Name: 620-92-8|4,4'-Methylenediphenol|98%
Brand: Ambeed
SKU: A222523
Price: 5.0 USD
Availability: InStock
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1
[ 50-00-0 ]
[ 620-92-8 ]
[ 13653-12-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In water; at 65℃; for 2h;pH 9 - 10;	EXAMPLE 2: Preparation of compound 9 [0045] About 100 grams of bisphenol F and 270 grams of formalin solution (37percent concentration) were mixed in a five-neck reaction flask fitted with a condenser, mechanical stirrer, dropping funnel, and a thermometer. The reaction was started by adding 100 mL of 40percent sodium hydroxide solution drop wise, and the pH of the reaction mixture was adjusted to pH 10. The reaction mixture was heated to about 65 °C for 2 hours, and the pH was maintained between pH 9 and pH 10. At the end of this period, the reaction mixture was cooled and neutralized with cold (5-10 °C) solution of sodium dihydrogen phosphate. An oily viscous layer was separated from the reaction mixture, dissolved in ethanol, desalted, and dried with molecular sieves. The product was evaporated by rotary evaporators and dried under vacuum to obtain the tetrahydroxymethyl bisphenol compound. The number of hydroxymethyl groups in the resin was determined by Moisture Evolution Analysis (MEA) and DSC ( Perkin Elmer). [0046] About 32 grams (0.1 mole) of the above obtained bisphenol compound was mixed with 86 grams (0.4 mole) of acrylic acid anhydride (analar grade) and 0.1 gram of tert-butylhydroquinone in a reaction vessel. The reaction mixture was heated to about 60 °C and the tetrahydroxymethyl bisphenol solution in THF was slowly added from the dropping funnel with mixing for one hour. The reaction was continued at about 60 °C for two hours, and at the end of this period the temperature was raised to about 80 °C for one hour. The excess of unreacted acrylic anhydride and acrylic acid by-products were distilled under vacuum, and a viscous acrylated bisphenol compound (compound 9) was obtained. The product was characterized and evaluated by DSC . The above product can also be prepared by substituting acrylic acid with acryloyl chloride and carrying out the reaction in the presence of triethylamine as a solvent and HC1, at ambient temperature (25 °C ).

Reference： [1]Tetrahedron,1994,vol. 50,p. 12159 - 12184
[2]Kogyo Kagaku zasshi / Journal of the Society of Chemical Industry,1953,vol. 56,p. 890
Chem.Abstr.,1955,p. 6889
[3]Tetrahedron Letters,1990,vol. 31,p. 107 - 110
[4]Patent: WO2014/126625,2014,A1 .Location in patent: Paragraph 0045; 0046

2
[ 611-99-4 ]
[ 620-92-8 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2004,vol. 12,p. 2759 - 2772
[2]New Journal of Chemistry,2017,vol. 41,p. 8443 - 8450
[3]Chemical Communications,2017,vol. 54,p. 156 - 159
[4]Journal of the American Chemical Society,1947,vol. 69,p. 1254
[5]Journal of Organic Chemistry,1957,vol. 22,p. 85

3
[ 620-92-8 ]
[ 107870-37-1 ]

Yield	Reaction Conditions	Operation in experiment
	Hydrogenation;	Example 4; Hydrogenation of Optionally Substituted Bisphenols to Cycloaliphatic Diols

Reference： [1]Chemische Berichte,1931,vol. 64,p. 2621,2624
[2]Journal of the American Chemical Society,1951,vol. 73,p. 1267,1270
[3]Patent: US2012/116099,2012,A1 .Location in patent: Page/Page column 8

4
[ 122-25-8 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
	beim Erhitzen ueber den Schmelzpunkt;
	With alkali
	With copper(I) oxide; N,N,N,N,-tetramethylethylenediamine In 1-methyl-pyrrolidin-2-one at 185℃; for 20h;

Reference： [1]Clemmensen; Heitman [Journal of the American Chemical Society, 1911, vol. 33, p. 740]
[2]Clemmensen; Heitman [Journal of the American Chemical Society, 1911, vol. 33, p. 740]
[3]Current Patent Assignee: GOVERNMENT OF THE UNITED STATES - US9517987, 2016, B1 Location in patent: Page/Page column 10

5
[ 122-25-8 ]
[ 620-92-8 ]
[ 860756-97-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide at 140℃; im Einschlussrohr;

Reference： [1]Clemmensen; Heitman [Journal of the American Chemical Society, 1911, vol. 33, p. 740]

6
[ 620-92-8 ]
[ 98-88-4 ]
[ 21886-63-5 ]

Yield	Reaction Conditions	Operation in experiment
86%	With triethylamine; In tetrahydrofuran; at 0 - 20℃; for 1h;	Example 3 9.6 g (48 mmol) of bis(4-hydroxyphenyl)methane, 11.8 g (117 mmol) of triethylamine, 200 mL of tetrahydrofuran were charged into a 200 mL reaction flask and cooled to 0°C. 14.9 g (106 mmol) of benzoyl chloride was added and the mixture was stirred at room temperature for 1 hour. Triethylamine hydrochloride was removed by filtration and the reaction mixture was evaporated. After the residue was dissolved in methylene chloride, the reaction mixture was washed with water for three times, and dried over magnesium sulfate. After removal of solvent under reduced pressure, the crude product was recrystallized from hexane/ethyl acetate to give 16.8 g of a faintly yellow needle crystal A (isolated yield 86percent).

Reference： [1]Patent: EP1997798,2008,A1 .Location in patent: Page/Page column 9-10
[2]Justus Liebigs Annalen der Chemie,1878,vol. 194,p. 318

7
[ 50-00-0 ]
[ 108-95-2 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
97.1%	With MIL-101(Cr/Al)A-f; at 60℃; for 0.5h;Kinetics;	Hydroxyalkylation of phenol with formaldehyde to bisphenol F wascarried out in reactor with magnetic stirring. Typical experimentalprocesses were summarized as follows: 0.465 g (5.7 mmol) of formaldehydesolution, 8.12 g of phenol and 0.12 g of catalyst were addedinto the reactor and the reaction mixture was heated to the desiredtemperature. After a certain time interval, 0.03 g of the suspension wastaken out and then diluted with 10 mL of methanol. The composition ofthe product was confirmed by HPLC with a Shimadzu LC-20AT systemconnected with a SPD-20A UV/Vis detector and a Phenomenex LunaC18 column (250×4.6 mm, 5 mm); A mixture of methanol and waterwith 65:35 v/v was used as the mobile phase with a constant flow rateof 0.6 mL/min. The injective volume of the sample was 100 muL.
89.4%	With sulfonic acid and mercapto bifunctional modified mesoporous SBA-15 molecular sieve catalyst; In water; at 80℃; for 2h;Inert atmosphere;	The procedure was the same as in Example 1 except that the (3-mercaptopropyl) trimethoxysilane was added during the catalyst preparation to give a mass yield of bisphenol F of 89.4%, wherein the 4-4' isomer bisphenol F, the percentage of mass is 44%.
80%		50.2 g (0.1 mol) of ionic liquid catalyst N,N-di(4-indenyl)butyl-N,N,N,N-tetramethyl-1,3-propanediamine bisulfate (molecular weight 502) And 56.4 g (0.6 mol) of phenol (molecular weight 94) was added to a three-necked flask, filled with nitrogen, and stirred at a reaction temperature of 90C for 15 minutes.After mixing well, 8.1 g (0.1 mol) of a 37% by mass aqueous solution of formaldehyde (molecular weight 30) is added dropwise.That is, the molar ratio of phenol to ionic liquid to formaldehyde is 6:1:1.The reaction was refluxed at 90C for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with water. The water in the aqueous phase was evaporated to recover the ionic liquid catalyst.N,N-bis(4-indenyl)butyl-N,N,N,N-tetramethyl-1,3-propanediammonium bisulfite,The organic phase was distilled under reduced pressure to recover phenol. After cooling the distillation concentrate, the yield of bisphenol F bisphenol F was 77%, and the selectivity of 4,4?-bisphenol F was 61%. Similar to Example 1, the only difference is that the molar ratio of phenol to ionic liquid to formaldehyde in the synthesis of bisphenol FAt 10:1:1, the rest of the procedure was the same, the yield of bisphenol F obtained was 80%, and the selectivity of 4,4?-bisphenol F was 62%.

48%	With ZnO(at)ZrO2(at)CdS(at)Fe3O4; In water; toluene; at 20 - 40℃; for 48h;	The new composite catalyst ZnO ZrO2 CdS Fe3O4 was used in the synthesis of bisphenol F: phenol (10mmol), ZnO ZrO2 CdS Fe3O4 (10 mg) was added to the reaction vessel, stirred at room temperature, 100 mL of toluene was added, and 37%Aqueous formaldehyde (3 mmol) and heated to 40 C. The reaction time is 48 hours. After the reaction, cool to room temperature through the magnetThe catalyst was obtained. The crude product was distilled off to recover the solvent, and the remaining phenol was distilled off under reduced pressure. The remaining product was recovered with recycledOnce the toluene was crystallized again, 4,4-dihydroxydiphenylmethane was obtained in a yield of 48%.
	With silicotungstic acid hydrate; 1-dodecylthiol; In water; at 40 - 50℃; for 5h;	Phenol (28.4 g, 302 mmol) was warmed to 40 ° C. to melt, and then silicotungstic acid (0.11 g, 0.032 mmol) and n-dodecyl mercaptan (0.61 g, 3.0 mmol) were added. . Thereafter, while maintaining the internal temperature at 50 ° C., formalin 37percent by mass aqueous solution (4.89 g, 60.2 mmol) was dropped over 4 hours. After dropping, the mixture was heated and stirred for 1 hour to be aged. The obtained reaction solution was partially taken and subjected to LC and GC analysis. The aldehyde conversion was 100percent, and the formation rate of 4,4'-substituted product was 45percent.

Reference： [1]Applied Catalysis A: General,2018,vol. 559,p. 138 - 145
[2]Patent: CN105669384,2016,A .Location in patent: Paragraph 0055-0056
[3]RSC Advances,2014,vol. 4,p. 33466 - 33473
[4]Patent: CN105016980,2017,B .Location in patent: Paragraph 0026; 0027; 0029; 0030; 0031; 0032; 0033-0044
[5]Patent: CN106146259,2016,A .Location in patent: Paragraph 0012; 0013
[6]Journal of Polymer Science, Part A: Polymer Chemistry,2011,vol. 49,p. 1443 - 1452
[7],1936,vol. 16,p. 177,184
Chemisches Zentralblatt,1937,vol. 108,p. 1291
[8]Patent: US2464207,1944,
[9]Angewandte Chemie,1923,vol. 36,p. 515
[10]RSC Advances,2016,vol. 6,p. 74028 - 74038
[11]Patent: JP2019/85399,2019,A .Location in patent: Paragraph 0187; 0209

8
[ 620-92-8 ]
[ 106-93-4 ]
[ 116077-92-0 ]

Reference： [1]Journal of the American Chemical Society,1988,vol. 110,p. 6204

9
[ 50-00-0 ]
[ 108-95-2 ]
[ 2467-02-9 ]
[ 2467-03-0 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
7.03%; 18.73%; 74.24%		The procedure was the same as in Example 9 except that the reaction time for the synthesis of bisphenol F was 0.5 hour, giving a bisphenol F yield of23.72%. The mass percentages of 2,4'-, 4,4 ', 2,2'-isomers were 18.73%, 74.24% and 7.03%, respectively. Example 9The procedure was the same as in Example 7 except that the amount of phosphotungstic acid added in the catalyst preparation was 1.17 g (0.41 mmol)The yield of bisphenol F was 67.01%. The mass percentages of 2,4 ', 4,4', 2,2'-isomers were 30.52%54.23%, 15.25%.Example 7The procedure was the same as in Example 1 except that the raw material for the preparation of the catalyst was 39.67 g (2.20 mol) of deionized water,(0.24 mol) of phosphotungstic acid, 0.71 g (7.10 mmol) of chromium trioxide, 1.47 g (7.10 mmol) of trimesic acid,From room temperature to 220 C, 220 C for 96 hours to obtain catalyst B, the rest of the process steps and parameters unchanged,The yield of bisphenol F was 74.81%. The mass percentages of 2,4 ', 4,4', 2,2'-isomers were21.27%, 41.05% and 37.68% respectively. Example 1(1) Preparation of catalystInto a 100 mL polytetrafluoroethylene liner, 25.02 g (1.39 mol) of deionized water, 2.02 g (5.00 mmol) of 9(0.24 mol) of phosphotungstic acid and 0.71 g (3.35 mmol) of trimesic acid were added and stirred for 30 min. From room temperatureHeated to 160 C, kept at 160 C for 12 hours, cooled, cautious, and then refiled with 60 C 95% ethanol 3Hour, treated with deionized water at 70 C for 3 hours, and finally dried at 150 C for 24 hours to obtain catalyst A.
51.19%; 33.70%; 15.11%		To a three-necked round bottom flask equipped with a condenser reflux tube, thermometer and magnetic stirrer was added 14.1 g (0.15 mol) of phenol,And 0.3g catalyst, constant temperature 80 , stirring 15min, adding a one-time percentage of 37% formaldehyde aqueous solution 0.41g(5 mmol). The yield of bisphenol F was 89.26% after reacting at 80 for 4 hours. Among them, 2,4 '-, 4,4', 2,2 'The mass percentages of the isomers were 33.70%, 15.11% and 51.19%, respectively.
30.11%; 50.55%; 19.34%		The procedure was the same as in Example 1, except that the reaction time for the synthesis of bisphenol F was 0.5 hour, so that the yield of bisphenol F was57.86%. The mass percentages of 2,4'-, 4,4 ', 2,2'-isomers were 50.55%, 19.34% and 30.11%, respectively.2) Synthesis of bisphenol FTo a three-necked round bottom flask equipped with a condenser reflux tube, thermometer and magnetic stirrer was added 14.1 g (0.15 mol) of phenol,And 0.3g catalyst, constant temperature 80 , stirring 15min, adding a one-time percentage of 37% formaldehyde aqueous solution 0.41g(5 mmol). The yield of bisphenol F was 89.26% after reacting at 80 for 4 hours. Among them, 2,4 '-, 4,4', 2,2 'The mass percentages of the isomers were 33.70%, 15.11% and 51.19%, respectively.

8.1%; 45.9%; 31.2%	With phosphoric acid; In water; at 85 - 100℃;Inert atmosphere;	Example 5To a 1000 ml flask were added 248 g of 95% phenol, 159 g of 77% phosphoric acid and 39-68 g of water. The mixture was stirred and heated up to 85-100 C under a nitrogen atmosphere. 33.8 g of 37% formaldehyde was added at a uniform rate and kept stirring until the reaction was completed. The reaction mixture was cooled to room temperature. The aqueous layer was separated. The organic layer was neutralized with sodium bicarbonate, and then the excess phenol was removed. The products were analyzed by high performance liquid chromatography (HPLC). The water content in the reaction mixture was varied from 12 to 23 wt%.
4.7%; 13.3%; 25.4%	With phosphoric acid; In methanol; at 45℃; for 2h;	Unlabeled phenol (5 mg, 0.053 mmol) was placed in a 5 mL pear-shaped flask,1.5 muL of a 37% formaldehyde solution (mass fraction of 37%) and 4 muL of phosphoric acid solution (85% by mass) were added and 70 muL of dichloromethane was added as the reaction solvent. And stirred at 45 C for 2 hours. At this time, the reaction product was viscous in a white color, and 3 mL of dichloromethane was added with stirring. A small amount of anhydrous Na2SO4 was added to remove water and extracted with dichloromethane (5 x 3 mL). The extracts were combined and concentrated under reduced pressure to 200 muL. The concentrate was first separated by Agela medium pressure silica gel preparative chromatography to recover unreacted phenol. The procedure was followed by elution with n-pentane: dichloromethane = 30: 70 (v / v) as eluent to remove The reaction product is less polar byproducts; followed by elution of the phenol with methylene chloride; then the mixture of the target bisphenol F and its by-product is washed out with pure methanol. The methanol-eluted mixture was concentrated by rotary evaporation and purified by preparative silica gel plate (GF254, 180 mm x 200 mm x 1 mm, Duran). Expanded agent selected n-pentane: dichloromethane: isopropyl alcohol: acetic acid (80: 70: 6: 3), started three times. Wherein the Rf value of the 4,4'-BPF is 0.25, the Rf value of the 4'-BPF is 0.38. But 2,2'-BPF of Rf = 0.75 is still a mixture and needs to be purified again. This column was scraped with silica gel and extracted with methanol (5 x 10 mL) and then separated by preparative silica gel. The developing solvent was selected from n-pentane: isopropanol: acetic acid (200: 10: 1) -BPF Rf = 0.48. The three bisphenol F isomers were scraped off and extracted five times with methanol (5 x 10 mL). The extract and the recovered phenol were concentrated and analyzed by high performance liquid chromatography (HPLC). The results showed that the yield of the three bisphenol F was 4,4'-BPF, 25.4%; 2,4'-BPF, 13.3%; 2,2'-BPF, 4.7%. The recovery of phenol was 37% of the amount of phenol put. The chemical purity of the three bisphenol F isomers and phenol was greater than 99%.
	With Al-SBA-15; In water; at 80℃; for 4h;	General procedure: The hydroxyalkylation of phenol with formaldehyde to bisphenol F was carried out in a 100 ml magnetically stirred glass reactor equipped with a reflux condenser. Typically, 9.4 g of phenol, 0.2703 g of 37% aqueous formaldehyde and 0.1 g of the M-SBA-15 catalyst were added into the reactor which then was heated to 80 C keeping for 4 h. The reaction products were analyzed by an Agilent 7890A GC with the internal standard method. The yield and selectivity of bisphenol Fwere calculated on consumed formaldehyde [14].
	With N-ethyl sulfamic acid functionalized polyvinyl chloride-coated nano-silica; In water; at 70℃; for 1h;Catalytic behavior;	The hydroxyalkylationof phenol with formaldehyde to BPF was performed in a magneticallystirred glass reactor fitted with a reflux condenser andan arrangement for temperature control. In a typical procedure, 0.2 mol of phenol, 0.01 mol of formaldehyde and catalyst(0.02 g, 0.25 mol%, based on the acid density of the catalyst)were added into the reactor. No other solvent was needed. Thereaction mixture was heated to 70 C. After 1 h, the reactionwas stopped and cooled to room temperature, then the solidcatalysts were separated by filtration, washed with aqueousethanol, and then was dried overnight at 60 C in a vacuumdrying oven for reuse. The unreacted formaldehyde was determinedusing a UV-2450 spectrophotometer (Shimadzu, Kyoto,Japan) using an acetylacetone spectrophotometric method.23,24The compositions of the hydroxyalkylated products were determinedon an Agilent 1100 HPLC (Agilent, USA) with an externalstandard method14,15 and the specific operation conditionswere as follows: 4.6 x 250mm of Agilent SB-C 18 chromatographiccolumn, methanol/water 65:35 (v/v) of mobile phase,1.0ml/min of flow rate, the UV detector 270 nm, column temperature30 C, injection volume 20 muL. The activity of catalystwas evaluated in terms of formaldehyde conversion and theselectivity of bisphenols F, which were calculated as follows:Conversion % moles of reacted formaldehydemoles of formaldehyde x100%Selectivity % moles of bisphenols FP moles of all products x100%

Reference： [1]Patent: CN104211580,2016,B .Location in patent: Paragraph 0028; 0041; 0042; 0045; 0046; 0047; 0048
[2]Patent: CN104211580,2016,B .Location in patent: Paragraph 0029
[3]Patent: CN104211580,2016,B .Location in patent: Paragraph 0029; 0037; 0038
[4]Patent: WO2015/41614,2015,A1 .Location in patent: Page/Page column 15
[5]RSC Advances,2016,vol. 6,p. 92716 - 92722
[6]Patent: CN106699518,2017,A .Location in patent: Paragraph 0038-0039
[7]Journal of Organic Chemistry USSR (English Translation),1985,vol. 21,p. 2198 - 2201
Zhurnal Organicheskoi Khimii,1985,vol. 21,p. 2403 - 2407
[8]Journal of Organic Chemistry USSR (English Translation),1985,vol. 21,p. 2198 - 2201
Zhurnal Organicheskoi Khimii,1985,vol. 21,p. 2403 - 2407
[9]Catalysis Communications,2015,vol. 67,p. 21 - 25
[10]RSC Advances,2016,vol. 6,p. 34625 - 34632
[11]RSC Advances,2016,vol. 6,p. 34625 - 34632
[12]RSC Advances,2016,vol. 6,p. 34625 - 34632
[13]Bulletin of the Chemical Society of Japan,2019,vol. 92,p. 1394 - 1403

10
[ 75-09-2 ]
[ 108-95-2 ]
[ 2467-03-0 ]
[ 620-92-8 ]
[ 603-44-1 ]
[ 76176-97-1 ]

Yield	Reaction Conditions	Operation in experiment
	at 15℃; for 48h; Irradiation; Further byproducts given;

Reference： [1]Latowski, Tadeusz; Latowska, Elzbieta; Poplawska, Barbara; Przytarska, Miroslawa; Walczak, Maria; Zelent, Bogumil [Polish Journal of Chemistry, 1980, vol. 54, # 5, p. 1073 - 1080]

11
[ 6068-70-8 ]
[ 620-92-8 ]
[ 169179-44-6 ]
C₆₄H₇₂N₄O₄*C₅₃H₄₀O₄ [ No CAS ]

Reference： [1]Chemistry - A European Journal,1999,vol. 5,p. 2692 - 2697

12
[ 620-92-8 ]
[ 106-96-7 ]
bis(4-(prop-2-yn-1-yloxy)phenyl)methane [ No CAS ]

Reference： [1]Chemistry - A European Journal,2001,vol. 7,p. 3572 - 3583
[2]New Journal of Chemistry,2017,vol. 41,p. 8443 - 8450
[3]Chemical Communications,2017,vol. 54,p. 156 - 159

13
[ 620-92-8 ]
[ 96-32-2 ]
[ 65329-07-9 ]

Reference： [1]Chemical and Pharmaceutical Bulletin,2005,vol. 53,p. 444 - 447

14
[ 201230-82-2 ]
[ 108-95-2 ]
[ 620-92-8 ]
[ 603-44-1 ]
[ 123-08-0 ]
[ 90-02-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 80% 2: 6%	With hydrogen fluoride; boron trifluoride at 45℃; for 4.5h;

Reference： [1]Willemse, J. Alexander; Bezuidenhoudt, Barend C. B.; Holzapfel, Cedric W. [Synthesis, 2006, # 15, p. 2543 - 2550]

15
[ 620-92-8 ]
[ 16523-28-7 ]

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 8146 - 8156
[2]Journal of the American Chemical Society,1935,vol. 57,p. 128

16
[ 620-92-8 ]
bis-(2-methyl-benzoxazol-5-yl)-methane [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 8146 - 8156

17
[ 620-92-8 ]
C₃₁H₂₆N₆O₈ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 8146 - 8156

18
[ 620-92-8 ]
C₂₁H₂₄N₂O₂⁽²⁺⁾*2C₇H₇O₃S^(1-) [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 8146 - 8156

19
[ 620-92-8 ]
C₃₅H₃₄N₄O₂⁽²⁺⁾*2C₇H₇O₃S^(1-) [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 8146 - 8156

20
florisil [ No CAS ]
[ 100-39-0 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide;	Example XXVIII Preparation of C-10 Carbon-Substituted Monomer 34 of the Present Invention The carboxylic acid 33 (23 mg, 0.074 mmol), potassium carbonate (20 mg, 0.147 mmol), and benzyl bromide (25 mg, 0.147 mmol) were dissolved in dry N,N-dimethylformamide (1 mL). The reaction was stirred at room temperature overnight. The solution was then diluted with diethyl ether (2 mL) and distilled water (3 mL). The aqueous layer was separated and extracted with diethyl ether (3*5 mL). The combined organic phase was dried over magnesium sulfate, concentrated under reduced pressure, and then chromatographed through Florisil (10percent ethyl acetate in hexanes) to provide the ester 34 (20 mg, 67percent yield) as a white solid. Mp: 84-86° C. [alpha]D25 =+52.5 (c=1.21, CHCl3). HPLC: 15:85 ethyl acetate:hexanes, 3 mL/minutes, 254 nm, Rt 3.4 minutes. 1 H NMR (CDCl3, 400 MHz) delta: 7.28-7.40 (m, 5H), 5.27 (s, 1H), 5.23 (d, J=12.8 Hz, 1H), 5.18 (d, J=12.8 Hz, 1H), 4.06 (d, J=11.2 Hz, 1H), 2.68-2.77 (m, 1H), 2.37 (ddd, J=4.0, 13.6, 14.8 Hz, 1H), 2.03 (ddd, J=2.8, 4.8, 14.4 Hz, 1H), 1.85-1.91 (m, 1H), 1.68-1.73 (m, 2H), 1.52-1.59 (m, 1H), 1.44 (s, 3H), 1.21-1.50 (m, 4H), 0.98-1.08 m, 1H), 0.95 (d, J=6.4 Hz, 3H), 0.75 (d, J=7.2 Hz, 3H). 13 C NMR (CDCl3, 100 MHz) delta: 169.7, 135.6, 128.5, 128.3, 128.2, 104.3, 91.9, 79.9, 75.6, 66.5, 51.9, 45.5, 37.2, 36.1, 33.9, 30.5, 25.9, 24.6, 21.2, 20.2, 13.0. IR (CHCl3): 2926, 1752, 1456, 1376, 1280, 1183, 1088, 1048, 879 cm-1.

Reference： [1]Patent: US6160004,2000,A

21
methylene chloride-water [ No CAS ]
[ 35718-08-2 ]
[ 620-92-8 ]
Bis(4-propargyloxycarbonyloxyphenyl)methane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93.6%	With trimethylamine; In dichloromethane;	EXAMPLE 1 Bis(4-propargyloxycarbonyloxyphenyl)methane A flask equipped with a stirrer, thermoter, nitrogen gas tube and reflux condenser was charged with 20.0 g of bis(4-hydroxyphenyl)methane, 50.0 g of methylene chloride and 23.0 g of trimethylamine. To the flask was added 26.0 g of propargyl chloroformate dropwise over one hour and the mixture was allowed to react for 6 hours at 30° C. After the reaction, the reaction mixture was treated with methylene chloride-water mixture and the organic phase was separated followed by drying over magnesium sulfate overnight. After filtering, the filtrate was evaporated in a rotary evaporator. The resulting crystals were recrystallized to give the title compound melting at 60° C. at a yield of 93.6percent of theory. The structure of the product was identified by the IR spectrum and 1 H-NMR (in CDCl3, trimethylsilane standard). IR: 2980 cm-1 (--CH2 --); 3300 cm-1, 2100 cm-1 (CHC--); 1738 cm-1 (--OCOO--); 1600 cm-1, 1500 cm-1 (Phe); 1450 cm-1 (--CH2 --). 1 H-NMR: delta(ppm) 2.41 (CHC--); 4.87 (--CH2 --); 6.96, 7.15 (Phe); 2.54 (--CH2 --).
93.6%	With trimethylamine; In dichloromethane;	Example 1 Bis(4-propargyloxycarbonyloxyphenyl)methane A flask equipped with a stirrer, thermoter, nitrogen gas tube and reflux condenser was charged with 20.0 g of bis(4-hydroxyphenyl)methane, 50.0 g of methylene chloride and 23.0 g of trimethylamine. To the flask was added 26.0 g of propargyl chloroformate dropwise over one hour and the mixture was allowed to react for 6 hours at 30 °C. After the reaction, the reaction mixture was treated with methylene chloride-water mixture and the organic phase was separated followed by drying over magnesium sulfate overnight. After filtering, the filtrate was evaporated in a rotary evaporator. The resulting crystals were recrystallized to give the title compound melting at 60 °C at a yield of 93.6 percent of theory. The structure of the product was identified by the IR spectrum and 1H-NMR (in CDCl3, trimethylsilane standard). IR: 2980 cmmin1 (-CH2-); 3300 cmmin1, 2100 cmmin1 (CH.ident.C-); 1738 cmmin1 (-OCOO-); 1600 cmmin1, 1500 cmmin1 (Phe); 1450 cmmin1 (-CH2-) 1H-NMR: delta (ppm) 2.41 (CH.ident.C-); 4.87 (-CH2-); 6.96, 7.15 (Phe); 2.54 (-CH2-)

Reference： [1]Patent: US5194653,1993,A
[2]Patent: EP457334,1991,A1

22
[ 620-92-8 ]
[ 100-39-0 ]
[ 51572-31-7 ]

Yield	Reaction Conditions	Operation in experiment
0.9 g (31%)	With sodium methylate; In methanol; ethyl acetate; acetone;	(1) To a solution of 2.0 g (10 mmol) of 4,4'dihydroxydiphenylmethan in 100 ml dry acetone was added 29.4 ml of 0.34M NaOMe in MeOH. After the reaction mixture had been stirred for 20 min 1.7 g (10 mmol) of benzylbromide was added. The reaction was stirred at room temperature for 15 h. 250 ml EtOAc was added and then extracted with 250 ml 0.5M HCl, 250 ml H2 O and 50 ml saturated NaCl(aq). Drying (MgSO4), evaporation of the EtOAc and purification on silica gave 0.9 g (31%) of 4'-benzyloxy-4-hydroxydiphenyl methan.
	In ethanol; sodium ethanolate;	A. 30.00 g of bis-(4-hydroxy-phenyl)-methane were dissolved in 240 ml of 0.82M sodium ethylate solution in ethanol, treated with 19.80 ml of benzyl bromide and stirred at reflux for 4 hours. After cooling to room temperature, the mixture was worked up extractively with ice-water, dilute hydrochoric acid and methylene chloride. The thus-obtained crude product was chromatographed on silica gel with methylene chloride and ether. There was thus obtained 4-(4-benzyloxy-benzyl)-phenol, MS: m/z 290.0 ([M]+).

Reference： [1]Patent: US5567728,1996,A
[2]Patent: US5830920,1998,A

23
[ 5292-43-3 ]
[ 620-92-8 ]
di-tert-butyl 4,4'-methylene-bis-phenoxyacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In acetonitrile;	A. A solution of 0.4 g of bis-(4-hydroxyphenyl)-methane in 8 ml of acetonitrile was treated under argon with 0.3 g of powdered potassium carbonate and 0.4 g of tert-butyl bromoacetate and stirred at room temperature for 2.5 hours. An additional 0.13 g of tert-butyl bromoacetate was added and the mixture was stirred at room temperature for 70 hours. The reaction mixture was concentrated and the residue was chromatographed on silica gel with methylene chloride/ether (95:5) and yielded di-tert-butyl 4,4'-methylene-bis-phenoxyacetate as a colourless solid, MS: m/z 428 ([M]+).

Reference： [1]Patent: US5521160,1996,A

24
[ 5292-43-3 ]
[ 620-92-8 ]
tert.-butyl 4-(4-hydroxy-benzyl)-phenoxyacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In acetonitrile;	A. 0.4 g of bis-(4-hydroxy-phenyl)-methane dissolved in 8 ml of acetonitrile was treated under argon with 0.3 g of powdered potassium carbonate and 0.4 g of tert.-butyl bromoacetate and stirred at room temperature for 2.5 hours. Subsequently, a further 0.13 g of tert.-butyl bromoacetate was added and the mixture was stirred at room temperature for 70 hours. Thereupon, the reaction mixture was concentrated and the residue was chromatographed on silica gel with methylene chloride/ether (95:5); there was thus obtained tert.-butyl 4-(4-hydroxy-benzyl)-phenoxyacetate as a colorless solid, MS: m/z 314 ([M]+).

Reference： [1]Patent: US5830920,1998,A

25
[ 75-77-4 ]
phenol (C₆ H₅ OH) [ No CAS ]
[ 109-79-5 ]
[ 107-06-2 ]
[ 843-55-0 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane; cyclohexanone;	EXAMPLE I Preparation of 1,1-Bis(p-hydroxyphenyl)cyclohexane (Bisphenol Z) in the Presence of a Thiol Catalyst A mixture of 98.15 grams of cyclohexanone, 470 grams of phenol (C6 H5 OH), 1.0 gram of butanethiol, and 150 milliliters of 1,2-dichloroethane was charged into a 2-liter 3-necked round-bottomed flask fitted with a mechanical stirrer, a dropping funnel, and a reflux condenser. To the reaction flask was added 108 grams of chlorotrimethyl silane through the dropping funnel over a period of 5 minutes, and the resulting mixture was stirred, and heated in an oil bath at 50 to 55 C. under a nitrogen atmosphere. The colorless reaction mixture turned brown in color after 5 minutes of heating, and evolution of HCl gas was observed. Precipitation of the product from the reaction medium was noted after about 15 minutes. During this time, the temperature of the reaction mixture rose gradually, and reached a final temperature of 65 C. after 60 minutes. The stirring and heating were continued for another 1.5 hours before the oil bath was removed. After cooling to room temperature, the mixture was filtered by suction filtration, and the crude solid product obtained was slurried up in 500 milliliters of methylene chloride and filtered. The filtered product was further washed twice with methylene chloride. Recrystallization from a methanol and water mixture afforded 218 grams of the above pure bisphenol (Z) product with a melting point of 195 to 197 C. Also, High Performance Liquid Chromatography (HPLC) analysis indicated that the product had a purity of 99.2 percent.

Reference： [1]Patent: US4766255,1988,A

26
[2,2-bis(4-hydroxyphenyl)hexafluoropropane]in [ No CAS ]
[ 620-92-8 ]
[ 16420-13-6 ]
4,4-(hexafluoroisopropylidene)bisbenzenethiol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; potassium hydroxide; In N-methyl-acetamide; methanol; water; benzene;	To a solution of 112 grams (0.33 mole) of Bisphenol AF [2,2-bis(4-hydroxyphenyl)hexafluoropropane]in 700 milliliters of benzene was added 43.5 grams (0.66 mole) of 85% potassium hydroxide. The resulting solution was refluxed with a trap to remove water; benzene was then removed at reduced pressure. To the resulting salt was added 700 milliliters of dimethylformamide, the mixture was then cooled to 0 C., and then 100 grams (0.81 mole) of N,N-dimethylthiocarbamyl chloride was added. The resulting mixture was heated to room temperature, then to 60 C., and maintained at 60 C. for one hour. The product mixture was diluted with three liters of water and extracted twice with an 80:20 benzene/hexane solution. The organic phase was evaporated under reduced pressure to obtain a solid crystalline residue. The residue was recrystallized from a 5:1 methanol/ benezene solution to obtain 125 grams of a product melting at about 209-211 C. This product was the O-thiocarbamate ester of Bisphenol AF. Fifteen grams (0.3 mole) of the O-thiocarbamate ester of bisphenol AF was placed in a reaction vessel, and heated at 250 C. under argon for one hour. After cooling the product to room temperature, the glassy residue was recrystallized from 60 milliliters of methanol to obtain 11 grams of a product having a melting point of 141-144 C. This product was the S-thiocarbamate ester of the bisbenzenethiol derivative. Seventy-five grams (0.15 mole) of the above S-thiocarbamate ester was then placed in 400 milliliters of methanol, and a solution of 75 grams of potassium hydroxide in 200 milliliters of water was added. This mixture was refluxed for one hour, cooled and diluted with two liters of water. A solution of 165 milliliters of concentrated HCl in one liter of water was then added. A precipitate was obtained which was recrystallized from a 3:1 methanol-water mixture to obtain 50 grams of the product 2,2-bis(4-mercaptophenyl)hexafluoropropane (Compound 6). The dipotassium salt of Compound 6 was formed by reacting Compound 6 with a potassium-containing base.

Reference： [1]Patent: US4695655,1987,A

27
[ 486-25-9 ]
[ 108-95-2 ]
[ 620-92-8 ]
[ 3236-71-3 ]

Yield	Reaction Conditions	Operation in experiment
97%	With hydrogenchloride; In Zinc chloride; water; isopropyl alcohol;	EXAMPLE 3 9,9-bis-(4-hydroxyphenyl)-fluorene 30 moles of phenol containing 9% by weight of water were stirred in an autoclave and then 2 moles of zinc chloride and 10 moles of fluorenone were dissolved therein. Then, 10 moles of gaseous hydrogen chloride were added to the stirred mixture and the mixture was reacted at 80 C. for one hour and then at 70 C. for 3 hours. The reaction mixture was then dissolved in 5 liters of isopropanol at 60 C. and the solution was then poured with vigorous stirring into a ten-fold volume of water whereby the resulting bisphenol precipitated as 3.4 kg (97% yield) of the product in the form of a yellow product.
81%	In Zinc chloride; water; isopropyl alcohol;	EXAMPLE 6 9,9-bis-(4-hydroxyphenyl)-fluorene 15 moles of phenol containing 9% by weight of water were stirred in an autoclave at 50 C. and then one mole of zinc chloride and 5 moles of fluorenone were dissolved therein. The mixture was saturated with gaseous hydrogen chloride and the mixture was reacted at room temperature for 2 days. The mixture was dissolved in 2.5 liters of isopropanol at 60 C. and the solution was poured with vigorous stirring into a 10 fold volume of water to obtain 1.6 kg (92% yield) of the desired bisphenol in the form of a light yellow product. Crystallization from toluene gave an 81% yield of crystalline product with a purity equal to that of Example 5.

Reference： [1]Patent: US4467122,1984,A
[2]Patent: US4467122,1984,A

28
[ 620-92-8 ]
[ 100-44-7 ]
[ 834-25-3 ]
[ 51572-31-7 ]

Yield	Reaction Conditions	Operation in experiment
	In <i>N</i>-methyl-acetamide; ethanol; water; mineral oil	2.A Step A: Step A: α-(p-benzyloxyphenyl)-p-cresol To a stirred suspension of 3.36 g of sodium hydride (in mineral oil) in 50 ml of dimethylformamide is added dropwise at room temperature a solution of 15 g bis-(p-hydroxyphenyl)-methane in 50 ml dimethylformamide. The resulting solution is stirred at room temperature for one hour. Ten grams of benzyl chloride is added dropwise and the stirring is continued at room temperature overnight. After evaporation of the solvent under reduced pressure, the residue is treated with 100 ml of water and extracted twice with diethyl ether. The combined ether extracts are combined, dried over anhydrous magnesium sulfate, evaporated to dryness, and the resulting oil dissolved in hot ethanol. Bis-p-(benzyloxy)phenyl-methane (m.p. 109.5°-110°C) crystallizes upon cooling and is collected by filtration. The mother liquors are evaporated to dryness and the crystalline mono-addition product is obtained by chromatography on silica gel with chloroform. After separation, the mono-benzyl ether is recrystallized from isopropyl ether, m.p. 95°-96°C.

Reference： [1]Current Patent Assignee: SHANDOZ - US3932481, 1976, A

29
[ 620-92-8 ]
[ 27006-76-4 ]
[ 862564-54-3 ]

Yield	Reaction Conditions	Operation in experiment
		Reference Production Example 28; 0.4 g of sodium hydride (60percent in oil) was suspended to 15 ml of N, N-dimethylformamide, 1.3 g of bis (4-hydroxyphenyl) methane was added at room temperature, and then the mixture stirred at 70 °C for two hours. After that, to the said mixture was added 5 ml of N, N-dimethylformamide solution of 1.0 g of 5-chloro-1, 3-dimethyl-lH-pyrazole-4-carbaldehyde over ten minutes at 70 °C, and then the mixture was stirred at 70 C for seven hours. After that, aqueous solution of saturated ammonium chloride was added to the reaction mixture which was cooled to room temperature, and extracted with ethyl acetate. The organic layer was successively washed with diluted hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.2 g of the compound shown by the formula (xxviii). H-NMR (CDCl3, TMS) 5 (ppm): 2.45 (3H, s), 3.63 (3H, s), 3.88 (2H, s), 6. 75-6.78 (2H, m), 6.90-6. 92 (2H, m), 7.02-7. 04 (2H, m), 7.13-7. 15 (2H, m), 9.51 (lH, s)

Reference： [1]Patent: WO2005/75433,2005,A1 .Location in patent: Page/Page column 178

30
[ 620-92-8 ]
[ 1885-14-9 ]
[ 53184-77-3 ]

Reference： [1]Molecules,2010,vol. 15,p. 3661 - 3682

31
[ 106-20-7 ]
[ 620-92-8 ]
[ 7693-46-1 ]
[ 1182705-78-7 ]

Yield	Reaction Conditions	Operation in experiment
76.8%	Stage #1: bis-(4-hydroxyphenyl)methane; 4-Nitrophenyl chloroformate With triethylamine In dichloromethane at 20℃; for 48h; Inert atmosphere; Stage #2: 2-ethyl-N-(2-ethylhexyl)-1-hexanamine With triethylamine In dichloromethane at 20℃; Inert atmosphere;

Reference： [1]Location in patent: experimental part Misuraca, M. Cristina; Grecu, Tudor; Freixa, Zoraida; Garavini, Valentina; Hunter, Christopher A.; Van Leeuwen, Piet W.N.M.; Segarra-Maset, M. Dolores; Turega, Simon M. [Journal of Organic Chemistry, 2011, vol. 76, # 8, p. 2723 - 2732]

32
[ 591-87-7 ]
[ 620-92-8 ]
bis(4-(allyloxy)phenyl)methane [ No CAS ]
[ 114896-84-3 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;5%-palladium/activated carbon; triphenylphosphine; In water; isopropyl alcohol; at 85℃; for 8h;Inert atmosphere;	Synthesis Example 1Synthesis of a Diallyl Ether of Bisphenol F200 Grams (0.999 mol) of bisphenol F ST (manufactured by Mitsui Chemicals, Inc.), 2.13 g (0.499 mol) of 50percent-water-containing 5percent-Pd/C-STD type (manufactured by N.E. CHEMCAT Corporation), 2.62 g (9.99 mmol) of triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.), 276 g (2.00 mol) of potassium carbonate (manufactured by Asahi Glass Co., Ltd.), 220 g (2.20 mol) of allyl acetate (manufactured by Showa Denko K.K.) and 200 g of isopropanol were put into a 2000-mL eggplant type flask, and were reacted under nitrogen atmosphere at 85° C. for 8 hours. After the reaction was finished, the reaction solution was partly sampled, diluted with ethyl acetate and analyzed by gas chromatography to determine that the ratio of bisphenol F diallyl ether to monoallyl ether was up to 99:1.Thereafter, 400 g of toluene was added to the reaction solution, Pd/C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by using an evaporator. The reaction and the after-treatment were repeated four times to obtain 748 g of a distillate (isolation yield 66percent, bisphenol F diallyl ether 98.7percent, the remainder being monoallyl ether) and 368 g of a non-distillate (bisphenol F diallyl ether 88percent) by using a molecular distillation apparatus (manufactured by Taika Kogyo Co., Ltd.). The viscosity of the distillate at 25° C. was 25 mPa*s. The ratio of the isomers was o,o'-:o,p'-:p,p'-=17:52:31.

Reference： [1]Patent: US2011/263882,2011,A1 .Location in patent: Page/Page column 5

33
[ 620-92-8 ]
[ 91-22-5 ]

Yield	Reaction Conditions	Operation in experiment
61%	With caesium carbonate; sodium iodide; In N,N-dimethyl-formamide;	Step 2An N2 purged flask was charged with the bromide (738 mg, 2.5 mmol), bisphenol (1 g, 2.4 mmol), Cs2CO3 (1.21 g, 3.7 mmol) and NaI (72 mg, 0.48 mmol).To this mixture was added DMF (24 mL) and the heterogeneous mixture was heated in a preheated 65° C. oil bath.After 2 h very little of the bromide remained.Additional bromide (141 mg, 0.48 mmol) was added to the reaction and heating continued for 16 h.The reaction was complete, as determined by LC/MS, the next day.The reaction was cooled to room temperature and diluted with EtOAc.This mixture was extracted with 5percent LiCl (aq.) basified with a small amount of sat. NaHCO3(aq.) (2) and brine (1).The organic phase was then dried over Na2SO4 with a small amount of MgSO4.After removal of the drying agents by vacuum filtration, the quinoline was isolated from the filtrate (800 mg, 61percent) as a yellow-brown solid. LC/MS=548.26 (M++1).

Reference： [1]Patent: US2011/306541,2011,A1

34
[ 620-92-8 ]
[ 91903-21-8 ]

Yield	Reaction Conditions	Operation in experiment
> 99%	With oxygen; ascorbic acid; In water; acetonitrile; at 20℃; for 48h;pH 7;Na-phosphate buffer; Enzymatic reaction;	General procedure: A panel of phenols (Fig. 7) were oxidized, including para-cresol 1, 4-ethyl phenol 2, 4-tert-butyl phenol 3, 4-sec-butyl phenol 4, 2,4-di-tert-butyl phenol 5, meta-cresol 6, 3,4-dimethyl phenol 7, 4-chloro phenol 8, 4-chloro-2-methyl phenol 9, 2-methoxy-4-methyl phenol 10, 2-methoxy phenol 11, 3-(4-hydroxyphenyl)propionic acid 12, 4-hydroxyphenylacetic acid 13, bis(4-hydroxyphenyl)methane 14 and tyrosol 15. As a general procedure phenol (0.05 mmol), tyrosinases (263-526 IU) and AA (1.5 equiv) were placed in 0.1 M Na-phosphate buffer pH 7.0 (5.0 mL) in vigorous stirring at room temperature. For insoluble aqueous phenols 3, 5, 14 substrates were dissolved in CH3CN (1.0 mL) and then added to the buffer solutions. Oxidations were performed using homogeneous and heterogeneous conditions. Reactions were monitored by thin layer chromatography (TLC). After the disappearance of the substrate, the reaction mixture was acidified with a solution of HCl 1.0 N and extracted twice with EtOAc. The organic extracts were treated with a saturated solution of NaCl and dried over anhydrous Na2SO4, then filtered and concentrated under vacuum to yield a colored crude. In the case of immobilized enzyme, biocatalyst was first recovered by filtration and the solution was subjected to the same work up described above. The obtained colored residue was treated with pyridine, HMDS and TMCS (HMDS-TMCS, 2:1 v/v) under vigorous stirring at room temperature for 30 min, then allowed to stand for 5 min.50 All products were identified by 1H NMR, 13C NMR and GC-MS. 1H NMR and 13C NMR were recorded on a Bruker 200 MHz spectrometer using CDCl3 as solvent. All chemical shift are expressed in parts per million (delta scale). GC-MS analysis were performed on a GCMS-QP5050 Shimadzu apparatus using a SPB column (25 m .x. 0.25 mm and 0.25 mm film thickness) and an isothermal temperature profile of 100 °C for 2 min, followed by a 10 °C/min temperature gradient to 280 °C for 25 min. The injector temperature was 280 °C. Chromatography-grade helium was used as the carrier gas with a flow of 2.7 mL/min. Mass spectra were recorded with an electron beam of 70 eV.

Reference： [1]Bioorganic and Medicinal Chemistry,2012,vol. 20,p. 157 - 166

35
[ 620-92-8 ]
[ 91903-21-8 ]
[ 14235-78-0 ]

Yield	Reaction Conditions	Operation in experiment
53%; 41%	With oxygen; ascorbic acid; In water; acetonitrile; at 20℃; for 24h;pH 7;Na-phosphate buffer; Enzymatic reaction;	General procedure: A panel of phenols (Fig. 7) were oxidized, including para-cresol 1, 4-ethyl phenol 2, 4-tert-butyl phenol 3, 4-sec-butyl phenol 4, 2,4-di-tert-butyl phenol 5, meta-cresol 6, 3,4-dimethyl phenol 7, 4-chloro phenol 8, 4-chloro-2-methyl phenol 9, 2-methoxy-4-methyl phenol 10, 2-methoxy phenol 11, 3-(4-hydroxyphenyl)propionic acid 12, 4-hydroxyphenylacetic acid 13, bis(4-hydroxyphenyl)methane 14 and tyrosol 15. As a general procedure phenol (0.05 mmol), tyrosinases (263-526 IU) and AA (1.5 equiv) were placed in 0.1 M Na-phosphate buffer pH 7.0 (5.0 mL) in vigorous stirring at room temperature. For insoluble aqueous phenols 3, 5, 14 substrates were dissolved in CH3CN (1.0 mL) and then added to the buffer solutions. Oxidations were performed using homogeneous and heterogeneous conditions. Reactions were monitored by thin layer chromatography (TLC). After the disappearance of the substrate, the reaction mixture was acidified with a solution of HCl 1.0 N and extracted twice with EtOAc. The organic extracts were treated with a saturated solution of NaCl and dried over anhydrous Na2SO4, then filtered and concentrated under vacuum to yield a colored crude. In the case of immobilized enzyme, biocatalyst was first recovered by filtration and the solution was subjected to the same work up described above. The obtained colored residue was treated with pyridine, HMDS and TMCS (HMDS-TMCS, 2:1 v/v) under vigorous stirring at room temperature for 30 min, then allowed to stand for 5 min.50 All products were identified by 1H NMR, 13C NMR and GC-MS. 1H NMR and 13C NMR were recorded on a Bruker 200 MHz spectrometer using CDCl3 as solvent. All chemical shift are expressed in parts per million (delta scale). GC-MS analysis were performed on a GCMS-QP5050 Shimadzu apparatus using a SPB column (25 m × 0.25 mm and 0.25 mm film thickness) and an isothermal temperature profile of 100 C for 2 min, followed by a 10 C/min temperature gradient to 280 C for 25 min. The injector temperature was 280 C. Chromatography-grade helium was used as the carrier gas with a flow of 2.7 mL/min. Mass spectra were recorded with an electron beam of 70 eV.

Reference： [1]Bioorganic and Medicinal Chemistry,2012,vol. 20,p. 157 - 166

36
[ 620-92-8 ]
[ 26487-67-2 ]
bis{4-[2-(azepan-1-yl)ethoxy]phenyl}methane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%		To a solution of bis(4-hydroxyphenyl)methane (39.2 mg, 0.196 mmol) in DMF (1.96 mL) at 0 °C was added 60percent sodium hydride (dispersion in paraffin liquid, 47.0 mg, 1.18 mmol). The reaction mixture was stirred for 25 min at 50 °C and then <strong>[26487-67-2]N-(2-chloroethyl)hexahydro-1H-azepine hydrochloride</strong> (128 mg, 0.646 mmol) was added in portions at room temperature. After the reaction mixture had been stirred for 3.5 h at 50 °C, saturated aqueous ammonium chloride was added at 0 °C. The mixture was extracted with dichloromethane, and the organic layer was washed with water and brine, and dried over sodium sulfate. After filtration of the mixture and evaporation of the solvent, the crude product was purified by thin layer chromatography on silica (eluant; ammoniacal chloroform/methanol = 9/1) to afford RID-F-S*4 (compound 25) (54.8 mg, 62percent) as an orange oil

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 71,p. 290 - 305

37
[ 620-92-8 ]
methylenebis(4,1-phenylene) bis(sulfamate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81.6%	With sulphamoyl chloride; In N,N-dimethyl acetamide; at 0 - 20℃;	General procedure: To a solution of 4,4?-(dimethylsilanediyl)diphenol (9a) (200mg, 0.82mmol) in N,N-dimethylacetamide (1mL) was added sulfamoyl chloride (283mg, 2.46mmol) at 0°C. The mixture was stirred at room temperature for 3h. The reaction was quenched with H2O aq, and the whole was extracted with ethyl acetate. The extract was successively washed with water and brine, and then dried over MgSO4. The solvent was evaporated, and the residue was purified by means of silica gel column chromatography (hexane/ethyl acetate=2:1 to 1:1) to afford a white solid. This was recrystallized from chloroform/hexane to give 3a (154.4mg, 46.8percent) as colorless crystals.

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 2244 - 2252

38
[ 7766-50-9 ]
[ 620-92-8 ]
C₃₅H₅₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		General procedure: p-Benzenediol (Hydroquinone, defined as BP1 here) (2.2 g,20 mmol) and sodium hydroxide (2.4 g, 60 mmol) were dissolved in 120 mL DMF in a 250-mL round bottomed Schlenk flask, then themixture was stirred for 30 min, and a solution of 11-bromo-1-undecene (12 g, 51.5 mmol) in DMF (120 mL) was added dropwise over 10 min. The resulting reaction mixture was heated at 70 C and left stirring for more than 8 h. Subsequently, the reaction was cooled to RT and quenched with addition of diethyl ether (100 mL) and water (100 mL). The aqueous phase was extracted with diethyl ether (300 mL 2), and the combined organic fractions were washed with brine and dried over MgSO4 and concentrated. The residue was recrystallized from EtOH twice to obtain 6.1 g BP1-M1. Yield: 74percent.

Reference： [1]Polymer,2015,vol. 64,p. 76 - 83

39
[ 620-92-8 ]
[ 146733-97-3 ]
2,2-dimethyl-5,11-diphenyl-4,6,10,12-tetraoxa-5,11-diphospha-1,3,7,9(1,4)-tetrabenzenacyclododecaphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	In toluene; at 90 - 95℃; for 4h;	2,2-Dimethyl-5,11-diphenyl-4,6,10,12-tetraoxa-5,11-diphospha-1,3,7,9(1,4)-tetrabenzenacyclodo-decaphane (6). Bisphenol 2 or 1, 2 mmol, was added to a solution of 2 mmol of compound 4 or 5, respec-tively, in 50 mL of anhydrous toluene. The mixture was heated for 4 h at 9095°C, the solvent was removed under reduced pressure (water-jet pump), and the residue was kept for 2 h under reduced pressure (1 mm) at 9095°C. Yield 83percent, unstable oily sub-stance. IR spectrum, nu, cm?1: 1440 (PC), 1190 (OC). 1H NMR spectrum, delta, ppm: 1.64 s (6H, CH3), 3.95 s (2H, CH2), 6.77 d and 7.04 d (4H, C6H4CMe2), 6.91 d and 6.99 d (4H, C6H4CH2), 7.57 m (3H, Ph), 7.94 m (2H, Ph). 31P NMR spectrum: deltaP 165.80 ppm, d. Mass spectrum: m/z 663.40 [M + Na]+.

Reference： [1]Russian Journal of Organic Chemistry,2016,vol. 52,p. 612 - 614
Zh. Org. Khim.,2016,vol. 52,p. 623 - 624,2

40
[ 620-92-8 ]
[ 1636-14-2 ]
4,4′-methylenedi(benzene-4,1-diyl) bis(N,N-diethyl-P-phenylphosphonamidite) [ No CAS ]
[ 109-89-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	In neat (no solvent); at 115 - 120℃; for 2h;	Compounds 4 and 5 were synthesized according to the procedures described in [2, 8, 9]. A mixture of 1.8 mmol bisphenol 1 or 2 and 3.6 mmol of 3 was heated for 2 h at 115120°C until the amount of evolved diethylamine attained nearly theoretical value, and the mixture was kept for 1 h under reduced pres-sure (1 mm) at that temperature; compounds 4 and 5 were obtained in 9697percent yield as viscous materials.

Reference： [1]Russian Journal of Organic Chemistry,2016,vol. 52,p. 612 - 614
Zh. Org. Khim.,2016,vol. 52,p. 623 - 624,2

41
[ 620-92-8 ]
[ 106131-61-7 ]
C₃₀H₂₀N₈O₄ [ No CAS ]
C₄₅H₃₀N₁₂O₆ [ No CAS ]

Reference： [1]Organic Letters,2016,vol. 18,p. 2668 - 2671

42
[ 50-00-0 ]
[ 1606-67-3 ]
[ 620-92-8 ]
C₄₉H₃₄N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71.2%	In toluene; at 95℃; for 3h;	At room temperature pyrene amine (4.34g, 20.0mmol), bisphenol F (2.00g, 10.0mmol) was added to a three-neck flask, stirred and dissolved in 100ml of toluene. Paraformaldehyde (1.2g, 40.0mmol) was added portionwise three-neck flask, kept stirred to mix, and then gradually warmed to 95 reflux. The reaction is stopped after 3 hours, left to cool to give a reddish brown solution. After 1mol / LNaOH, deionized water, toluene was removed by rotary evaporation, followed by vacuum dried for 24 hours, the resulting solid product is the amine pyrene - Bisphenol F benzoxazine, yield 71.2percent.

Reference： [1]Patent: CN104230837,2016,B .Location in patent: Paragraph 0083; 0084; 0085

43
[ 620-92-8 ]
[ 74-89-5 ]
C₁₇H₂₆N₄O₄P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35.2%		In a 30 ml two-necked flask equipped with a rotor, a reflux tube, and an inlet for introducing N2 were put 0.03 g (0.3 mmol) of magnesium chloride, 2.00 g (10 mmol) of 4,4?-methylenediphenol, and 30.67 g (200 mmol) ofphosphorus oxychioride. The reaction mixture was heated until reflux while introducing N2, followed by stirring overnight at that temperature. The introduced N2 was vented from the upper end of the reflux tube and bubbled through an aqueous sodium hydroxide solution to have the by-produced hydrogen chloride trapped. After the reaction, the excess phosphorus oxychloride was removed in an evaporator to leave yellow liquid (intermediate). The intermediate product was dissolved in 10 ml of dehydrated tetrahydrofuran to prepare a THF solution of the intermediate product. Then, a 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was thoroughly dried, purged with nitrogen, and charged with 18.08 g (42 mmol) of a methylamine tetrahydrofuran solution and 4.25 g (42 mmol) of triethylamine while cooling in a salt-ice-water bath. Afier stirring for 5 minutes, the THF solution of the intermediate product was added thereto dropwise using a syringe taking care not to let the reaction temperature exceed 20° C. Afier the addition, the stirring was continued for 1 hout The salt-ice-water bath was removed,and the reaction mixture was stirred at room temperature overnight. Afier completion of the reaction, the solvent and the excess of the starting material were removed in an evaporator to give pale yellow solid. The crude product was purified by colunm chromatography (stationary phase: silica gel, mobile phase: ethyl acetate/methanol=5/1 by volume, Rf=0. 29) to yield the desired phosphorus-containing compound [1-9] as white solid (overall yield: 35.2percent). The results of the identification analyses are shown in FIG. 10 (?H-NMR) and FIG. 11 (31P-NMR).

Reference： [1]Patent: US2016/200747,2016,A1 .Location in patent: Paragraph 0060

44
[ 17392-83-5 ]
[ 620-92-8 ]
(R)-2-[4-(4-hydroxybenzyl)phenoxy]propionic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
37%	With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran;Cooling with ice; Inert atmosphere;	General procedure: To an ice-bath cooled mixture of (R)-or (S)-methyl lactate(4.8 mmol), bis(4-hydroxyphenyl)methane (4.8 mmol), and triphenylphosphine(4.8 mmol) in anhydrous THF (30 mL), a solutionof diisopropyl azodicarboxylate (DIAD, 4.8 mmol) in anhydrous THF(20 mL) was added dropwise under nitrogen atmosphere. Themixture was allowed to warm to room temperature and stirred forovernight. The solvent was evaporated affording an oil which waschromatographed on a silica gel column (n-hexane/ethyl acetate9:1 as eluent) to give the target methyl esters as white solids.

Reference： [1]European Journal of Medicinal Chemistry,2017,vol. 127,p. 379 - 397

45
[ 27871-49-4 ]
[ 620-92-8 ]
(S)-2-[4-(4-hydroxybenzyl)phenoxy]propionic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran;Cooling with ice; Inert atmosphere;	General procedure: To an ice-bath cooled mixture of (R)-or (S)-methyl lactate(4.8 mmol), bis(4-hydroxyphenyl)methane (4.8 mmol), and triphenylphosphine(4.8 mmol) in anhydrous THF (30 mL), a solutionof diisopropyl azodicarboxylate (DIAD, 4.8 mmol) in anhydrous THF(20 mL) was added dropwise under nitrogen atmosphere. Themixture was allowed to warm to room temperature and stirred forovernight. The solvent was evaporated affording an oil which waschromatographed on a silica gel column (n-hexane/ethyl acetate9:1 as eluent) to give the target methyl esters as white solids.

Reference： [1]European Journal of Medicinal Chemistry,2017,vol. 127,p. 379 - 397

46
[ 5445-17-0 ]
[ 620-92-8 ]
2-[4-(4-hydroxybenzyl)phenoxy]propionic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
36%		A suspension of NaH (0.009 mol) in anhydrous THF (20 mL) wascooled to 0 °C and added with a solution of commercially availablebis(4-hydroxyphenyl)methane or 11 (0.009 mol) in anhydrous THF(15 mL). After 30 min, a solution of methyl or ethyl 2-bromopropionate (0.009 mol) in anhydrous THF (15 mL) wasadded dropwise and the mixture warmed at 60 °C for 96 h. Thesolvent was evaporated and the residue was added with ice andextracted with ethyl acetate. The organic layer was washed with2 N HCl and twice with brine, dried over Na2SO4, filtered andevaporated to dryness. The solid residue was chromatographed ona silica gel column (n-hexane/ethyl acetate 85:15 as eluent)affording the desired compounds as colorless oils.9.5.1. 2-[4-(4-Hydroxybenzyl)phenoxy]propionic acid methyl ester(12)36percent Yield; GC/MS, m/z (percent): 286 (M, 100), 227 (C15H15O2, 64),199 (C13H11O2, 62), 107 (C7H7O, 54); 1H NMR: 1.60 (d, J 6.88, 3H,CH-CH3), 3.75 (s, 3H, COOCH3), 3.83 (s, 2H, CH2), 4.72 (q bs,J 6.88, 2H, CH3-CH OH, D2O exchanged), 6.73-6.80 (m, 4H,aromatics), 7.00-7.07 (m, 4H, aromatics).

Reference： [1]European Journal of Medicinal Chemistry,2017,vol. 127,p. 379 - 397

47
[ 156578-22-2 ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
84%	With potassium hydrogen difluoride; In methanol; at 20℃; for 2h;	General procedure: In an oven-dried 25 mL round-bottom flask, a mixture of silyl ether 12 (0.266 g, 1 mmol) and KHF2 (0.195 g, 2.5 mmol) in anhydrous MeOH (10.0 mL) was stirred at r.t. The reaction was monitored by TLC using 40percent EtOAc in hexanes and was found tobe complete within 1 h. The mixture was evaporated under reduced pressure and loaded onto a silica column (100?200mesh) packed with hexanes (adequate caution was exercised to ensure complete transfer of the crude material). Elution with hexanes, followed by 30percent EtOAc in hexanes.

Reference： [1]Synlett,2017,vol. 28,p. 381 - 385

48
[ 124-73-2 ]
[ 620-92-8 ]
4,4'-bis(tetrafluoroethoxy)phenylmethane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%		At room temperature to 500mL thick-walled pressure bottle in order to join4,4'-dihydroxydiphenylmethane (20.1 g, 100 mmol), KOH (13.44 g, 240 mmol)DMSO (250 mL)And BrCF2CF2Br (114.3 g, 440 mmol),Then tighten the reaction bottle,The temperature was raised to 60 ° C for 20 h.After the reaction is cooled to room temperature,The reaction solution was poured into water,Ethyl acetate extraction (300 mL x 3),Saturated sodium chloride solution,Dried over anhydrous magnesium sulfate, filtered and dried to give a yellow solid.The yellow solid was dissolved in 300 mL of acetic acid,After heating to 50 ° C, zinc powder was added thereto in portions,After 36 h of reaction, the supernatant was decanted,Add appropriate amount of water,Petroleum ether extraction (300 mL x 3), saturated sodium chloride solution, dried over anhydrous magnesium sulfate, spin dry,Column chromatography,Petroleum ether as eluent to give 33.2 g (83.0percent) of a white solid.

Reference： [1]Patent: CN106631716,2017,A .Location in patent: Paragraph 0176; 0177; 0178; 0179

49
[ 50-00-0 ]
[ 620-92-8 ]
C₁₅H₁₃NO₃ [ No CAS ]
[ 101-77-9 ]
C₁₃₇H₁₁₈N₁₀O₁₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 10h;	Weighed 25.5 g (0.1 mol) of ortho-norbornene-functionalized phenol obtained from the previous reaction,(0.15 mol) of 4,4-dihydroxydiphenylmethane, 39.6 g (0.2 mol) of 4,4-diaminodiphenylmethane (DDM)Paraformaldehyde 24 g (0.8 mol) was charged into a reaction flask equipped with a stirrer, a thermometer and a condenser tube,To the reaction flask was added xylene as the reaction solvent, and gradually heated to 120 ° C for stirring. After 10 h,The reaction was stopped, the solvent was removed by suspending,The product was then dried in a vacuum oven for 12 h to give 91.1 g of a yellow solid product in 87percent yield.

Reference： [1]Patent: CN106699748,2017,A .Location in patent: Paragraph 0041; 0042; 0043; 0044; 0045; 0046

50
4,4'-methylenebis[phenol-2,3-dicarboxylic acid] [ No CAS ]
[ 620-92-8 ]

Yield	Reaction Conditions	Operation in experiment
63%	With quinoline; copper(I) oxide; 1,10-Phenanthroline; In 1-methyl-pyrrolidin-2-one; at 190℃; for 1h;Sealed tube; Microwave irradiation;	A reactor was charged with the 4,4'-methylenebis[phenol-2,3- dicarboxylic acid] starting material (300 mg), copper(I) oxide (24 mg), 1, 10- phenanthroline (60 mg), NMP (1200 muIota_) and quinoline (330 pL). The reactor was sealed, heated to 190 °C with microwave heating, and held for 1 hours, with stirring. The reaction mixture was cooled to ambient temperature then added to a stirred 1M solution of aqueous hydrochloric acid, and the organics were extracted with ethyl acetate (2x10ml). The combined organics were washed with water, dried (Na2S04), filtered and reduced by rotary evaporation to obtain the desired product as a light brown oil (101 mg, 63percent). The structure of the product as bisphenol F (bis(4-hydroxyphenyl)methane) was confirmed by 1H NMR.

Reference： [1]Patent: WO2017/111598,2017,A1 .Location in patent: Page/Page column 25

51
[ 620-92-8 ]
3-chloro-6-nitropyridazine [ No CAS ]
4,4'-bis(6-nitro-3-pyridazinyloxy)diphenylmethane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In N,N-dimethyl acetamide; at 60℃; for 6h;Inert atmosphere;	(1) 54.40 mmol (11.99 g) of 4,4'-dihydroxydiphenylmethane was added under conditions of room temperature and nitrogen protection,130.56 mmol (20.83 g)3-chloro-2-nitropyridazine and 130.56 mmol (18.04 g) of potassium carbonate were dissolved in 1935 mmol(180 ml) of N, N'-dimethylacetamide, the total mass fraction of the solid in the system is 10percent to 50percent and then heated to 60 ° C for 6 hours. After lowering to room temperature, the reaction is poured into mass fraction In a 5percent sodium hydroxide solution, filtered and the resulting solid was usedThe deionized water was repeatedly washed until the washing solution was neutral to give the dinitro-crude product as 15 g;The dinitro-crude product was mixed with 6 g of activated carbon in 861 mmol (80 ml) of N, N'-dimethylacetamide,Heated to 70 ~ 90 , 30 minutes after the hot filter, the filtrate by adding water to the solution saturated, filtered,The resulting solid was vacuum treated at 80 ° C for 8 hours to give a structure containing pyridazine4,4'-bis (6-nitro-3-pyridazinyloxy) diphenylmethane;

Reference： [1]Patent: CN107056711,2017,A .Location in patent: Paragraph 0031; 0032

52
[ 598-09-4 ]
[ 620-92-8 ]
C₂₁H₂₄O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 8h;

Reference： [1]Furutani, Masahiro; Kakinuma, Ayaru; Arimitsu, Koji [Journal of Polymer Science, Part A: Polymer Chemistry, 2018, vol. 56, # 2, p. 237 - 241]

53
[ 80-05-7 ]
[ 620-92-8 ]
[ 124-41-4 ]
[ 106-50-3 ]
C₄₇H₇₀N₁₁O₁₇P₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		A three-port 2000 ml glass reactor equipped with a stirring device was charged with 1 mol hexachlorocyclotriphosgene, 300 ml acetone and 4 mol sodium methoxide. While stirring,The temperature was raised to 60 ° C., 620 g of 20percent sodium hydroxide solution was added dropwise over 60 min,Maintain the temperature of 60 ,The reaction was stirred for 8 hours,P-phenylenediamine was added 1mol, the reaction was stirred for 5 hours, then bisphenol F 1mol, the reaction was stirred for 8 hours,Then add hexachlorocyclotriphosphazene 1mol, the reaction was stirred for 4 hours,Add bisphenol A1mol, the reaction was stirred for 5 hours,Then add hexachlorocyclotriphosphazene 1mol, the reaction was stirred for 6 hours,Then sodium methylate 9mol, stirring was continued for 8 hours.After the reaction, the inorganic components and the moisture in the system were removed physically and the solvent in the system was distilled off to obtain 1 mol of the phosphazene compound D having an amino equivalent of 670 g / eq in the above structure.

Reference： [1]Patent: CN107522744,2017,A .Location in patent: Paragraph 0103-0106

54
[ 13352-76-6 ]
[ 108-95-2 ]
[ 2467-02-9 ]
[ 2467-03-0 ]
[ 620-92-8 ]