cooled to 70°C and mixed with 100 g of water (Caution: C02 gas evolution) The reaction mixture is then stirred for further 10-15 min at 70°C to dissolve potassium carbonate. The stirrer is stopped and phases are separated at about 70°C. The organic phase is washed with 100 g of 5% w/w aqueous solution of NaOH at 80- 90°C for at least 1 h (Caution: C02 gas evolution), followed by washing with water (each 100 mL) at 70°C, until the pH of the washing water is neutral (pH 7). 15 g of charcoal is optionally added to the organic phase and the mixture is stirred at 70°C for 30 min. Then the warm solution is filtered through Celite. The clear and slightly yellowish filtrate is cooled to RT and product crystallizes in the form of thin platelets. The solid is filtered off, washed with toluene and dried. 142-170 g (72.4- 86.7%) of the title compound are obtained as a white, dry solid. |
84.1% | With potassium carbonate In toluene at 110℃; for 10h; | 1 Production of Crystal of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene> In a glass reactor equipped with a stirrer, a condenser, and a thermometer,180 g (0.629 mol) of (RS) -1,1'-bi-2-naphthol, 127 g (1.439 mol) of ethylene carbonate, 9.0 g of potassium carbonate and 180 g of toluene were charged and stirred at 110 ° C. for 10 hours. After 1300 g of toluene was added to the reaction product, the organic layer was washed with an aqueous solution of sodium hydroxide while maintaining the temperature at 80 ° C. Next, this organic layer was washed with water until the washing water became neutral. The obtained organic layer was dehydrated under reflux using a Dean Stark apparatus to obtain a toluene solution in which (RS) -2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene was dissolved. Thereafter, when the solution was cooled, crystals precipitated at 63 ° C. all at once, making it difficult to stir, 1200 g of toluene was added to make it into a slurry state containing crystals and allowed to stir, and then cooled further to 30 ° C. This was filtered and the crystals were further washed with 200 g of toluene, and the obtained crystals were dried to obtain 198 g of pale yellow crystals of (RS) -2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene The yield was 84.1%, the HPLC purity was 99.1%, the total content of organic substances having a boiling point of 250 ° C. or lower at 101.3 kPa: 0.1%). Differential scanning calorimetry and powder X-ray diffraction measurement were performed on the obtained crystals. The differential scanning calorimetry chart and the powder X-ray diffraction pattern of the obtained crystal are shown in FIGS. 1 and 2, respectively |
84.9% | With N,N-dimethyl acetamide; potassium carbonate In toluene at 100℃; for 6h; | 1 Example 1 In a 500 mL four-necked flask,Add (±)-1,1'-link (2-naphthol) 28.6 g (0.1 mol),50g toluene,4g of N,N-dimethylacetamide,1.9 g of potassium carbonate and ethylene carbonate 22 g (0.25 mol).After 6 hours of reaction at 100oC,The content of (±) -2,2'-bis- (2-hydroxyethoxy) -1,1'-binaphthyl was less than 0.1%Stop the reaction.Adding toluene,Water to neutral,Cooling precipitates solids,After vacuum drying for 12 hours,31.8 g of (±) -2,2'-bis- (2-hydroxyethoxy) -1,1'-binaphthyl was obtained,The yield is 84.9%.High-performance liquid chromatography (HPLC) analysis of 99.2% purity,Loss on drying at 120 degrees is 0.10% |
84.5% | With potassium carbonate In toluene at 110℃; for 10h; | 1-4; 1; 2 Example 1 In a glass reactor equipped with a stirrer, cooler and thermometer,286 g (1 mol) of (RS) -1,1'-bi-2-naphthol;194 g (2.2 mol) of ethylene carbonate,Charge 15 g of potassium carbonate and 450 g of toluene,The reaction was performed at 110 ° C. for 10 hours. After diluting the reaction solution by adding 540 g of toluene,The organic solvent layer was washed by adding 290 g of a 10% by mass aqueous sodium hydroxide solution.Subsequently, the washing with water was repeated using 500 g of water until the washed water became neutral. After washing with water, trisodium phosphate dodecahydrate 1. 6 g was added and the mixture was stirred for 30 minutes. Thereafter, the mixture was cooled from 80 ° C. to 30 ° C. at a rate of 0.5 ° C./min, filtered under reduced pressure (50 kPa) and dried,(RS) -2,2'-bis (2-hydroxyethoxy)-1,1'-binaphthalene317 g (yield: 84.5% by mass, purity: 99.6%, D50: 58 μm) of white crystals of the compound were obtained. The phosphorus content in the obtained crystals was 47 mass ppm. |
83.3% | With potassium carbonate In toluene at 110℃; for 10h; | 1 stirrer, condenser, and a glass reactor equipped with a thermometer, (RS)-1,1'-bi-2-naphthol 32.0 g (0.112 mol), ethylene carbonate 22. 5g (0.256mol), was charged with potassium carbonate 1.6g and toluene 32g, after a heated slurry state up to 110 , and reacted for 10 hours at 110 .A result that was confirmed by HPLC, the remaining amount of 1,1'-bi-2-naphthol was 0.1% or less.After dilution with toluene 416g to the reaction mixture, the organic solvent phase containing the reaction mixture was washed with 10% aqueous sodium hydroxide 48 g, then the wash water was washed with water until neutral.After washing with water, was refluxed dehydrated organic solvent phase, then cooled to room temperature, filtered, the white crystals dried to (RS)-2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene compound obtained (83.3% yield, HPLC purity 99.7%, YI value: 2.8). |
83.6% | With potassium carbonate In toluene at 110℃; for 10h; | 1 In a glass reactor equipped with a stirrer, a condenser, and a thermometer,180 g (0.629 mol) of (RS) -1,1'-bi-2-naphthol,127 g (1.439 mol) of ethylene carbonate,9.0 g of potassium carbonate and 180 g of toluene,And reacted at 110 ° C. for 10 hours. As a result of HPLC measurement,0.1% of 1,1'-bi-2-naphthol,89.4% of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene,The polymer was 6.9%, the others were 1 mol adduct and 3 mol adduct.620 g of toluene was added to this reaction mixture and diluted,270 g of a 9.7 wt% sodium hydroxide aqueous solution was added to the organic solvent phase containing the reaction mixture, and the mixture was stirred at 85 ° C. for 1 hour, and then the aqueous phase was separated off and removed.As a result of measuring the organic solvent layer by HPLC,It was 96.2% of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene, and no polymer was detected.Next, this organic solvent layer was washed with water until the washing water became neutral.After refluxing and dehydrating the obtained organic solvent phase, it was cooled to room temperature, filtered and dried to obtain (RS) -2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene as white crystals (Yield 83.6%, HPLC purity 99.6%, YI value: 2.9). |
83.5% | With potassium carbonate In toluene at 110℃; for 10h; | 1-4; 1; 2 Example 1 In a glass reactor equipped with a stirrer, cooler and thermometer,286 g (1 mol) of (RS) -1,1'-bi-2-naphthol;194 g (2.2 mol) of ethylene carbonate,Charge 15 g of potassium carbonate and 450 g of toluene,The reaction was performed at 110 ° C. for 10 hours. After 540 g of toluene was added to this reaction solution to dilute it, 290 g of a 10% by mass aqueous sodium hydroxide solution was added to wash the organic solvent layer. continue,Washing with 500 g of water was repeated until the washed water became neutral. After washing with water, 1.0 g of an aqueous solution of sodium silicate (trade name: sodium silicate solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the organic solvent layer, and the mixture was stirred for 30 minutes. Thereafter, the mixture was cooled from 80 ° C. to 30 ° C. at a rate of 0.5 ° C./min, filtered under reduced pressure (50 kPa) and dried,(RS) -2,2'-bis (2-hydroxyethoxy)-1,1'-binaphthaleneCompound313 g of white crystals(Yield: 83.5% by mass, purity: 99.6%, D50: 55 μm).The silicon content in the obtained crystals was 73 mass ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In acetone; for 24h;Reflux; | The R or S configuration 1,1'-bi-2-naphthol (28.6g, 0.1mol, 1.0eq), 3,5- dibromo-benzyl bromide (40.78g, 0.12mol, 1.2eq) and K2CO3(41.4g, 0.3mol, 3.0eq) charged into a 3L round bottom flask, 1L of anhydrous acetone was stirred at reflux for 24 hours.Followed by cooling to room temperature, using a rotary evaporator and concentrated in vacuo to remove the organic solvent and obtain a crude product, ethyl acetate / petroleum ether (volume ratio of 1) as the mobile phase and the resulting crude product was purified by column chromatography on at 50 vacuum dried to give R or S configuration of 2,2 '- (1', 3 '- dibenzyl-oxo-5' - bromophenyl) -1,1'-binaphthyl (42g, 0.09mol, yield 90%), the reaction equation is as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8%; 85% | With ammonium hydroxide; ammonium sulfite monohydrate; at 200℃; for 5h;Autoclave; | General procedure: Racemic 2,2'-dihydroxy-1,1'-binaphthyl (rac-BINOL, 5.0 g, 17.5 mmol), ammonium sulfite monohydrate (AR, 23.5 g, 175 mmol) and aqueous ammonia (32 mL, 464 mmol)Was placed in an autoclave.The mixture in the autoclave was stirred at the reaction temperature and reaction time described in Table 1. The reaction mixture was cooled to 25 C., and the resulting solid was washed with water and filtered.By recrystallizing the filtrate with benzene,Racemic 2-amino-2'-hydroxy-1,1'-binaphthyl (rac-NOBIN) and DBC were separated.The reaction yield was calculated by chiral HPLC. In addition, the isolation yield of the compound after recrystallization from benzene was calculated. These reaction yields and isolation yields are described in Table 1. |
With ammonium sulfite monohydrate; ammonia; In water; at 200℃;Autoclave; | 1 (2.0 g, 6.9 mmol) and the aminating reagent (AR; (NH4)2SO3·H2O:NH3aq. = 1:2.6 mol/mol, equivalent ratio of 1:AR = 1:10 to 1:36 mol/mol) were placed in the autoclave. The mixture was stirred at 200 or 220 C at various reaction times. After the mixture was cooled to 25 C, the crude products were washed with water, and were collected by filtration. Separation of 2 and 3 was achieved by recrystallization from benzene. Reaction time, reaction temperature, equivalent ratio of 1:AR, reaction conversion, and isolated yields for each experiment were listed in Table 1. 2: 1H-NMR (300 MHz, CDCl3): delta = 3.75 (s, 2H, binaphthyl-NH2), 5.18 (s, 1H, binaphthyl-OH), 7.03-7.06 (d, 1H, J = 7.2 Hz, aromatic ring), 7.14-7.40 (m, 8H, aromatic ring), 7.79-7.94 (m, 4H, aromatic ring); 13C-NMR (75 MHz, CDCl3): delta = 108.65, 114.19, 117.68, 118.15, 122.75, 123.62, 123.71, 124.49, 126.39, 127.28, 128.21, 128.31, 128.35, 129.46, 130.33, 130.55, 133.15, 134.60, 143.54, 151.78. 3: mp: 159 C (lit.S3 156-159 C); 1H-NMR (400 MHz, CDCl3): delta = 7.54 (dd, 2H, J = 8.0, 7.2 Hz, aromatic ring), 7.64 (d, 2H, J = 8.8 Hz, aromatic ring), 7.70 (dd, 2H, J = 7.2, 7.2 Hz, aromatic ring), 7.87 (d, 2H, J = 8.8 Hz, aromatic ring), 8.05 (d, 2H, J = 7.6 Hz, aromatic ring), 8.68 (s, 1H, DBC-NH), 9.23 (d, 2H, J = 8.4 Hz, aromatic ring); 13C-NMR (75 MHz, CDCl3): delta = 112.56, 117.62, 123.27, 125.15, 125.43, 126.78, 129.17, 129.92, 136.10; FT-IR (nu cm-1): 3400, 3000, 1600, 1400, 900, 675; HRMS calcd. for C20H13N ([M+Na]+): 290.0940, found: 290.0940. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With triethylamine; In dichloromethane; at 0 - 20℃; for 3h;Inert atmosphere; | Example 2 BINOL-Menthyl Carbonate Coupling To a flame-dried 50 mL 3-neck flask was added 0.35 mmol of (R)-menthyl chloroformate. The flask was evacuated and backfilled with N2 three times, and submerged in an ice bath. 5 mL of a 0.07 M solution of racemic BINOL (0.35 mmol) in anhydrous dichloromethane (DCM) was cooled to 0 C. in an ice bath, and added via syringe to the flask under positive N2 pressure. 0.121 mL of TEA was then added to the reaction flask. The mixture was stirred under N2 and allowed to return to room temperature over 3 hours. The reaction was quenched with 5 mL of 1M HCl, stirred for 15 minutes, and extracted three times with DCM. The organic layer was then washed with brine, and dried over Na2SO4. Liquid was removed under vacuum to yield a pale waxy solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; di(tert-butyl)chlorophosphine; 1,5-diphenyl-1,5-cyclooctadiene; caesium carbonate; tricyclohexylphosphine tetrafluoroborate In toluene at 120℃; for 24h; Inert atmosphere; | 2 Example 2: Synthesis of 3,3'-diphenylbinaphthol aw materials la (56 mg, 0.2 mmol) and 2b (113 mg, 0.72 mmol) were sequentially added to the reaction flask, and cesium carbonate was added.(130 mg, 2. Oeq), double dilute ligand L2_l (2.6 mg, 5 mol 1%), tricyclohexylphosphine tetrafluoroborate (1.8 mg, 2.5 mol 1%), [Rh (cod) Cl] 2 ( 2.5 mg, 2 · 5 mol %), di-tert-butylphosphonium chloride (18 mg, 0 · 1 mmol) and toluene (2 mL), stirred at 120 ° C for 24 hours under nitrogen atmosphere, cooled to room temperature, and added ethyl acetate (5 mL) was diluted, and 1 M diluted hydrochloric acid (2 mL) was added dropwise, and brine (5 mL) was washed. The organic phase was dried over anhydrous magnesium sulfate. =1/15), product 3a is white solid 72mg, yield 82% |
Stage #1: 1,1'-bi-2-naphthol With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; (2,2’-bi(1,3,2-dioxaborolane)); triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran at 80℃; for 12h; Glovebox; Sealed tube; Stage #2: bromobenzene With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In 1,4-dioxane; 1,2-dimethoxyethane; water at 80℃; for 12h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; di(tert-butyl)chlorophosphine; C22H22; caesium carbonate; tricyclohexylphosphine tetrafluoroborate In toluene at 120℃; for 24h; Inert atmosphere; | 16 Example 16: Synthesis of 3,3'-diphenylbinaphthol Raw materials la (56 mg, 0.2 mmol) and 2c (147 mg, 0.72), cesium carbonate (130 mg, 2.0 eq), dilute ligand Ll-1 (2.9 mg, 5 mol%), tricyclohexyl group were sequentially added to the reaction flask. Phosphine tetrafluoroborate (1.8 mg, 2.5 mol %), [Rh(cod) Cl] 2 (2.5 mg, 2.5 mol%), di-tert-butylphosphonium chloride (18 mg, 0.1 mmol) and toluene (2 mL) In a nitrogen atmosphere, the mixture was stirred at 120 ° C for 24 hours, cooled to room temperature, diluted with ethyl acetate (5 mL), diluted with 1M diluted hydrochloric acid (2 mL), and washed with brine (5 mL). Drying with magnesium sulfate, spin-drying and column chromatography, eluent (ethyl acetate / petroleum ether = 1 / 15), product 3a as white solid79mg, yield 90% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With potassium tert-butylate; In water; for 6h;pH 13;Inert atmosphere; Irradiation; | General procedure: The following procedure is representative of all the photoinduced reactions. The reactions were carried out in a 50-mL three-neck round-bottomed flask equipped with a nitrogen inlet and magnetic stirrer. To 5 mL of degassed water (using a water vacuum pump), potassium t-butoxide (44.6 mg, 0.398 mmol) or KOH (33.4 mg, 0.596 mmol) was added. After total dissolution of the base, 2-naphthol (42.9 mg, 0.298 mmol) was added and the mixture stirred for 5 min, and then 4 (28.2 mg, 0.108 mmol) was added. The reaction mixture was irradiated for 360 min. Irradiation was conducted in a reactor equipped with two Philips HPI-T 400-W lamps (λ ≥ 350 nm, cooled with water) or with an LED lamp (LED Lustrous Colour Xnes lamp, λ= 400 ± 20 nm, 9.4 V, 1050 mA) (see Reactors section in the Supplementary Material). After that, the reaction was stopped by adding an excess of ammonium nitrate and 10 mL of water. The crude was then extracted with ethyl acetate; the organic layer was dried over Na2SO4, filtered, and vacuum-concentrated. Products were isolated using column chromatography (pentane/acetone 80/20). The halide ion concentration in the aqueous solution was determined by potentiometric titration. Dark reactions were carried out by covering the vessel with aluminium foil before degasification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 1,1'-bi-2-naphthol With sodium hydride In tetrahydrofuran; N,N-dimethyl acetamide; mineral oil at 20℃; for 0.166667h; Stage #2: 1,2-Diiodobenzene In tetrahydrofuran; N,N-dimethyl acetamide; mineral oil at 20℃; for 1h; | 9 Example 9 Suspend sodium hydride (60% in oil, 72 mg, 1.8 mmol, 6 eq.) in THF (1 mL), add phenol for 2h (86 mg, 0.3 mmol, 1 eq.) under regular stirring and add phenol to DMA (0.4 mL After adding the solution in ), stir at room temperature for 10 minutes, then add a solution of 1a (297 mg, 0.9 mmol, 3 eq.) in THF (0.6 mL), react at room temperature for 1 hour, quench with water, and use ethyl acetate The ester was extracted three times, the organic layers were combined, dried over sodium sulfate, evaporated to dryness, and purified by column chromatography to obtain the product iodo aryl ether 3ah with a yield of 89% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate; In N,N-dimethyl-formamide; at 100℃; for 10h;Inert atmosphere; | S1. Weigh binaphthol, cesium carbonate, 4-fluoro, 4-bromo-benzophenone and dissolve in N,N-dimethylformamide in a 100 mL round bottom flask at a molar ratio of 1:2:1. Under the protection of nitrogen, the above reactants were heated to 100 C. and reacted for 10 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was extracted 3 times with ethyl acetate and saturated brine. Take the organic phase and evaporate ethyl acetate under reduced pressure to obtain a crude product. Then through silica gel column chromatography with ethyl acetate/n-hexane as the eluent for separation and purification, Intermediate 2 is obtained. The structural formula of Intermediate 2 is shown below: |
Tags: 602-09-5 synthesis path| 602-09-5 SDS| 602-09-5 COA| 602-09-5 purity| 602-09-5 application| 602-09-5 NMR| 602-09-5 COA| 602-09-5 structure
A290939[ 18531-94-7 ]
(R)-[1,1'-Binaphthalene]-2,2'-diol
Reason: Racemic-enantiomer
A436587[ 18531-99-2 ]
(S)-[1,1'-Binaphthalene]-2,2'-diol
Reason: Racemic-enantiomer
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P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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