Name: 834-25-3|1-(Benzyloxy)-4-methylbenzene|97%
Brand: Ambeed
SKU: A790723
Rating: 95 (32 reviews)

1
[ 106-44-5 ]
[ 3204-68-0 ]
[ 834-25-3 ]

Reference： [1]Journal of the Indian Chemical Society,1926,vol. 3,p. 102
Chemisches Zentralblatt,1926,vol. 97,p. 1643

2
[ 834-25-3 ]
[ 716-96-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With aluminium(III) triflate at 70℃;
	With sulfuric acid; benzene

Reference： [1]Cullen, Adam; Muller, Alfred J.; Williams, D. Bradley G. [RSC Advances, 2017, vol. 7, # 67, p. 42168 - 42171]
[2]Bailey-Wood; Cullinane [Chemistry and industry, 1959, p. 543]

3
[ 106-44-5 ]
[ 100-44-7 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate In ethanol at 78℃; for 5h;
95%	With potassium hydroxide; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate at 25℃; for 2h;
82%	With sodium hydroxide; diphenylether; tetrabutylammomium bromide In water; toluene at 90℃; for 3h; low energy microwave irradiation;

81%	With sodium hydroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate at 80℃; for 0.25h;
	With potassium carbonate; acetone
	With potassium carbonate; toluene
	With sodium ethanolate
	With sodium hydroxide
	With potassium hydroxide 1.) methanol, 2.) DMF, 80 deg C, 2 h; Yield given. Multistep reaction;
	With sodium carbonate In tetrahydrofuran for 18.5h; Heating / reflux;	1 Preparation of p-tolyloxy-benzyl ether (VI) EXAMPLE 1 Preparation of p-tolyloxy-benzyl ether (VI) A three-necked round-bottom flask equipped with condenser, magnetic stirrer, thermometer, is loaded with p-cresol (100 g; 0.925 mol) and tetrahydrofuran (300 ml) under nitrogen stream. Sodium carbonate (166 g; 1.20 mol) is added, keeping the suspension under stirring. The resulting mixture is then refluxed while benzyl chloride (158.1 g; 0.925 mol) is dropped therein in 30 minutes. After 18 hours, water is added (300 ml), the phases are separated and the aqueous phase is extracted with toluene (3*200 ml). The combined organic phases are dried over sodium sulfate and evaporated to dryness. 156.1 g of p-tolyloxy-benzyl ether are obtained as a solid crude, which is dried under vacuum at 50° C. 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.49-7.31 (m, 5H), 7.12 (d, 2H,), 6.91 (d, 2H), 5.07 (s, 2H), 2.29 (s, 3H)
	With N-benzyl-N,N,N-triethylammonium chloride; caesium carbonate In acetonitrile at 100℃; for 0.666667h; Microwave irradiation;
	With sodium carbonate In tetrahydrofuran for 18h; Heating / reflux;	1 Example 1: Example 1: Preparation of p-tolyloxy-benzyl ether (VI) A three-necked round-bottom flask equipped with condenser, magnetic stirrer, thermometer, is loaded with p-cresol (100 g; 0.925 mol) and tetrahydrofuran (300 ml) under nitrogen stream. Sodium carbonate (166 g; 1.20 mol) is added, keeping the suspension under stirring. The resulting mixture is then refluxed while benzyl chloride (158.1 g; 0.925 mol) is dropped therein in 30 minutes. After 18 hours, water is added (300 ml), the phases are separated and the aqueous phase is extracted with toluene (3 x 200 ml). The combined organic phases are dried over sodium sulfate and evaporated to dryness. 156.1 g of p-tolyloxy-benzyl ether are obtained as a solid crude, which is dried under vacuum at 50°C. 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.49-7.31 (m, 5H), 7.12 (d, 2H,), 6.91 (d, 2H), 5.07 (s, 2H), 2.29 (s, 3H)

Reference： [1]Brǎtulescu, George; Bigot, Yves L.E.; Delmas, Michel; Pogany, Iuliu [Revue Roumaine de Chimie, 1998, vol. 43, # 4, p. 321 - 326]
[2]Xu, Zhen Yuan; Xu, Dan Qian; Liu, Bao You [Organic Preparations and Procedures International, 2004, vol. 36, # 2, p. 156 - 161]
[3]Yadav, Ganapati D.; Bisht, Priyal M. [Synthetic Communications, 2004, vol. 34, # 16, p. 2885 - 2892]
[4]Wen, Xinmin [Journal of Chemical Research, 2005, # 10, p. 663 - 664]
[5]Elkobaisi; Hickinbottom [Journal of the Chemical Society, 1959, p. 1873,1875]
[6]Claisen [Justus Liebigs Annalen der Chemie, 1925, vol. 442, p. 243][Angewandte Chemie, 1923, vol. 36, p. 478]
[7]Baggaley; Fears; Hindley; Morgan; Murrell; Thorne [Journal of Medicinal Chemistry, 1977, vol. 20, # 11, p. 1388 - 1393]
[8]Cullinane,N.M. et al. [Journal of the Chemical Society, 1962, p. 2995 - 3000]
[9]Paventi, Martino; Hay, Allan S. [Journal of Organic Chemistry, 1991, vol. 56, # 20, p. 5875 - 5882]
[10]Current Patent Assignee: DIPHARMA FRANCIS S.R.L. - US2006/189827, 2006, A1 Location in patent: Page/Page column 4
[11]Location in patent: experimental part Keglevich, Gyoergy; Balint, Erika; Karsai, Eva; Varga, Judit; Gruen, Alajos; Balint, Maria; Greiner, Istvan [Letters in Organic Chemistry, 2009, vol. 6, # 7, p. 535 - 539]
[12]Current Patent Assignee: DIPHARMA FRANCIS S.R.L. - EP1693361, 2006, A1 Location in patent: Page/Page column 7

4
[ 78-32-0 ]
[ 100-39-0 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
49%	With potassium hydroxide In N,N-dimethyl-formamide for 1h; Heating;

Reference： [1]Ohta, Akihiro; Iwasaki, Yoko; Akita, Yasuo [Synthesis, 1982, # 10, p. 828 - 829]

5
[ 834-25-3 ]
[ 538-51-2 ]
[ 135505-48-5 ]

Yield	Reaction Conditions	Operation in experiment
36%	With sodium; N,N-dimethyl-formamide at 75℃; for 0.5h;

Reference： [1]Paventi, Martino; Hay, Allan S. [Journal of Organic Chemistry, 1991, vol. 56, # 20, p. 5875 - 5882]

6
[ 140-39-6 ]
[ 100-39-0 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium methylate In N,N-dimethyl-formamide for 0.5h; Ambient temperature;

Reference： [1]Oriyama, Takeshi; Noda, Kojiro; Yatabe, Kaori [Synlett, 1997, vol. 1997, # 6, p. 701 - 703]

7
[ 2830-53-7 ]
[ 109588-48-9 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 56% 2: 13%	With 2,2'-azobis(isobutyronitrile); 1,1,2,2-tetraphenyldisilane In m-xylene for 22h; Heating;
1: 42% 2: 10%	With azobis(2-cyanobutane); tri-n-butyl-tin hydride In cyclohexane Heating;

Reference： [1]Ryokawa, Atsushi; Togo, Hideo [Tetrahedron, 2001, vol. 57, # 28, p. 5915 - 5921]
[2]Bowman, Russell; Mann, Emma; Parr, Jonathan [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 17, p. 2991 - 2999]

8
[ 106-44-5 ]
[ 100-39-0 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: p-cresol With cholin hydroxide In water at 20℃; for 0.25h; Stage #2: benzyl bromide In water at 20℃; for 24h;	the synthesis of O-substituted phenolic derivatives.[13] General procedure: A typical procedure: A flask was charged with phenol (3.0 mmol) and choline hydroxide (0.66 mL). Then, the mixture was stirred at room temperature in open air for 15 min. Next, benzyl bromide (3.0 mmol) was added into the flask, then the resulting mixture (two phases: top ChOH layer and bottom benzyl bromide layer) allowed to stir at room temperature for 24 h. The reaction mixture (two phases: top product layer and bottom aqueous ChOH layer) was extracted with diethyl ether (3 × 10 mL). The combined organic layers were washed with water, then dried with anhydrous Na2SO4, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/ethyl acetate). Benzyl phenyl ether (3a); 1H NMR (400 MHz, CDCl3) δ (ppm): 7.48-7.40 (m, 4H), 7.37-7.28 (m, 3H), 7.03-6.97 (m, 3H), 5.10 (s, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm): 158.8, 137.1, 129.5, 128.6, 127.9, 127.5, 120.9, 114.9, 69.9.
95%	With potassium carbonate In acetone for 12h; Reflux; Sealed tube;
93%	With sodium hydroxide In acetonitrile at 80℃; for 1.5h;	2.3 Benzylation and allylation of phenols usingLGMPS Cu (0) nanocluster in acetonitrile at 80 C General procedure: To a stirred solution of phenol (0.5 mmol) in acetonitrile,benzyl bromide/allyl bromide (1 mmol),sodium hydroxide (2 mmol) and SiO2-Cu(0) (0.2 g)were added at refluxing temperature. The progress ofthe reaction was monitored through TLC and uponcompletion, the reaction mixture was cooled to roomtemperature and filtered off to remove the catalyst.The catalyst was washed with water followed by EtOAc (3 9 10 mL). The product was obtained afterthe removal of the solvent under reduced pressurefollowed by passing through a column of silica andelution with EtOAc: pet ether (1:100).

91%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 5.5h; Inert atmosphere;
91%	With potassium carbonate In acetonitrile Reflux;
91%	With potassium carbonate In acetonitrile Reflux;
90%	With caesium carbonate In acetonitrile at 100℃; for 0.5h; Microwave irradiation;
88%	With potassium carbonate In acetonitrile for 72h; Reflux;
80%	With choline chloride; urea; potassium hydroxide at 80℃; for 2h; Green chemistry;	Representative reaction condition General procedure: Phenol (0.5 mmol), benzyl bromide(1.2 mmol) and KOH (2.0 mmol) was added to the DES (1 mL) and heated at temperature (80°C) for 2 h. After cooling to room temperature water was added and the product was extracted with ethyl acetate (1 3 mL) andanalyzed by GC-MS after the addition of hexamethylbenzene as an internal standard. The product was purified using column chromatography on silica gel(hexane/EtOAc::99:1). The pure product was characterized by 1H NMR and 13CNMR.Table 4 Comparison of different methodologies for benzylation of phenols with benzyl bromide
74%	With potassium phosphate; tetrabutylammomium bromide In water at 20℃; for 2h; Sealed tube; Green chemistry;	2 4.2.2 Benzyl 4-methylphenyl ether (3ba) General procedure: General procedure for benzylation of phenols: Phenol (0.5mmol), benzyl bromide (1.2equiv), TBAB (0.5equiv), K3PO4 (1.5equiv), and water (2mL) were added to a reaction vessel. The mixture was stirred at room temperature for 2h under air. After the reaction was completed, the mixture was diluted with water and extracted with CH2Cl2 (15mL×3). The combined organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by thin layer chromatography (TLC) on silica gel GF254 (ethyl acetate/petroleum ether) to give the pure product.
54%	Stage #1: p-cresol With sodium hydride In tetrahydrofuran for 0.5h; Heating; Stage #2: benzyl bromide In tetrahydrofuran for 4h; Heating; Further stages.;
	Stage #1: p-cresol With potassium carbonate In N,N-dimethyl-formamide for 2h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 60℃; for 12h;
	With cesiumhydroxide monohydrate; tetra-(n-butyl)ammonium iodide In water; dimethyl sulfoxide at 100℃; for 12h; Inert atmosphere;

Reference： [1]Joo, Seong-Ryu; Kim, Seung-Hoi; Kwon, Gyu-Tae; Park, Soo-Youl [Bulletin of the Korean Chemical Society, 2020, vol. 41, # 12, p. 1200 - 1205]
[2]Bering, Luis; Jeyakumar, Kirujan; Antonchick, Andrey P. [Organic Letters, 2018, vol. 20, # 13, p. 3911 - 3914]
[3]Chowhan, Bushra; Gupta, Manjulla; Gupta, Monika; Paul, Satya [Journal of Chemical Sciences, 2022, vol. 134, # 1]
[4]Ohsawa, Kosuke; Yoshida, Masahito; Doi, Takayuki [Journal of Organic Chemistry, 2013, vol. 78, # 7, p. 3438 - 3444]
[5]Velasco, Rocío; Silva López, Carlos; Nieto Faza, Olalla; Sanz, Roberto [Chemistry - A European Journal, 2016, vol. 22, # 42, p. 15058 - 15068]
[6]Sedano, Carlos; Velasco, Rocío; Feberero, Claudia; Suárez-Pantiga, Samuel; Sanz, Roberto [Organic Letters, 2020, vol. 22, # 16, p. 6365 - 6369]
[7]Location in patent: experimental part Keglevich, Gyoergy; Balint, Erika; Karsai, Eva; Varga, Judit; Gruen, Alajos; Balint, Maria; Greiner, Istvan [Letters in Organic Chemistry, 2009, vol. 6, # 7, p. 535 - 539]
[8]Karreman, Steve; Karnbrock, Simon B. H.; Kolle, Sebastian; Golz, Christopher; Alcarazo, Manuel [Organic Letters, 2021, vol. 23, # 6, p. 1991 - 1995]
[9]Singh, Abhilash S.; Shendage, Suresh S.; Nagarkar, Jayashree M. [Tetrahedron Letters, 2014, vol. 55, # 52, p. 7243 - 7246]
[10]Wang, Hailei; Ma, Yuping; Tian, Heng; Yu, Ajuan; Chang, Junbiao; Wu, Yangjie [Tetrahedron, 2014, vol. 70, # 16, p. 2669 - 2673]
[11]Bowman, Russell; Mann, Emma; Parr, Jonathan [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 17, p. 2991 - 2999]
[12]Chakraborti, Asit K.; Chankeshwara, Sunay V. [Journal of Organic Chemistry, 2009, vol. 74, # 3, p. 1367 - 1370]
[13]Yang, Kai; Li, Zheng; Wang, Zhaoyang; Yao, Zhiyi; Jiang, Sheng [Organic Letters, 2011, vol. 13, # 16, p. 4340 - 4343]

9
[ 106-44-5 ]
[ 53772-44-4 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
82%	With 2,6-dimethyl-1,4-benzoquinone In dichloromethane at 20℃; for 0.5h;

Reference： [1]Shintou, Taichi; Kikuchi, Wataru; Mukaiyama, Teruaki [Chemistry Letters, 2003, vol. 32, # 1, p. 22 - 23] Shintou, Taichi; Kikuchi, Wataru; Mukaiyama, Teruaki [Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 8, p. 1645 - 1667] Shintou, Taichi; Mukaiyama, Teruaki [Journal of the American Chemical Society, 2004, vol. 126, # 23, p. 7359 - 7367]

10
1-((allyloxy)methyl)-4-(benzyloxy)benzene [ No CAS ]
[ 834-25-3 ]
[ 836-43-1 ]
[ 836-42-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 57% 2: 4% 3: 9%	With titanium(IV) isopropylate; chloro-trimethyl-silane; magnesium In tetrahydrofuran at 20℃; for 5h;

Reference： [1]Ohkubo, Mutsumi; Mochizuki, Sayaka; Sano, Takeshi; Kawaguchi, Yuuki; Okamoto, Sentaro [Organic Letters, 2007, vol. 9, # 5, p. 773 - 776]

11
[ 106-44-5 ]
[ 100-39-0 ]
[ 834-25-3 ]
[ 716-96-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 82% 2: 6 % Chromat.	With 1-butyl-3-methylimidazolium hydroxide at 70℃; for 2h;
1: 45% 2: 13%	Stage #1: p-cresol With lithium hydroxide In water for 0.25h; Cooling with ice; Stage #2: benzyl bromide In water at 20℃; Cooling with ice;	4.1. General procedure A (GPA) for the dearomatization reaction in aqueous conditions General procedure: To an aqueous solution of 1 M LiOH (1 mL) on an ice bath phenol (1 mmol) was added and the mixture stirred for 15 min. Then water (1 mL) and BnBr (1.2 mmol) was added, the reaction mixture warmed up to room temperature and stirred overnight. To the reaction mixture water (5 mL) was added, pH adjusted to ~7 and the mixture was extracted with EtOAc. The combined organic layers were washed with brine and dried with phase separator or on MgSO4 and filtered if necessary. Then solvent was removed with rotary evaporator and the products were obtained after flash chromatography on silica gel (petroleum ether/EtOAc).

Reference： [1]Mohanazadeh, Farajollah; Aghvami, Majid [Monatshefte fur Chemie, 2007, vol. 138, # 1, p. 47 - 49]
[2]Lopušanskaja, Eleana; Kooli, Anni; Paju, Anne; Järving, Ivar; Lopp, Margus [Tetrahedron, 2021, vol. 83]

12
[ 4397-53-9 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylsilane In acetone

Reference： [1]Mandal, Pijus K.; McMurray, John S. [Journal of Organic Chemistry, 2007, vol. 72, # 17, p. 6599 - 6601]

13
[ 100-51-6 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: n-BuLi / tetrahydrofuran; hexane / 1 h / 20 °C 1.2: tetrahydrofuran; hexane / 1 h / 20 °C 2.1: 82 percent / 2,6-dimethyl-1,4-benzoquinone / CH₂Cl₂ / 0.5 h / 20 °C

Reference： [1]Shintou, Taichi; Mukaiyama, Teruaki [Journal of the American Chemical Society, 2004, vol. 126, # 23, p. 7359 - 7367]

14
[ 834-25-3 ]
(E)-N-benzylidenebenzenamine [ No CAS ]
[ 135505-48-5 ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; N,N-dimethyl-formamide	8 N-(4-methylphenyl)-N-phenyl-benzenemethanamine STR26 EXAMPLE 8 N-(4-methylphenyl)-N-phenyl-benzenemethanamine STR26 Methyl-4-(phenylmethoxy)benzene (1.98 g, 0.01 mol) and N-(phenylmethylene)benzenamine (1.81 g, 0.01 mol) were reacted in Na/DMF (1 g: 50 mL) at 75° C. for 30 min. Aqueous work-up, extraction with petroleum ether, 3*100 mL, and chromatography with petroleum ether/ethyl acetate 95:5 afforded a total of 1 g. of solid which by HPLC chromatography contained N,N-diphenyl-benzenemethanamine and the title compound in the ratio (6:94 (51% yield by HPLC). The purer fractions from chromatography on silica were combined and the solvent removed. The residual oil was dissolved in methanol and some petroleum ether. On cooling this crystallized the title compound. Two recrystallizations from methanol gave the title compound (98.1% pure; 36% yield), mp 85-6° C. 1 H NMR (200 MHz, CDCl3)δ (assignment): 2.29 (s, 3H, methyl), 4.97 (s, 2H, --NCH2 Ph), 6.80-6.97 (m, 3H, aromatic) 7.06-7.27 (d, 4 H, J=1.37 Hz, --NC6 H4 CH3), 7.14-7.36 (m, 7H, aromatic). MS [m/e (70 eV, % of base peak)] PhCH2 N(Ph)(C6 H4)CH3 273 (M+., 96.5), 196 (M+. --Ph., 31.7), 182 (M+. --PhCH3., 100), 167 (M+. --PhCH2. --CH3., 81.2), 91 (C7 H7+, 98.3). FTIR (CDCl3): 3089, 3064, 3030, 2924, 2864, 1596, 1572, 1512, 1497, 1453 cm-1.

Reference： [1]Current Patent Assignee: Hay; Allan S.; Paventi; Martino - US5011998, 1991, A

15
[ 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

16
[ 834-25-3 ]
C₁₄H₁₃LiO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at 0℃;	2 Example 2: Example 2: Diisopropyl-(3-phenyl-3-p-tolyloxy-propyl)-amine [(II) X is CH2; R is N(isopropyl)2] A three-necked round-bottom flask equipped with condenser, magnetic stirrer, thermometer, is loaded under nitrogen stream with p-tolyloxy-benzyl ether (11.2 g; 0.0589 mol), tetramethylenediamine (6.8 g; 0.0589 mol) and tetrahydrofuran (50 ml), then cooled to 15°C under stirring. A 2.5 M solution of butyl lithium (24 ml 0.0589 mol) in hexane is dropped therein, keeping the temperature below 0°C. After completion of the addition, temperature is kept at 0°C for a further hour and a solution of chloroethyl diisopropylamine (9.6 g; 0.0589 mol) in tetrahydrofuran (10 ml) is added. The mixture is left to warm to room temperature, then after an hour is poured in an ammonium chloride saturated solution (50 ml), the phases are separated and the aqueous phase is extracted with toluene (3 x 30 ml). The combined organic phases are dried over sodium sulfate and evaporated to dryness. The resulting diisopropyl-(3-phenyl-3-p-tolyloxy-propyl)-amine is purified by flash chromatography. 9.9 g of product, as a pale yellow oil, are obtained. 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.36-7.17 (m, 5H), 6.96 (d, 2H), 6.74 (d, 2H), 5.22 (dd, 1H), 3.05 (m, 2 H), 2.65 (m, 2H), 2.21 (s, 3H), 2.15-1.85 (m, 2H), 1.0 (m, 12H).

Reference： [1]Current Patent Assignee: DIPHARMA FRANCIS S.R.L. - EP1693361, 2006, A1 Location in patent: Page/Page column 7

17
[ 834-25-3 ]
[ 106-44-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium <i>tert</i>-butylate; diphenylphosphane In N,N-dimethyl-formamide at 80℃; for 12h; Sealed tube;
66%	With triphenylphosphine hydrobromide In acetonitrile at 100℃; for 0.5h; Microwave irradiation; sealed tube;
52%	With thiophene; sodium hydrogen sulfate; silica gel for 4h; Heating;

With sulfosuccinic acid functionalized mesoporous silica In ethanol at 100℃;

Reference： [1]Pan, Wenjing; Li, Chenchen; Zhu, Haoyin; Li, Fangfang; Li, Tao; Zhao, Wanxiang [Organic and Biomolecular Chemistry, 2021, vol. 19, # 35, p. 7633 - 7640]
[2]Location in patent: experimental part Ramanathan, Mani; Hou, Duen-Ren [Tetrahedron Letters, 2010, vol. 51, # 47, p. 6143 - 6145]
[3]Zhou, Linna; Wang, Wenjing; Zuo, Li; Yao, Shanyan; Wang, Wei; Duan, Wenhu [Tetrahedron Letters, 2008, vol. 49, # 33, p. 4876 - 4878]
[4]Sachdev, Divya; Wilson, G. Robin; Srivastava, Neel Mani; Dubey, Amit [Catalysis Communications, 2014, vol. 51, p. 90 - 94]

18
[ 1023285-97-3 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
83%	With allyl(cyclopentadiene)palladium(II); bis[2-(diphenylphosphino)phenyl] ether In toluene at 60℃; for 3.08333h; Inert atmosphere;

Reference： [1]Kuwano, Ryoichi; Kusano, Hiroki [Organic Letters, 2008, vol. 10, # 10, p. 1979 - 1982]

19
[ 506-96-7 ]
[ 834-25-3 ]
[ 140-39-6 ]

Yield	Reaction Conditions	Operation in experiment
86%	With lithium bromide In dichloromethane at 30 - 35℃; for 12h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Chakraborti, Asit K.; Chankeshwara, Sunay V. [Journal of Organic Chemistry, 2009, vol. 74, # 3, p. 1367 - 1370]

20
[ 106-38-7 ]
[ 100-51-6 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium phosphate; copper(l) iodide; 8-quinolinol at 20 - 110℃; Inert atmosphere;
20 %Spectr.	Stage #1: para-bromotoluene With potassium phosphate; N,N'-bis(2,5-dimethylpyrrol-1-yl)oxalamide; copper(I) bromide In dimethyl sulfoxide at 20℃; Inert atmosphere; Glovebox; Sealed tube; Stage #2: benzyl alcohol In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere; Sealed tube; Glovebox;

Reference： [1]Niu, Jiajia; Guo, Pengran; Kang, Juntao; Li, Zhigang; Xu, Jingwei; Hu, Shaojing [Journal of Organic Chemistry, 2009, vol. 74, # 14, p. 5075 - 5078]
[2]Ray, Ritwika; Hartwig, John F. [Angewandte Chemie - International Edition, 2021, vol. 60, # 15, p. 8203 - 8211][Angew. Chem., 2021, vol. 133, # 15, p. 8284 - 8292,9]

21
[ 106-38-7 ]
[ 100-44-7 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: para-bromotoluene With copper(l) iodide; 2-methyl-8-quinolinol; tetra(n-butyl)ammonium hydroxide In water; dimethyl sulfoxide at 130℃; Stage #2: benzyl chloride With tetra(n-butyl)ammonium hydroxide In water; dimethyl sulfoxide at 100℃;

Reference： [1]Location in patent: experimental part Paul, Rajesh; Ali, Md Ashif; Punniyamurthy, Tharmalingam [Synthesis, 2010, # 24, p. 4268 - 4272]

22
[ 834-25-3 ]
[ 60805-11-0 ]
[ 1360544-05-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	In acetonitrile at 80℃; for 6h; Inert atmosphere;

Reference： [1]Yanai, Hikaru; Ogura, Hiroshi; Fukaya, Haruhiko; Kotani, Akira; Kusu, Fumiyo; Taguchi, Takeo [Chemistry - A European Journal, 2011, vol. 17, # 42, p. 11747 - 11751]

23
[ 106-44-5 ]
[ 5197-95-5 ]
[ 834-25-3 ]
[ 622-60-6 ]

Reference： [1]Letters in Organic Chemistry,2011,vol. 8,p. 22 - 27

24
[ 624-31-7 ]
[ 100-51-6 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
80%	With 1,10-Phenanthroline; copper(II) ferrite; caesium carbonate at 110℃; for 12h; Inert atmosphere;	4.2 General procedure for the coupling reactions of aryl halides with alkyl alcohols General procedure: A 25-mL Synthware pressure tube was flame-dried under vacuum and filled with argon after cooling to room temperature. To this tube were added aryl halide (0.5 mmol), CuFe2O4 (2.5 mol %), ligand (5.0 mol %), Cs2CO3 (1.0 mmol, 2.0 equiv). The tube was then evacuated and backfilled with argon (3 cycles). Then, 1.0 mL alkyl alcohol was loaded into a plastic syringe. After the tube was purged with argon, the n-butyl alcohol was injected into bottom of the tube using a long needle syringe. The rubber septum was replaced with a Teflon screwcap, and the flask was sealed and placed into the preheated 110 °C oil bath stirring for 12 h. When the reaction was cooled down to room temperature, the mixture was filtered through a short plug of silica gel and washed with 40 mL CH2Cl2. The combined organic phase was concentrated under vacuum. The product was purified through flash column chromatography on 200-300 mesh silica gel with petroleum ether/ethyl acetate as eluant with a suitable ratio according to the TLC experiments. The identity and purity of the product were ascertained by GC-MS, FT-IR, 1H, and 13C NMR spectroscopy.

Reference： [1]Yang, Shuliang; Xie, Wenbing; Zhou, Hua; Wu, Cunqi; Yang, Yanqin; Niu, Jiajia; Yang, Wei; Xu, Jingwei [Tetrahedron, 2013, vol. 69, # 16, p. 3415 - 3418]

25
[ 834-25-3 ]
[ 4885-02-3 ]
[ 53389-98-3 ]

Yield	Reaction Conditions	Operation in experiment
76%	With silver trifluoromethanesulfonate In dichloromethane at -78℃; for 0.166667h; Inert atmosphere;

Reference： [1]Ohsawa, Kosuke; Yoshida, Masahito; Doi, Takayuki [Journal of Organic Chemistry, 2013, vol. 78, # 7, p. 3438 - 3444]

26
[ 834-25-3 ]
[ 1454880-69-3 ]
[ 1454880-58-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 2,2′-diiodo-5,5′-dimethoxy-1,1′-biphenyl; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 3h;

Reference： [1]Ito, Motoki; Kubo, Hiroko; Itani, Itsuki; Morimoto, Koji; Dohi, Toshifumi; Kita, Yasuyuki [Journal of the American Chemical Society, 2013, vol. 135, # 38, p. 14078 - 14081]

27
[ 834-25-3 ]
C₁₄H₁₃FO [ No CAS ]
[ 77249-33-3 ]

Yield	Reaction Conditions	Operation in experiment
	With Selectfluor In acetonitrile at 80℃; for 1h; Overall yield = 60 %;	4.3 Fluorination of 4-alkyl-substituted phenols and aromatic ethers with CFS (1), Selectfluor F-TEDA-BF₄ (2) or Accufluor NFTh (3); general procedure General procedure: To a solution of substrate 4 (1mmol) in 10mL of solvent (MeCN or MeOH) was added reagents 1, 2, or 3 (1.1mmol). The reaction mixture was further-stirred under reflux for 2h. The solvent was distilled off under reduced pressure. The crude reaction mixture was dissolved in 50mL of CH2Cl2, insoluble reaction products filtered off, filtrate washed with water (30mL), the organic layer dried over Na2SO4, and solvent evaporated. The crude reaction mixture was analyzed by 1H and 19F NMR spectroscopy. Relative distribution of fluorinated products and their overall yield was determined from 19F NMR of crude reaction mixtures using octafluoronaphthalene (OFN) as internal standard. Products were identified by comparison of their NMR spectroscopic data with those known from literature, independently prepared products or they were transformed to known compounds. 2-Fluoro-4-alkyl substituted phenols or alkoxy benzenes (5, Scheme 1) were thus transformed with an excess of reagents to 2,2-difluoro-4-alkyl-3,5-cyclohexadienones (unknown compounds 8b or 8c [19]) or hydrolyzed to 2-fluoro-4-methylphenol (4aa). 4-Fluoro-4-alkyl-2,5-cyclohexadienones 6a, 6b, and 6c were isolated from crude mixtures using preparative TLC (SiO2, CH2Cl2/petroleum ether 4/1) and identified according to their spectroscopic data, while 4-fluoro alkoxy benzene derivatives were hydrolyzed to 4-fluorophenol or compared to independently prepared compounds.

Reference： [1]Pravst, Igor; Stavber, Stojan [Journal of Fluorine Chemistry, 2013, vol. 156, p. 276 - 282]

28
N,N,N-trimethyl-1-(4-phenylmethoxylphenyl)methanaminium trifluoromethanesulfonate [ No CAS ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
78%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; 4,5-dimethyl-1,3-bis-(2,4,6-trimethylphenyl)-3H-imidazol-1-ium chloride; sodium isopropylate In 1,4-dioxane at 100℃; for 2h; Inert atmosphere; Glovebox; Sealed tube;

Reference： [1]Yi, Yuan-Qiu-Qiang; Yang, Wen-Cheng; Zhai, Dan-Dan; Zhang, Xiang-Yu; Li, Shuai-Qi; Guan, Bing-Tao [Chemical Communications, 2016, vol. 52, # 72, p. 10894 - 10897]

29
[ 834-25-3 ]
α-deuteriobenzyl 4-methylphenyl ether [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 4-methylphenyl benzyl ether With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.416667h; Schlenk technique; Inert atmosphere; Stage #2: With deuteromethanol In tetrahydrofuran; water; pentane Schlenk technique; Inert atmosphere;

Reference： [1]Velasco, Rocío; Silva López, Carlos; Nieto Faza, Olalla; Sanz, Roberto [Chemistry - A European Journal, 2016, vol. 22, # 42, p. 15058 - 15068]

30
[ 834-25-3 ]
[ 94-30-4 ]
[ 16765-38-1 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 4-methylphenyl benzyl ether With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.416667h; Schlenk technique; Inert atmosphere; Stage #2: ethyl 4-methoxybenzoate In tetrahydrofuran; pentane at -78 - 20℃; Schlenk technique; Inert atmosphere;

Reference： [1]Velasco, Rocío; Silva López, Carlos; Nieto Faza, Olalla; Sanz, Roberto [Chemistry - A European Journal, 2016, vol. 22, # 42, p. 15058 - 15068]

31
[ 106-44-5 ]
2-(benzyloxy)-1,3-diphenyl-1,3,2-diazaphospholidine [ No CAS ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
67%	With di-isopropyl azodicarboxylate In dichloromethane at 40℃; for 36h; Inert atmosphere;

Reference： [1]Huang, Hai; Kang, Jun Yong [Organic Letters, 2017, vol. 19, # 3, p. 544 - 547]

32
[ 883-93-2 ]
[ 834-25-3 ]
[ 1454287-80-9 ]

Yield	Reaction Conditions	Operation in experiment
63%	With N-hydroxyphthalimide; oxygen; palladium diacetate In chlorobenzene at 80℃; for 2.5h;

Reference： [1]Pipaliya, Bhavin V.; Chakraborti, Asit K. [Journal of Organic Chemistry, 2017, vol. 82, # 7, p. 3767 - 3780]

33
[ 6793-92-6 ]
[ 74-88-4 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
40%	With nickel(II) iodide; 4,4'-dimethyl-2,2'-bipyridines; tetra-(n-butyl)ammonium iodide; magnesium chloride; zinc In N,N-dimethyl acetamide at 20℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube;

Reference： [1]Wang, Jiawang; Zhao, Jianhong; Gong, Hegui [Chemical Communications, 2017, vol. 53, # 73, p. 10180 - 10183]

34
[ 207500-64-9 ]
[ 74-88-4 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
36%	With 1,1'-bis-(diphenylphosphino)ferrocene; (1,2-dimethoxyethane)dichloronickel(II); tetra-(n-butyl)ammonium iodide; lithium chloride; zinc In N,N-dimethyl acetamide at 40℃; for 12h; Schlenk technique; Inert atmosphere; Sealed tube;

Reference： [1]Wang, Jiawang; Zhao, Jianhong; Gong, Hegui [Chemical Communications, 2017, vol. 53, # 73, p. 10180 - 10183]

35
[ 80-48-8 ]
[ 207500-64-9 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	With 1,1'-bis-(diphenylphosphino)ferrocene; (1,2-dimethoxyethane)dichloronickel(II); tetra-(n-butyl)ammonium iodide; lithium chloride; zinc In N,N-dimethyl acetamide at 40℃; for 12h; Schlenk technique; Inert atmosphere; Sealed tube;

Reference： [1]Wang, Jiawang; Zhao, Jianhong; Gong, Hegui [Chemical Communications, 2017, vol. 53, # 73, p. 10180 - 10183]

36
[ 6793-92-6 ]
[ 80-48-8 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
93%	With nickel(II) iodide; 4,4'-dimethyl-2,2'-bipyridines; tetra-(n-butyl)ammonium iodide; magnesium chloride; zinc In N,N-dimethyl acetamide at 20℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube;

Reference： [1]Wang, Jiawang; Zhao, Jianhong; Gong, Hegui [Chemical Communications, 2017, vol. 53, # 73, p. 10180 - 10183]

37
[ 834-25-3 ]
[ 716-96-1 ]
[ 41389-83-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 81% 2: 6%	With nitrosonium tetrafluoroborate In sulfolane; dichloromethane at 20℃; for 0.75h; Sealed tube; Overall yield = 87 %; regioselective reaction;

Reference： [1]Bering, Luis; Jeyakumar, Kirujan; Antonchick, Andrey P. [Organic Letters, 2018, vol. 20, # 13, p. 3911 - 3914]

38
4,4,5,5,-tetramethyl-2-[4-(phenylmethoxy)phenyl]-1,3,2-dioxaborolane [ No CAS ]
[ 74-88-4 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
87%	With C₂₁H₃₀ClNPPd; potassium <i>tert</i>-butylate In tert-Amyl alcohol at 65℃; for 18h; Sealed tube; Inert atmosphere; Glovebox;

Reference： [1]Haydl, Alexander M.; Hartwig, John F. [Organic Letters, 2019, vol. 21, # 5, p. 1337 - 1341]

39
[ 5720-05-8 ]
[ 100-39-0 ]
[ 834-25-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 4-methylphenylboronic acid With dihydrogen peroxide; N,N,N-trimethyl-2-hydroxyethyl-ammonium hydroxide In lithium hydroxide monohydrate at 20℃; for 1h; Green chemistry; Stage #2: benzyl bromide In lithium hydroxide monohydrate at 20℃; for 2h; Green chemistry;	Representative one-pot procedure General procedure: A flask was charged with phenylboronic acid (4.0 mmol), choline hydroxide (aq. 40-50 wt%, 2.0 mL), and H2O2 (aq. 30 wt%, 0.8 mL). Then, the mixture was stirred at room temperature in open air for 1 h. Next, 0.34 g of benzyl bromide (2.0 mmol) was added into the flask at room temperature, then the resulting mixture was allowed to stir at room temperature for 2 h. Quenched with 3 M HCl solution, then extracted with extracted with diethyl ether (3 * 10 mL). The combined organic layers were washed with brine, dried with anhydrous Na2SO4, and the volatile solvent was evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes only).
75%	Stage #1: 4-methylphenylboronic acid With magnetite nanoparticles; dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 0.0833333h; Stage #2: benzyl bromide at 20℃; for 3h;	2. General procedure for ipso-hydroxylation of arylboronic acids General procedure: To a 25 mL round-bottom flask equipped with a magnetic stir bar, phenylboronic acid (3.0 mmol), Fe3O4 (20mol%), 30 wt% aq. H2O2 (3.0 mmol) were added. Then, the mixture was stirred at room temperature in open airfor 5 min. The reaction mixture was filtered out the catalyst for reuse. The aqueous layer was acidified with 3MHCl aqueous solution and then extracted with diethyl ether (3 X 10 mL). The combined organic layers weredried with anhydrous Na2SO4, then evaporated under reduced pressure. The crude mixture was purified bycolumn chromatography on silica gel (hexanes/ diethyl ether).

Reference： [1]Joo, Seong-Ryu; Kim, Seung-Hoi; Lim, In-Kyun [Tetrahedron Letters, 2020, vol. 61, # 34]
[2]Cho, Hyun-A.; Lee, Yong-Ki; Kim, Seung-Hoi [Synlett, 2022]

40
[ 834-25-3 ]
2-deuterio-1-(deuterio(phenyl)methoxy)-4-methylbenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: 4-methylphenyl benzyl ether With tert.-butyl lithium In tetrahydrofuran; pentane at 0℃; for 0.333333h; Schlenk technique; Inert atmosphere; Stage #2: With deuteromethanol In tetrahydrofuran; pentane at -50℃; for 0.166667h; Schlenk technique; Inert atmosphere;