Home Cart 0 Sign in  
X

[ CAS No. 2628-16-2 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
3d Animation Molecule Structure of 2628-16-2
Chemical Structure| 2628-16-2
Chemical Structure| 2628-16-2
Structure of 2628-16-2 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

* Shipping: {[proInfo.prShipping]}

Quality Control of [ 2628-16-2 ]

Related Doc. of [ 2628-16-2 ]

Alternatived Products of [ 2628-16-2 ]
Product Citations

Product Details of [ 2628-16-2 ]

CAS No. :2628-16-2 MDL No. :MFCD00075734
Formula : C10H10O2 Boiling Point : -
Linear Structure Formula :C2H3C6H4OCOCH3 InChI Key :JAMNSIXSLVPNLC-UHFFFAOYSA-N
M.W : 162.19 Pubchem ID :75821
Synonyms :

Calculated chemistry of [ 2628-16-2 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 12
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.1
Num. rotatable bonds : 3
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 48.03
TPSA : 26.3 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.5 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.26
Log Po/w (XLOGP3) : 2.52
Log Po/w (WLOGP) : 2.15
Log Po/w (MLOGP) : 2.47
Log Po/w (SILICOS-IT) : 2.5
Consensus Log Po/w : 2.38

Druglikeness

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

Water Solubility

Log S (ESOL) : -2.61
Solubility : 0.403 mg/ml ; 0.00248 mol/l
Class : Soluble
Log S (Ali) : -2.72
Solubility : 0.31 mg/ml ; 0.00191 mol/l
Class : Soluble
Log S (SILICOS-IT) : -2.91
Solubility : 0.2 mg/ml ; 0.00123 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.42

Safety of [ 2628-16-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H317-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 2628-16-2 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 2628-16-2 ]

[ 2628-16-2 ] Synthesis Path-Downstream   1~101

  • 1
  • [ 2628-16-2 ]
  • [ 2628-17-3 ]
YieldReaction ConditionsOperation in experiment
96% With ethanol; sodium hydroxide at 20℃; for 4h; Inert atmosphere; 1.1; 2.1 (1)
Preparation of Hydroxystyrene 0.275 mol of sodium hydroxide was put in a 500 ml round-bottom flask and dissolved by adding 60 ml of anhydrous ethanol thereto, and 0.065 mol of acetoxystyrene was then added thereto and stirred for 4 hours in a nitrogen atmosphere at room temperature. Thereafter, 50 ml of distilled water was added and 30 ml of acetyl acetate was added to extract an organic layer, and the organic layer extraction was repeated three times. Anhydrous magnesium sulfate was added to dry and filter the extracted organic layer so that remaining moisture was removed. Thereafter, the solvent was removed under reduced pressure to obtain 7.54 g (96% yield) of yellow solid hydroxystyrene. 1H nuclear magnetic resonance spectroscopic data of the purified hydroxystyrene are as follows. 1H-NMR (500 MHz, CDCl3) δ 7.31-7.29 (d, J=9.5, 1H), δ 6.80-6.78 (d, J=8.5, Ar-H, 2H), δ 6.68-6.62 (q, J=9.5, 1H), δ 5.62-5.58 (d, J=17.5, 1H), δ 5.13-5.11 (d, J=11, 1H), δ 4.75 (s, 1H).
96% With sodium hydroxide In tetrahydrofuran; water monomer at 20℃; for 4h; Cooling with ice; Inert atmosphere; Schlenk technique;
96% With ethanol; sodium hydroxide at 20℃; for 4h; Inert atmosphere; 1.1 1) Preparation of 4-hydroxystyrene In a 500 ml round-bottom flask, 0.275 mol of sodium hydroxide was added, and 60 ml of absolute ethanol was added to dissolve, and then 0.065 mol of 4-acetoxystyrene was added, followed by stirring at room temperature under a nitrogen atmosphere for 4 hours. After that, 50 ml of distilled water was added and 30 ml of ethyl acetate was added to extract the organic layer, and the organic layer extraction was repeated 3 times. The extracted organic layer was dried with anhydrous magnesium sulfate, and filtered to remove residual moisture. Then, the solvent was removed under reduced pressure to obtain 7.54 g (yield 96%) of 4-hydroxystyrene as a yellow solid. The 1H nuclear magnetic resonance spectroscopy data of purified 4-hydroxystyrene are as follows
94.59% With methanol; sodium hydroxide at 20℃; for 0.5h; 1.3 Synthesis of (3) 4 4-acetoxystyrene (1.0 g, 6.17 mmol) was added to a 50 mL round bottom flask, and then dissolved in 10 mL of methanol, and then 10 mL of 20% sodium hydroxide solution was added thereto, and reacted at room temperature for 0.5 h, and then detected by TLC. The reaction is over. After adding 50 mL of water and extracting with ethyl acetate (50 mL×3), the organic phase was combined, washed with saturated brine (100 mL×3), and dried over anhydrous sodium sulfateThe solid yellow solid 4-hydroxystyrene (4) 0.7 g was solidified in a yield of 94.59%.
92% With sodium hydroxide In tetrahydrofuran; water monomer
92% With cucumber juice at 30 - 35℃; for 6h; Inert atmosphere; Green chemistry;
92% With sodium hydroxide In methanol; water monomer at -5℃; for 1.5h; Inert atmosphere; Large scale; 1-13; 1 Example 1 7.9 kg of PACS and 23.4 kg of methanol were put into a 100 L glass lining reaction vessel equipped with a thermometer, a cooling tube and a stirrer, and sealed with nitrogen. The contents were cooled with stirring, and the liquid temperature was set to -5 ° C. Then, the operation of depressurizing the inside of the reaction vessel and then double-pressurizing with nitrogen was repeated three times. An equimolar amount of 3M sodium hydroxide aqueous solution was prepared in a container separate from the reaction vessel, and this aqueous solution was bubbled with nitrogen for 1 hour. A nitrogen-bubbled sodium hydroxide aqueous solution was added dropwise into the reaction vessel over 100 minutes, and after the addition, stirring was continued for another 30 minutes to deprotect PACS and convert it to 4-HS. Next, 0.97 mol equivalent of 6M hydrochloric acid was added dropwise to the used PACS over 60 minutes, and after the addition, stirring was continued for another 30 minutes to neutralize the reaction solution. In addition, 6M hydrochloric acid was previously bubbled with nitrogen for 1 hour and dropped. Next, the temperature of the reaction solution after neutralization was raised to about 10 to 20 ° C., MTBE having a mass three times that of PACS was added thereto, the mixture was stirred for 15 minutes, allowed to stand for 15 minutes, and the aqueous layer was discharged. .. Next, ion-exchanged water 3% by mass of PACS was added, stirred for 15 minutes, allowed to stand for 15 minutes, and then the aqueous layer was discharged. Next, MTBE 2% by mass and 3% by mass of ion-exchanged water of PACS were added, stirred for 15 minutes, allowed to stand for 15 minutes, and the aqueous layer was discharged. Finally, ion-exchanged water 3% by mass of PACS was added, stirred for 15 minutes, allowed to stand for 15 minutes, and the operation of draining the aqueous layer was repeated twice. The organic layer after washing with water was transferred to another 100 L reaction vessel, and MEK 13% by mass of the first PACS was added. Distilling under reduced pressure at 25 ° C. or lower and 5 kPa to distill off organic impurities other than 4-HS such as tert-butylmethyl ether and reaction by-products and excess MEK, and finally the 4-HS concentration is 25% by mass. Finished in a solution. Then, the solution was passed through a polytetrafluoroethylene (PTFE) hollow fiber membrane filter having a pore size of 50 nm to obtain 21 kg of a 25 mass% 4-HS / MEK solution (yield 92%).
90% With Pseudomonas cepacia lipase; water monomer In tetrahydrofuran at 20℃; for 10h; Enzymatic reaction;
90% With Pseudomonas cepacia lipase; water monomer In tetrahydrofuran at 20℃; for 10h; Enzymatic reaction;
90% With potassium hydroxide In water monomer at 0℃; for 4h;
85% With sodium hydroxide In ethanol at 20℃; for 5h;
85% With sodium hydroxide In tetrahydrofuran; water monomer at 20℃; Schlenk technique; Inert atmosphere;
81% With ammonium hydroxide; magnesium(II) sulfate In tetrahydrofuran EXAMPLES The flask was charged with 4-acetoxy styrene (454 g, 2.8 mol) and 1820 grams tetrahydrofuran (THF). The addition funnel was charged with 240 mL of 12 molar aqueous ammonium hydroxide (approximately 3.5 mol). The flask was nitrogen flushed and kept under a nitrogen blanket as the ammonium hydroxide was added to the rapidly stirred solution over 30 minutes. A slight exotherm of about 10° C. was observed. The mixture was allowed to stir at room temperature overnight. The reaction mixture was transferred to a 6 liter separatory funnel and washed with one 2 liter portion of brine followed by four 1 liter brine extractions. The THF solution was dried by stirring overnight with 50 grams of anhydrous magnesium sulfate. After removing the magnesium sulfate the by filtration the solution was concentrated on the rotary evaporator using house vacuum and a bath temperature of 30° C. The concentrated solution (555 grams) contained 49.3 mole % 4-hydroxystyrene (81% yield) and 50.7 mole % of tetrahydrofuran by NMR analysis.
78% With sodium hydroxide In tetrahydrofuran; water monomer for 2h; Inert atmosphere; Cooling with ice; 3.3.1. Synthesis of the 4-Vinylphenol Preparation of 4-vinylphenol was realized according to the method of Ricks-Laskoski et al [48].To a dried three-necked, 2 L round bottom flask fitted with a dropping funnel and an mechanicalstirrer 4-acetoxystyrene (53.36 g, 0.33 mol, 1 eq.) and tetrahydrofuran (200 mL) were added under anargon atmosphere and ice-cooling. Ice-cooling was continued throughout the process. 5 M solutionof aqueous sodium hydroxide (100 mL, 0.8 mol, 2.4 eq.) was added dropwise to this solution. Theyellow solution was stirred for 2 h under ice-cooling until the reaction was completed as indicatedby TLC (SiO2: Rf = 0.75, 30 vol.% ethyl acetate/hexane). Then 1.5 M hydrochloric acid (340 mL) wasadded slowly to the crude reaction mixture until a pH of 7-5 was reached. The product was extractedwith cold ethyl acetate (5 × 50 mL), washed with distilled water (3 × 50 mL), dried over magnesiumsulfate and filtered. The product was distilled at reduced pressure while cooling with an ice bath toyield a crystalline solid (30.9 g, 78%). The product was stored at -20 °C under argon atmosphere andlight exclusion to suppress self-initiated polymerization.1H NMR (300 MHz, 298 K, DMSO-d6): δ/ppm = 9.53 (s, 1H), 7.28 (d, 2H, J = 9 Hz), 6.74 (d, 2H, J = 9Hz), 6.61 (dd, 1H, J = 12 Hz/18 Hz), 5.68 (d, 1H, J = 18 Hz), 5.04 (d, 1H, J = 12 Hz).13C{H} NMR (75.48 MHz, 298 K, DMSO-d6): δ/ppm = 157.3, 136.4, 128.2, 127.4, 115.3, 110.6.
60% With potassium hydroxide In ethanol; water monomer for 1.5h;
60% With potassium hydroxide; water monomer In methanol at 65℃; for 1.5h;
60% With methanol; potassium hydroxide; water monomer at 65℃; for 1.58333h; 7 7. Preparation of 4-chloroacetoxystyrene A flask was charged with 4-acetoxystyrene (10 g, 61.73 mmol), methanol (30 mL), and KOH (0.125 g, 2.23 mmol), and 1 drop of water. After the mixture was stirred for 5 minutes under N2, the temperature was raised to 65° C. The mixture was stirred for 1.5 h and then cooled to room temperature. Acetic acid (0.144 g, 2.44 mmol) in methanol (0.5 mL) was added slowly over S min. The mixture was stirred for another 5 min and then concentrated. The residue was dissolved in toluene and filtered. The filtrate was cooled to -78° C. and the 4-hydroxystyrene was precipitated, filtered and dried to give 4.5 g product (60%).
46% With water monomer; potassium hydroxide
45% Stage #1: p-acetoxystyrene With potassium hydroxide In methanol Stage #2: With acetic acid In methanol
With potassium hydroxide
With potassium hydroxide In ethanol at 20℃; for 1h;
With potassium hydroxide In ethanol for 1h;
With potassium hydroxide In methanol at 20℃;
With potassium hydroxide at 0℃;
With potassium hydroxide
hydrolysis;
With sodium hydroxide In ethanol
Stage #1: p-acetoxystyrene With water monomer; potassium hydroxide Stage #2: With carbon dioxide
Stage #1: p-acetoxystyrene With sodium hydroxide In tetrahydrofuran Schlenk technique; Stage #2: With hydrogenchloride In tetrahydrofuran; water monomer Schlenk technique;
With sodium hydroxide In tetrahydrofuran; water monomer for 4h; Cooling with ice;
With methanol; sodium methoxide In ethyl acetate at 20℃; for 3h; Cooling with ice; 1 100 parts of 4-acetoxystyrene was dissolved in 300 parts of ethyl acetate, 50 parts of 28% sodium methoxide in methanol solution was added dropwise to the solution in an ice bath, and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was subjected to three separate liquid cleansing with 200 parts of 1N hydrochloric acid aqueous solution, followed by further liquid separation with 200 parts of saturated brine, followed by drying with magnesium sulfate and filtration to obtain a filtrate. To this filtrate, 207 parts of EF-3000 (manufactured by Mitsubishi Materials) and 99.5 parts of triethylamine were added, and the mixture was kept at 5 °C or lower and stirred for 1 hour. Then, 102 parts of trifluoromethanesulfonamide, 100 parts of triethylamine And the mixture was stirred for 2 hours. The reaction solution was washed three times with 300 parts of 1N hydrochloric acid aqueous solution, and then washed three times with 300 parts of saturated saline solution, dried with sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography, followed by separation into 200 parts of a 10% aqueous sodium hydroxide solution. The mixture was further washed with saturated brine 300 parts, dried over sodium sulfate and concentrated to obtain 60 parts of X-57 precursor (Yield: 17.1%).
With sodium hydroxide In tetrahydrofuran; water monomer for 4h; Cooling with ice;
With 3,5-dihydroxyphenol; sodium hydroxide In methanol at 0 - 5℃; for 1.16667h; 1 In a four-necked flask having an inner volume of 1 liter equipped with a stirrer, room temperature (about 20 ° C.)100 g of 4-acetoxystyrene as a raw material compound and 300 g of methanol as a polymerization solvent were charged,0.50 g of 1,3,5-trihydroxybenzene as a polymerization inhibitor was added so as to be 0.5% by mass based on 4-acetoxystyrene.Then, the bottom of the flask was immersed in an ice bath and cooled while stirring (0 to 5 ° C.).In this state,While stirring the content of the flask,4-acetoxystyrene so that the molar ratio is 1.0,A sodium hydroxide aqueous solution having a concentration of 12% by mass as a base was gradually added dropwise over 40 minutes,after that,The reaction solution was obtained by stirring for 30 minutes.A small amount of the reaction solution was sampled,It was confirmed by 1 H-NMR that acetoxy group was completely eliminated from 4-acetoxystyrene.Subsequently, a hydrochloric acid aqueous solution having a concentration of 18% by mass was added so that the molar ratio became 0.8 with respect to the charged amount of 4-acetoxystyrene,Was added dropwise over 30 minutes,After completion of the dropwise addition, the mixture was stirred for 30 minutes.When pH was measured, the pH was 6. The reaction formula of this reaction is shown belowThen,The reaction solution was transferred into a 4-necked flask having an internal volume of 2 liters,Methyl-t-butyl ether (360 g) as an extraction solvent was added at room temperature (about 20 ° C.)And stirred for 15 minutes to obtain a mixed solution.The mixed solution was transferred to a separating funnel into an internal volume of 2 liters,The mixture was allowed to stand for 10 minutes to separate into two layers, the upper layer containing 4-hydroxystyrene was recovered,4-hydroxystyrene was extracted.Next, 330 g of purified water was added to the recovered upper layer, and the mixture was stirred at room temperature (about 20 ° C.) for 15 minutes,The separating funnel was allowed to stand for 10 minutes to separate the two layers, and the upper organic layer was recovered. To the organic layer methyl-t190 g of butyl ether and 330 g of purified water were added and washed with water. Room temperature (about 20 ° C.)For 15 minutes, and the separating funnel was allowed to stand for 10 minutes to collect 325 g of the upper organic layer.As a result of quantitative analysis by 1 H-NMR, the yield of 4-hydroxystyrene obtained wasIt was almost 100% of the theoretical value. Further, 4-hydroxystyrene solution was mixed with GPC · RI It was measured with a detector, and it was confirmed that no polymer was formed.
With potassium hydroxide In methanol; dichloromethane at 20℃; for 2h; Inert atmosphere; 2.2. Synthesis of monomer The synthesis of 4-(2-bromopropionyl)oxy styrene (BPOS) was based on the previous reportexcept that 4-hydroxystyrene was used in place of 2-hydroxyethyl acrylate [10]. To synthesizethe 4-hydroxystyrene, solution consisting of 4-acetoxystyrene (170 mmol) and KOH(255 mmol) in 260 mL methylene chloride was firstly prepared under nitrogen atmosphere.Then, 26 mL methanol was added with vigorous stirring at room temperature. After 2 h,300 mL water was added to the reaction mixture and the aqueous phase was separated. Acertain amount of 1N HCl was added for acidification, and extracted with 300 mL methylenechloride. The organic phase was separated, and washed with saturated aqueous sodiumchloride solution. Aftermethylene chloride was evaporated, 4-hydroxystyrene was obtainedas white solid. 1H NMR (300 MHz, CDCl3): δ 1.93 (d, J = 6.9 Hz, 3H), 4.58 (q, J = 6.9 Hz,1H), 5.25 (d, J = 10.8 Hz, 1H), 5.71 (d, J = 17.6 Hz, 1H), 6.69 (dd, J = 10.8, 17.6 Hz, 1H), 7.08(d, J = 8.6 Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H).
Stage #1: p-acetoxystyrene With potassium hydroxide In ethanol at 25℃; for 1h; Stage #2: With potassium etoxide In ethanol at 80℃; for 0.5h;
With sodium hydroxide In tetrahydrofuran; water monomer at 20℃; Inert atmosphere;

Reference: [1]Current Patent Assignee: LG CHEM CO.,LTD. - US2018/72851, 2018, A1 Location in patent: Paragraph 0129; 0130; 0133; 0134
[2]Wu, Feng; Zhu, Shifa [Organic Letters, 2019]
[3]Current Patent Assignee: LG CHEM CO.,LTD. - KR2021/52965, 2021, A Location in patent: Paragraph 0188-0191
[4]Current Patent Assignee: CHANGZHOU UNIVERSITY - CN108484374, 2018, A Location in patent: Paragraph 0017; 0018; 0038; 0043
[5]Amir, Roey J.; Zhong, Sheng; Pochan, Darrin J.; Hawker, Craig J. [Journal of the American Chemical Society, 2009, vol. 131, # 39, p. 13949 - 13951]
[6]Maity, Himadri Sekhar; Misra, Kaushik; Mahata, Tanushree; Nag, Ahindra [RSC Advances, 2016, vol. 6, # 29, p. 24446 - 24450]
[7]Current Patent Assignee: COSMO OIL CO LTD - WO2021/256551, 2021, A1 Location in patent: Paragraph 0098-0120
[8]Location in patent: experimental part Sarma, Kuladip; Goswami, Amrit; Goswami, Bhabesh C. [Tetrahedron Asymmetry, 2009, vol. 20, # 11, p. 1295 - 1300]
[9]Das, Ram Nath; Sarma, Kuladip; Pathak, Madan Gopal; Goswami, Amrit [Synlett, 2010, # 19, p. 2908 - 2912]
[10]Baillet, Julie; Gaubert, Alexandra; Bassani, Dario M.; Verget, Julien; Latxague, Laurent; Barthélémy, Philippe [Chemical Communications, 2020, vol. 56, # 23, p. 3397 - 3400]
[11]Sheng, Li; Higashihara, Tomoya; Maeda, Rina; Hayakawa, Teruaki; Ueda, Mitsuru [Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, # 10, p. 2216 - 2224]
[12]Ricks-Laskoski, Holly L.; Chaloux, Brian L.; Deese, Stephen M.; Laskoski, Matthew; Miller, Joel B.; Buckley, Mary A.; Baldwin, Jeffrey W.; Hickner, Michael A.; Saunders, Kaitlin M.; Christensen, Caroline M. [Macromolecules, 2014, vol. 47, # 13, p. 4243 - 4250]
[13]Current Patent Assignee: CENTRAL GLASS CO LTD; INTERNATIONAL BUSINESS MACHINES CORP - US9244345, 2016, B1
[14]Markwart, Jens C.; Battig, Alexander; Velencoso, Maria M.; Pollok, Dennis; Schartel, Bernhard; Wurm, Frederik R. [Molecules, 2019, vol. 24, # 21]
[15]Novak, Jan; Hasnik, Zbynek; Linhart, Igor [European Journal of Organic Chemistry, 2006, # 2, p. 507 - 515]
[16]Andrus, Merritt B.; Liu, Jing [Tetrahedron Letters, 2006, vol. 47, # 32, p. 5811 - 5814]
[17]Current Patent Assignee: BRIGHAM YOUNG UNIVERSITY - US2008/255382, 2008, A1 Location in patent: Page/Page column 25
[18]Location in patent: experimental part Rosengren-Holmberg, Jenny P.; Karlsson, Jesper G.; Svenson, Johan; Andersson, Hakan S.; Nicholls, Ian A. [Organic and Biomolecular Chemistry, 2009, vol. 7, # 15, p. 3148 - 3155]
[19]Location in patent: experimental part Ali, Dildar; Ahmed, Zaheer; Kazmaier, Peter; Buncel, Erwin [Canadian Journal of Chemistry, 2010, vol. 88, # 9, p. 910 - 921]
[20]Corson et al. [Journal of Organic Chemistry, 1958, vol. 23, p. 544,546]
[21]Bacher, Andreas; Bentley, Philip G.; Bradley, Donal D. C.; Douglas, Louise K.; Glarvey, Paul A.; Grell, Martin; Whitehead, Katherine S.; Turner, Michael L. [Journal of Materials Chemistry, 1999, vol. 9, # 12, p. 2985 - 2990]
[22]Cook, Anthony; Badriya, Samer; Greenfield, Simon; McKeown, Neil B. [Journal of Materials Chemistry, 2002, vol. 12, # 9, p. 2675 - 2683]
[23]Kato, Tadahiro; Saito, Naoko; Kashimura, Kaori; Shinohara, Mariko; Kurahashi, Takuma; Taniguchi, Kohji [Journal of Agricultural and Food Chemistry, 2002, vol. 50, # 22, p. 6307 - 6312]
[24]Cong, Lianhui; Allen, Christopher W. [Phosphorus, Sulfur and Silicon and the Related Elements, 2004, vol. 179, # 4-5, p. 961 - 963]
[25]Gable, Kevin P.; Zhuravlev, Fedor A. [Journal of the American Chemical Society, 2002, vol. 124, # 15, p. 3970 - 3979]
[26]Wang, Mingxing; Gonsalves, Kenneth E.; Rabinovich, Monica; Yueh, Wang; Roberts, Jeanette M. [Journal of Materials Chemistry, 2007, vol. 17, # 17, p. 1699 - 1706]
[27]Location in patent: scheme or table Lim, Ho; Chang, Ji Young [Journal of Materials Chemistry, 2010, vol. 20, # 4, p. 749 - 754]
[28]Location in patent: experimental part Qi, Peipei; Wang, Jincheng; Wang, Liandi; Li, Yun; Jin, Jing; Su, Fan; Tian, Yuzeng; Chen, Jiping [Polymer, 2010, vol. 51, # 23, p. 5417 - 5423]
[29]Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning [Journal of the American Chemical Society, 2015, vol. 137, # 18, p. 6059 - 6066]
[30]McLeod, David C.; Tsarevsky, Nicolay V. [Macromolecules, 2016, vol. 49, # 4, p. 1135 - 1142]
[31]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - KR2016/25611, 2016, A Location in patent: Paragraph 0727; 0731; 0732
[32]Hirschbeck, Vera; Gehrtz, Paul H.; Fleischer, Ivana [Journal of the American Chemical Society, 2016, vol. 138, # 51, p. 16794 - 16799]
[33]Current Patent Assignee: CENTRAL GLASS CO LTD - JP2016/98181, 2016, A Location in patent: Paragraph 0042-0045
[34]Lee, Jun Hyup [Molecular Crystals and Liquid Crystals, 2017, vol. 659, # 1, p. 46 - 51]
[35]Wang, Meng; Bao, Wei-Wei; Chang, Wen-Ying; Chen, Xu-Man; Lin, Bao-Ping; Yang, Hong; Chen, Er-Qiang [Macromolecules, 2019, vol. 52, # 15, p. 5791 - 5800]
[36]Snead, Russell F.; Nekvinda, Jan; Santos, Webster L. [New Journal of Chemistry, 2021, vol. 45, # 33, p. 14925 - 14931]
  • 2
  • [ 53744-50-6 ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
90% With 10H-phenothiazine; 1-ethyl-3-methylimidazolium hydrogensulfate at 150℃; for 6h; 1.c-1; 2.c-2; 3.c-3; 4.c-4; 5.c-5 Step c-3: Add 4-acetoxyphenylmethyl methanol (50g, 0.31mol), 0.15g phenothiazine and 1-ethyl-3-methylimidazolium hydrogen sulfate (200g) into the reaction flask After the reaction, the temperature was raised to 150°C and reacted for 6 hours. After the reaction, it was extracted three times with toluene (100×3), and 1-ethyl-3-methylimidazolium hydrogen sulfate was recovered. The organic phase was washed with 100mL of water and separated. Then, the organic phase was dried by adding 5 g of anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product. The crude product was supplemented with 0.1 g of phenothiazine and purified by distillation under reduced pressure to obtain p-acetoxystyrene (40.5 g, 90.0%, purity 99.70%).
79.3% With 4-tert-Butylcatechol; potassium hydroxide In N,N-dimethyl acetamide at 100 - 110℃; 1; 2; 5; 6 Synthesis of acetoxystyrene Add 4,500 g of DMAC (N, N-dimethylacetamide), 280 g of KOH, 900 g of 1- (4-acetoxyphenyl) ethanol, and 9.0 g of TBC to a 10-L reaction kettle, and raise the temperature to 100 to 110 ° C with stirring. reaction.At the end of the reaction, the solvent was recovered by distillation under reduced pressure, and 3600 g of DCM (dichloromethane) was added to the residue. Then, 4500 g of water was added under stirring, and the layers were separated. The organic layer was first briefly distilled to recover the solvent. 642 g of p-acetoxystyrene, GC purity 98.7%.
78% With tert-butylcatechol In toluene at 90℃; for 0.5h; Molecular sieve; 1-7 Example 1: In a three-necked flask, add 5.0g (0.028mol) p-acetoxyphenethyl alcohol, 5.0g Hβ molecular sieve catalyst, 100mL toluene and 0.05g tert-butylcatechol, stir and react at 90 °C for 30 minutes, filter out the catalyst The toluene was spin-dried, and 3.52g of p-acetoxystyrene was obtained by distillation under reduced pressure with a yield of 78%.
With potassium hydrogensulfate at 175 - 200℃;
With acetic anhydride In N,N-dimethyl-formamide at 50℃;

  • 4
  • [ 2628-16-2 ]
  • [ 66996-59-6 ]
  • Acetic acid 4-[(E)-2-(5-bromo-6-methoxy-naphthalen-2-yl)-vinyl]-phenyl ester [ No CAS ]
  • 5
  • [ 2628-16-2 ]
  • [ 22568-50-9 ]
YieldReaction ConditionsOperation in experiment
78% With 2,2,6,6-tetramethyl-piperidine-N-oxyl; dipotassium peroxodisulfate; sodium nitrite In 1,2-dichloro-ethane at 100℃; for 24h; Sealed tube; stereoselective reaction; General procedure for the synthesis of compounds 2 and 4 General procedure: To a 25 mL sealed tube were added alkenes 1 or 3 (0.5mmol) with NaNO2 (1.5 equiv.), K2S2O8 (2.0 equiv.), TEMPO (1.2 equiv.) and ClCH2CH2Cl (2 mL). The reaction mixture was stirred at 100 oC for 24 h. After the reaction was finished, the reaction was cooled to room temperature. Dichloromethane (2 mL) and water (5 mL) were added. The organic layer was separated, and the aqueous phase was extracted with dichloromethane (5 mL × 3). The combined organic layers were dried with anhydrous Na2SO4, filtered. After evaporating the solvent in vacuum, the residue was purified by column chromatography eluting with PE/EtOAc to obtain the pure nitroalkenes 2 or 4.
78% With dipotassium peroxodisulfate; trifluoroacetic acid; sodium nitrite In dichloromethane; water at 20℃;
62% With Oxone; potassium iodide; sodium nitrite In dichloromethane; water at 20℃; for 1.5h; Green chemistry;
38% With tetrafluoroboric acid; iodine; copper(II) oxide; sodium nitrite In acetonitrile at 20℃; for 7h;
67 %Chromat. With 1-butyl-3-methylimidazolium chloride; sodium nitrite at 80℃; for 1h; Schlenk technique; Sealed tube; Inert atmosphere;

  • 6
  • [ 2628-16-2 ]
  • 2-azido-1-(4-acetoxyphenyl)ethanone [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With trimethylsilylazide; diphenyl diselenide; rose bengal In acetonitrile at 20℃; for 2h; Irradiation; Green chemistry;
87% With trimethylsilylazide; diphenyl diselenide; oxygen; rose bengal In acetonitrile at 20℃; for 2h; Irradiation; 7 Example 7 At room temperature, 32.4 mg of 4-acetoxystyrene was sequentially added to a 15 mL reaction tube.Azide trimethylsilane 46mg, photocatalyst bengal rose red 2.03mg,Diphenyl diselenoate 3.14 mg and acetonitrile 2 ml,The mixture was evenly mixed, and then the reaction was stirred in the air for 2 hours under the irradiation of a 3w blue LED lamp.After completion of the reaction by TLC, the mixture was concentrated under reduced pressure (0.08 MPa) under vacuum to solvent.The crude product was obtained, and then washed with a mixed eluent of petroleum ether and ethyl acetate in a volume ratio of 15:1, and flash column chromatography on a silica gel column to obtain a hydrazine- azide product of the present example.It was 37.9 mg of a white oily solid, yield 87%.
78% With trimethylsilylazide; [Cu(2,9-bis(p-anisyl)-1,10-phenanthroline)Cl2] In acetonitrile at 25℃; for 18h; Irradiation; regioselective reaction;
75% With sodium azide; ammonium cerium(IV) nitrate; oxygen In methanol at 0℃;
62% With trimethylsilylazide; tetrabutylammonium tetrafluoroborate; oxygen In methanol at 10℃; for 3h; Electrochemical reaction;
57% With trimethylsilylazide; oxygen; copper(II) bis(trifluoromethanesulfonate) at 20℃; for 18h; Schlenk technique; Inert atmosphere; Green chemistry;
Multi-step reaction with 3 steps 1: N-Bromosuccinimide / acetonitrile; water / 4 h / 25 - 30 °C 2: 2-iodo-3,4,5,6-tetramethylbenzoic acid; oxone / acetonitrile; water / 10 h / 25 - 30 °C 3: sodium hydrogencarbonate; sodium azide / acetonitrile; water / 6 h / 25 - 30 °C

  • 7
  • [ 592-35-8 ]
  • [ 2628-16-2 ]
  • [ 439584-65-3 ]
  • Acetic acid 4-((S)-2-butoxycarbonylamino-1-hydroxy-ethyl)-phenyl ester [ No CAS ]
  • Acetic acid 4-((R)-2-butoxycarbonylamino-1-hydroxy-ethyl)-phenyl ester [ No CAS ]
  • Acetic acid 4-((S)-1-butoxycarbonylamino-2-hydroxy-ethyl)-phenyl ester [ No CAS ]
  • 8
  • [ 2628-16-2 ]
  • [ 2345-34-8 ]
YieldReaction ConditionsOperation in experiment
88% With Oxone; 2-iodo-3,4,5,6-tetramethylbenzoic acid In water; acetonitrile for 19h;
80% With tert.-butylhydroperoxide In water at 50℃; for 12h; Sealed tube; Green chemistry;
75% With Oxone In N,N-dimethyl-formamide at 25℃; for 3h;
30% With ammonium thiocyanate; oxygen In acetic acid at 25℃; for 8h; General procedure for the preparation of compound 3 General procedure: Themixture of styrene (2.0 mmol) and ammonium thiocyanate (1.0 mmol) in HOAc (3mL) was stirred in oxygen atmosphere at 25 oC for 8 h. After removalof solvent under reduced pressure, the residue waspurified by flash silica-gel column chromatography (eluted with petroleum ether/ acetone from 50/1 to 8/1 (v:v)) and afforded the desired phenacylthiocyanate 3. 4.3.5 4′-Acetoxybenzoic acid (3h)11 (0013) Yellow oil (54mg, 30% yield). 1H NMR (400MHz, CDCl3): δ 9.99 (s, 1H), 7.92 (d, J=8.0Hz, 2H), 7.28 (d, J=8.0Hz, 2H), 2.34 (s, 3H). 13C NMR (150MHz, CDCl3): δ 190.9, 168.7, 155.3, 134.0, 131.2, 122.4, 21.2. MS (ESI-TOF) m/z: (M+H)+ calcd for C9H9O4 181.0, found 181.0
With 1,2-dibutoxyethane; oxygen at 110℃; for 12h;

  • 9
  • [ 2628-16-2 ]
  • [ 39192-49-9 ]
  • [ 42206-94-0 ]
YieldReaction ConditionsOperation in experiment
70.1% With 4-methyl-morpholine;palladium diacetate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride; In para-xylene; at 120℃; for 3.5h; 18. Preparation of 3,5,4'-triacetoxy stilbene A 100 mL round bottom flask was charged with p-xylene (56 mL), Pd(OAc)2 (62.86 mg, 0.28 mmol), 1,3-bis-(2,6-diisopropylphenyl) imidazolinium chloride (119.53 mg, 0.28 mmol), 3,5-diacetoxybenzoyl chloride (7.19 g, 28 mmol), 4-acetoxystyrene (5.35 mL, 33.6 mmol), and N-methyl morphorline (4.2 mL, 33.6 mmol). The mixture was stirred at 120 C. for 3.5 h at nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography (15% EtOAc/hexane, 25% EtOAc/Hexene, then 35% EtOAc/hexane) and gave resveratrol triacetate (6.95 g, 70.1%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) delta 7.50 (d, 2H), 7.12-6.94 (m, 6H), 6.82 (t, 1H), 2.31 (s, 9H); 13C NMR (CDCl3, 75 MHz) 169.6, 169.2, 151.5, 150.6, 139.7, 134.7, 129.9, 127.9, 127.4, 122.1, 117.1, 114.6, 21.4; mp=116-118 C.; HRMS (EI+) found 354.1118 M+, calcd 354.1103 for C20H18O6; Anal. Calcd for C20H18O6: C, 67.79, H, 5.12. Found: C, 67.93, H, 5.26.
With N-ethylmorpholine;;palladium diacetate; In hexane; ethyl acetate; toluene; Example 24 (E)-3, 4',5-Triacetoxystilbene, [(E)-5-(4-acetoxystyryl)-1,3-phenylene diacetate] (24). 3,5-diacetoxybenzoyl chloride, 4-acetoxystyrene, N-ethylmorpholine and palladium diacetate (0.45 mole %) were dissolved in dry toluene (20 mL) and heated overnight at 120 C. under a nitrogen atmosphere. Upon cooling to room temperature, ethyl acetate was added and the reaction washed twice each with 0.1 M HCl and water, then dried, filtered and rotary evaporated to give a brown solid. Purification by isocratic elution from column chromatography with 1:1 hexane/Et2O gave a white solid. This material was purified by gradient elution chrmoatography (4:1 hexane/EtOAc to 2:1 hexane/EtOAc) to give E-5-(4-acetoxystyryl)-1,3-phenylene diacetate as a white solid. Rf 0.29 (2:1 hexane/EtOAc); mp 112.5-113.0 C., 1H NMR (CDCl3): delta 2.27 (s, 9H, 3*OAc), 6.80 (pseudo t, 1H, J=2.1 Hz, 4'), 6.93 (d, 1H, J=16.3 Hz, Htrans), 7.03 (d, 1H, J=trans, 16.3 Hz, Htrans), 7.04-7.09 (m, 4H, 3,5,2',6'), 7.44-7.47 (m, 2H, 2,6); 13C JMOD NMR trans, (CDCl3): delta 20.07 (3*CH3), 113.39 (4'), 115.88 (2',6'), 120.88 (3,5), 126.19, 126.64, 128.64 (2*Ctrans, 2, 6), 133.45 (1), 138.53 (1'), 149.46 (4), 150.34 (3', 5'), 167.91, 168.30 (3*C=O); LRESI positive ion mass spectrum; m/z 377 (MNa+, 100%), 378 (21%).
With N-ethylmorpholine;;palladium diacetate; In hexane; ethyl acetate; toluene; Example 26 (E)-3, 4',5-Triacetoxystilbene, (E)-5-(4-acetoxystyryl)-1,3-phenylene diacetate (26). 3,5-diacetoxybenzoyl chloride, 4-acetoxystyrene, N-ethylmorpholine and palladium diacetate (0.45 mole %) were dissolved in dry toluene and heated overnight at 120 C. under a nitrogen atmosphere. Upon cooling to room temperature, ethyl acetate was added and the reaction washed twice with 0.1 M HCl, then water and dried, filtered and rotary evaporated to a brown solid. Purification by isocratic elution from column chromatography (1:1 hexane/Et2O) gave a white solid. This material was purified by gradient elution chromatography (4:1 hexane/EtOAc to 2:1 hexane/EtOAc) to give (E)-5-(4-acetoxystyryl)-1,3-phenylene diacetate as a white solid. Rf 0.29 (2:1 hexane/EtOAc); mp 112.5-113.0 C., 1H NMR (CDCl3): delta 2.27 (s, 9H, 3*OAc), 6.80 (pseudo t, 1H, J=2.1 Hz, 4'), 6.93 (d, 1H, J=16.3 Hz, Htrans), 7.03 (d, 1H, J=16.3 Hz, Htrans), 7.04-7.09 (m, 4H, 3,5,2',6'), 7.44-7.47 (m, 2H, 2,6); 13C JMOD NMR (CDCl3): delta 20.07 (3*CH3), 113.39 (4'), 115.88 (2',6'), 120.88 (3,5), 126.19, 126.64, 128.64 (2*Ctrans, 2, 6), 133.45 (1), 138.53 (1'), 149.46 (4), 150.34 (3', 5'), 167.91, 168.30 (3*C=O); LRESI positive ion mass spectrum; m/z 377 (MNa+, 100%), 378 (21%).
6.071 g With N-ethylmorpholine;; palladium diacetate; In toluene;Reflux; A suspension of 3,5-diacetoxybenzoic acid (8.022 g, 33.71 mmol) in a mixture of toluene (130 mL),DMF (500 muL) and thionyl chloride (16.00 mL, 220.6 mmol) was heated at 100 C for three hours underan argon gas atmosphere. The solvents were removed by vacuum distillation and the residue re-suspendedin toluene (85 mL) and sonicated under vacuum to remove dissolved gases. 4-Acetoxystyrene (5.74 mL,37.5 mmol), N-ethylmorpholine (4.31 mL, 33.9 mmol) and palladium diacetate (35 mg, 0.16 mmol,0.46 mol %) were added and the reaction heated to reflux for 2 h. Further palladium diacetate (116 mg,0.52 mmol, 1.54 mol %) was added and the reaction left to reflux overnight. On return to roomtemperature, ethyl acetate (500 mL) was added, the solution washed with 0.1 M aq. HCl (2 × 300 mL)and water (300 mL) and then dried and evaporated to return a brown solid. Purification with columnchromatography (isocratically eluted with 2:1 Et2O/hexane) gave 7.888 g of a white solid, shown by1H-NMR spectroscopy to be predominantly the desired adduct. Further chromatography (gradienteluted starting with 4:1 hexane/EtOAc and finishing with 2:1 hexane/EtOAc) returned pure (E)-3,4?,5-triacetoxystilbene (6.071 g, 51%) as a white solid. Rf 0.29 (2:1 hexane/EtOAc); mp 112.5-113.0 C(lit. [17] mp 116 C); deltaH (CDCl3) 2.27 (s, 9H, 3 × OAc), 6.80 (pseudo t, 1H, J = 2.1 Hz, 4?-H), 6.93 (d,1H, J = 16.3 Hz, Htrans), 7.03 (d, 1H, J = 16.3 Hz, Htrans), 7.04-7.09 (m, 4H, 3-H, 5-H, 2?-H, 6?-H) and 7.44-7.47 (m, 2H, 2-H, 6-H); deltaC (CDCl3) 20.07, 113.39, 115.88, 120.88, 126.19, 126.64, 128.64,133.45, 138.53, 149.46, 150.34, 167.91 and 168.30; m/z (ESI) 377 ([M + Na]+, 100%), 378 (21%).

  • 10
  • [ 2628-16-2 ]
  • [ 593249-77-5 ]
  • [ 42206-94-0 ]
  • 11
  • [ 2628-16-2 ]
  • C10H9N2O4(1+)*BF4(1-) [ No CAS ]
  • [ 42206-94-0 ]
  • 12
  • [ 2628-16-2 ]
  • [ 65938-77-4 ]
  • N-(5-methyl-2-pyridinesulfonyl)(4-acetyloxyphenyl)aziridine [ No CAS ]
  • 13
  • [ 861446-17-5 ]
  • [ 2628-16-2 ]
  • [ 861446-18-6 ]
YieldReaction ConditionsOperation in experiment
59% With 4-methyl-morpholine; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In xylene at 120℃; for 3.5h;
59% With 4-methyl-morpholine In para-xylene at 120℃; for 3.5h; 3 3. Preparation of 4'-acetoxy-3,5-bis(methoxymethoxy)stilbene A 50 mL round bottom flask was charged with p-xylene (20 mL), Pd II catalyst (22.5 mg, 0.1 mmol), 1,3-bis-(2,6-diisopropylphenyl) imidazolinium chloride (42.7 mg, 0.1 mmol), 3,5-bis(methoxymethoxy)benzoyl chloride (2.42 g, 10 mmol), 4-acetoxystyrene (1.94 g, 12 mmol), and N-methyl morpholine (1.38 g, 12 mmol). The mixture was stirred at 120° C. for 3.5 h under nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography and gave the product (2.1 g, 59%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.48 (d, 2H), 7.08-6.93 (m, 4H), 6.86 (d, 2H), 6.66 (t, 1H), 5.19 (s, 4H), 3.50 (s, 6H), 2.30 (s, 3H); 13C NMR (CDCl3, 75 MHz) δ 169.5, 158.7, 150.3, 139.5, 135.0, 128.7, 128.5, 127.6, 121.9, 108.0, 104.5, 94.6, 56.2, 21.2; HRMS (EI+) found 358.1409 M+, calcd 358.1416 for C20H22O6.
3.15 g With N-ethylmorpholine;; 1,3-bis-(1-adamantyl)imidazolinium tetrafluoroborate; palladium diacetate In para-xylene at 115 - 120℃; for 3.5h; Inert atmosphere;
  • 14
  • [ 861446-22-2 ]
  • [ 2628-16-2 ]
  • [ 861446-23-3 ]
YieldReaction ConditionsOperation in experiment
70% With 4-methyl-morpholine; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In xylene at 120℃; for 3.5h;
70% With 4-methyl-morpholine In para-xylene at 120℃; for 3.5h; 13 13. Preparation of 3,4'-diacetoxy-5-levulinoxystilbene A 25 mL round bottom flask was charged with p-xylene (6 mL), Pd II catalyst (6.9 mg, 0.03 mmol), 1,3-bis-(2,6-diisopropylphenyl) imidazolinium chloride (12.9 mg, 0.03 mmol), 3-acetoxy-5-levulinoxybenzoyl chloride (0.936 g, 3 mmol), 4-acetoxystyrene (0.583 g, 3.6 mmol), and N-methyl morpholine (0.42 g, 3.6 mmol). The mixture was stirred at 120° C. for 3.5 h under nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography and gave the product (0.86 g, 70%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.48 (m, 2H), 7.12 (m, 6H), 6.81 (t, 1H, J=1.2 Hz), 2.85 (m, 4H), 2.31 (s, 1H), 2.30 (s, 1H), 2.23 (s, 1H), 13C NMR (CDCl3, 75 MHz) δ 206.4, 171.2, 169.5, 169.1, 151.5, 150.6, 140.0, 134.7, 129.8, 127.8, 127.4, 122.1, 117.14, 117.09, 114.6, 38.1, 30.0, 28.4, 21.32, 21.29.
  • 15
  • [ 2628-16-2 ]
  • [ 129714-97-2 ]
  • (E)-3,5-difluoro-4'-acetoxystilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With 4-methyl-morpholine; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In xylene at 120℃; for 3.5h;
74% With 4-methyl-morpholine In para-xylene at 120℃; for 3.5h; 20 20. Preparation of 4'-acetoxy-3,5-difluorostilbene A 25 mL round bottom flask was charged with p-xylene (10 mL), Pd(OAc)2 (11.3 mg, 0.05 mmol), 1,3-bis-(2,6-diisopropylphenyl) imidazolinium chloride (21.4 mg, 0.05 mmol), 3,5-difluorobenzoyl chloride (0.89 g, 5 mmol), 4-acetoxystyrene (0.97 g, 6 mmol), and N-methyl morpholine (0.69 g, 6 mmol). The mixture was stirred at 120° C. for 3.5 h under nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography and gave the product (1.02 g, 74%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.51 (d, J=8.4 Hz, 2H), 7.12-6.97 (m, 6H), 6.70 (t, 1H), 2.31 (s, 3H).
58% With N-ethylmorpholine;; palladium diacetate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 18h;
  • 16
  • [ 2628-16-2 ]
  • [ 130722-44-0 ]
  • [ 861446-29-9 ]
YieldReaction ConditionsOperation in experiment
88% With triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 100℃; for 24h;
88% With triethylamine In N,N-dimethyl-formamide at 100℃; for 24h; 27 27. Preparation of 4'-acetoxy-5-benzyloxy-3-fluorostilbene A mixture of 5-benzyloxy-3-fluorophenyl bromide (2.81 g, 10 mmol), Pd(OAc)2 (0.067 g, 0.3 mmol), tri-o-tolylphosphine (0.18 g, 0.6 mmol), 4-acetoxystyrene (2.03 g, 12.5 mmol), and Et3N (1.26 g, 12.5 mmol) in 20 mL dry DMF was stirred at 100° C. for 24 hours under N2. The dark mixture was distributed between EtOAc and 1N HCl. The organic layer was separated and washed with water and brine, dried over Na2SO4, filtered, and evaporated. After flash column, the desired product (3.19 g, 88%) was obtained. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.51-7.34 (m, 7H), 7.11-6.82 (m, 6H), 6.60 (dt, 1H); 13C NMR (CDCl3, 75 MHz) δ 169.66, 165.64, 162.40, 160.47, 150.58, 140.07 (d), 136.59, 134.76, 129.41, 128.91, 128.41, 128.04 (d), 127.79 (d), 122.11, 109.36 (d), 105.86 (d), 101.91 (d), 70.57, 21.37; 19F NMR (CDCl3, 282 MHz) δ-31675.70 (t); HRMS (EI+) found 362.1302 M+, calcd 362.1318 for C23H19FO3.
  • 17
  • [ 2628-16-2 ]
  • [ 27208-80-6 ]
  • 19
  • [ 397302-06-6 ]
  • [ 2628-16-2 ]
  • 4- [2- (1,1,1,3,3,3-hexafluoro-2-hydroxy)-propyl] styrene-co-4- hydroxystyrene copolymer [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: 1-(2,2,2-Trifluoro-1-trifluoromethyl-ethyl)-4-vinyl-benzene; p-acetoxystyrene With 1-dodecylthiol In tetrahydrofuran at 55 - 65℃; for 24h; Stage #2: With toluene-4-sulfonic acid In tetrahydrofuran; methanol at 20 - 64℃; for 5 - 6h; Heating / reflux; Stage #3: at 20℃; for 1h; 1,5 Synthesis Example 1 Preparation of [4- [2- (1,1,1,3,3, 3-hexafluoro-2-hydroxy)-propyl] styrene-co-4- hydroxystyrene copolymer (SE-1); Synthesis Example 5 Preparation of [4- [2- (1,1,1,3,3, 3-hexafluoro-2-hydroxy)-propyl] styrene-co-4- hydroxystyrene copolymer (SE-5) Into a [100-ML] three-necked round bottom flask the following ingredients were charged: 18.6 g of [4-HEXAFLUOROISOPROPYLSTYRENE] [(HFIPSTY),] 8.31 g of 4- acetoxystyrene (AS), 25.15 g of tetrahydrofuran (THF) and 0.30 g of 1- [DODECANETHIOL.] The flask was equipped with a magnetic stir bar, a thermocouple, a refluxing condenser and a glass stopper. The solution was stirred and heated to [55°C] then 0.98 g of 2,2'-azobis (2-methylbutyronitrile) was added to initiate the polymerization. The solution was heated to [65°C] for 24 h. The polymer solution was cooled to room temperature and 60 g of methanol and 0.244 g [P-TOLUENE] [SULFONIC] acid (pTSA) were added. The mixture was [REFLUXED] at [64°C] for 4 h. A Dean Stark condenser was inserted between the flask and the reflux condenser and the mixture was heated for two more hours with constant drainage of distillate and addition of fresh methanol to the mixture (-25 mL of distillate/methanol each time). Reaction completion was determined by the absence of a carbonyl stretch in the [IR] spectrum. After the mixture cooled to room temperature, 5.58 g of CR-20 ion- exchange resin (a product of Mitsubishi Chemical) was added and stirred for 1 h. The solution was filtered and precipitated in 1.4 L of [WATER/METHANOL] (70: 30). The wet solid was filtered and washed with 500 mL of water. The polymer was dried in a vacuum oven at [65°C] under vacuum for 24 h. The dry polymer weighed 16.35 g (82% recovery). Analytical data is included in the table below.; Into a 250-mL three-necked round bottom flask the following ingredients were charged: 20.17 g [OF HFIPSTY,] 7.74 g of AS, 34.75 g of THF and 0.37 g of 1- [DODECANETHIOL.] The flask was equipped with a magnetic stir bar, a thermocouple, a refluxing condenser and a glass stopper. The solution was stirred and heated to [55°C] then 1.23 g of 2,2'-azobis (2-methylbutyronitrile) was added to initiate the polymerization. The solution was heated to [65°C] for 24 h. The polymer solution was cooled to [50OC] and 67.1 g of methanol and 0.3153 g [PTSA] were added. A Dean Stark condenser was inserted between the flask and the reflux condenser The mixture was refluxed at [64°C] for 4 h. An IR spectrum of the mixture showed a carbonyl stretch so [REFLUXED] one more hour with constant drainage of distillate and addition of fresh methanol to the mixture [(-25] mL of distillate/methanol each time). A second [IR] spectrum of the mixture showed no carbonyl stretch, which indicated that the reaction was complete. After the mixture cooled to room temperature, 3.4 g of CR-20 resin was added and stirred for 1 h. The solution was filtered and precipitated in 0.7 L of water. The wet solid was filtered and dried in a vacuum oven at [65°C] under vacuum for 4 h. The polymer was dissolved in THF to make 100 mL solution and precipitated in 1.2 L of hexanes. The solid was filtered and dried in a vacuum oven at [60°C] under vacuum for 12 h. Analytical data is included in the table below.
  • 20
  • 3,5-diacetoxybromobenzene [ No CAS ]
  • [ 2628-16-2 ]
  • [ 42206-94-0 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;acetophenon-oxim derived palladium catalyst (CAS No. 32679-19-9); In DMF (N,N-dimethyl-formamide); at 150℃; for 15h;Product distribution / selectivity; Example 17 A 10 ml Schlenk tube equipped with a magnetic stirrer is charged with 218 mg (0.8 mmol) 3, 5-DIACETOXYBROMOBENZENE, 136 mg (0.84 mmol) 4-acetoxystyrene, 187 mg potassium carbonate (0.9 mmol) and 0.22 mg (0.1 mol%) of the acetophenon-oxim derived palladium catalyst CAS No. 32679-19-9 as used in Example 9. The tube was evacuated and flushed with argon three times and 1 ml de-aerated DMF was added under inert conditions. The reaction was carried out under stirring for 15 hours at 150C. Work-up WAS CONDUCTED FOLLOWING THE PROCEDURE OF EXAMPLE 4 AND TO GIVE (E) -3, 4 , 5- triacetoxystilbene.
  • 21
  • [ 2628-16-2 ]
  • [ 76478-30-3 ]
  • C20H18O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% With N-ethyl-N,N-diisopropylamine; johnphos In acetonitrile at 80℃; for 48h; 5 In a 50 mL round-bottomed flask fitted with condenser and magnetic stirrer were placed methyl 5-bromosalicylate (5.0 g, 21.64 mmol), Ac2O (2.65 g, 25.97 mmol), Et3N (2.63 g, 25.97 mmol) and catalytic amount of DMAP. The reaction mixture was stirred for 24 h at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried and concentrated to give methyl 2-acetoxy-5- bromobenzoate (5.9 g, 98%). To a stirred solution of methyl 2-acetoxy-5- bromobenzoate (5.9 g, 21.61 mmol) in acetonitrile (80 mL) were added 4- acetoxystyrene (3.68 g, 22.69 mmol), N,N-diisopropylethylamine (8.38 g, 64.82 mmol), biphenyl-2-yl-di-t-butyl phosphine (368 mg, 1.29 mmol) and palladium acetate (291 mg, 1.29 mmol) under N2. The reaction mixture was heated to 80 0C for 48 h and then cooled to room temperature. Water was added and the mixture was extracted with ethyl acetate. The organic layer was separated, washed with water, brine, dried and concentrated to give crude product, which was purified by column chromatography, using 20% ethyl acetate in hexane to give (3.19 g, 42%) of the di-acetoxy stillbene. To a solution of the di-acetoxy stillbene (500 mg, 1.41 mmol) in acetonitrile: THF (10 mL: 10 mL), NaOH (388 mg, 8.47 mmol) was added and stirred for 24 h at room temperature. The reaction mixture was neutralized by dilute HCI and extracted with ethyl acetate. The combined organic layers were washed with water, brine, dried and concentrated to give a crude EPO product, which was purified by crystallization in ethyl acetate and hexane to give 2-hydroxy-5-[(E)-2-(4-hydroxyphenyl)vinyl]benzoic acid (250 mg, 69%). MS (ES)m/z: 256.06 (M), 255.05 (M-1 ); 13C-NMR (CD3OD): δ 172.3, 161.1 , 157.1 , 132.7,129.6, 129.3, 128.0, 127.5, 127.1 , 124.3, 117.4, 115.3, 112.7. Mp. 241-243 0C.
  • 22
  • [ 1131622-49-5 ]
  • [ 2628-16-2 ]
  • C21H20O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% With N-ethyl-N,N-diisopropylamine; johnphos In acetonitrile at 80℃; for 48h; 7 In a 50 ml. round-bottomed flask fitted with condenser and magnetic stirrer were placed methyl 5-bromosalicylate (5.0 g, 21.64 mmol) , AC2O (2.65 g, 25.97 mmol), Et3N (2.63 g, 25.97 mmol) and catalytic amount of DMAP. The reaction mixture was stirred for 24 h at rt. The reaction mixture was poured into water and extracted with EtOAc. The organic layer was washed with water, dried and concentrated to give the acetoxy derivative (5.9 g, 98%). To a stirred solution of methyl 2-acetoxy-5-bromobenzoate (5.9 g, 21.61 mmol) in acetonitrile (80 ml_) were added 4-acetoxystyrene (3.68 g, 22.69 mmol), N1N- diisopropylethylamine (8.38 g, 64.82 mmol), biphenyl-2-yl-di-t-butyl phosphine (368 mg, 1.29 mmol) and palladium acetate (291 mg, 1.29 mmol) under N2. The reaction mixture was heated to 80 °C for 48 h and then cooled to rt. Water was added and the mixture was extracted with EtOAc. The organic layer was separated, washed with water, brine, dried and concentrated to give crude EPO product, which was purified by column chromatography, using 20% EtOAc in hexane to give (3.19 g, 42%) of the di-acetoxy stillbene. The di-acetoxystillbene (500 mg, 1.41 mmol) was treated with ammonia (2M solution in ethanol, 15 ml_) in a sealed tube at 115 0C for 12 h. The reaction mixture was cooled to rt. The solvent was removed and the crude product was purified by column chromatography using 50% EtOAc in hexane to give the product (200 mg, 50%).MS (ES) m/z: 284.12 (M), 283.14 (M-1 ); 13C-NMR (DMSO-d6): δ 169.5, 159.9,157.8, 133.2, 130.4, 129.9, 128.8, 128.4, 128.3, 127.8, 124.5, 118.6, 116.2, 115.9,113.9, 62.1 , 14.7; Mp. 269-271 °C.
  • 23
  • [ 2628-16-2 ]
  • [ 90532-00-6 ]
  • 4-[2-(2-methanesulfonyl)-4-methoxyphenylvinyl]phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
43% With N-ethyl-N,N-diisopropylamine; johnphos In acetonitrile at 80℃; for 15h; 9 To a stirred solution of 1-bromo-2-methanesulfonyl-4-methoxy benzene in anhyd. acetonitrile were added 4-acetoxystyrene (1.413 g, 8.715 mmol), Λ/,Λ/-diisopropylethylamine (3.218 g, 24.9 mmol), biphenyl-2-yl-di-tert- butylphophine (0.149 g, 0.5 mmol) and palladium acetate (0.112 g, 0.5 mmol). EPO The resulting mixture was stirred at 80 0C for 15 h under nitrogen. The mixture was cooled to rt, and the solvent was removed under reduced pressure. The residue was dissolved in 50 ml_ EtOAc, washed with water and brine and dried over anhydrous Na2SO4. Purification by column chromatography (SilicaGel 230 -400 mesh; 20% EtOAc in hexanes as an eluent) gave 4-[2-(2-methanesulfonyl)-4- methoxyphenylvinyl] phenyl acetate 1.245 g (43% yield).
  • 24
  • [ 2628-16-2 ]
  • [ 13031-43-1 ]
  • [ 99-93-4 ]
  • [ 53744-50-6 ]
YieldReaction ConditionsOperation in experiment
With acetic anhydride; In palladium-carbon; EXAMPLE 1 This example illustrates the preparation of 4-acetoxystyrene oxide from 4-acetoxystyrene under the invention, the latter compound having been prepared from 4-hydroxyacetophenone (4-HAP) as an intermediate. A solution of 136.2g (1.0 mol) of 4-hydroxyacetophenone and 400 ml of acetic anhydride was heated at reflux for 3 h under a nitrogen atmosphere. The acetic acid and acetic anhydride was distilled overhead in vacuo (30-41C, 2.6 mm Hg). The remaining oil was then distilled in vacuo (132-134C, 2.0 mm Hg) to yield 169.7g (95.2%) of white crystals identified as 4 -acetoxyacetophenone. 4-Acetoxyacetophenone (100.0 g, 0.56 mol) was hydrogenated in a Fluidtron Reactor with 5% Pd/C (3.94 g) at 100 psig. The hydrogenation was carried out at 60C for 5.25 hours. The reactor was depressurized and the catalyst removed via filtration to afford 1-(4--acetoxyphenyl)ethanol as an oil (93.6 g).
  • 25
  • [ 75-11-6 ]
  • [ 2628-16-2 ]
  • 4'-Cyclopropylphenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With diethylzinc In toluene at 20℃; for 17h; Heating / reflux; 18.A A. A. acetic acid 4-cyclopropyl-phenyl ester To a solution of diethylzinc (200 mL, 0.220 mol, 1.1 M in toluene) in toluene (270 mL) was added 4-acetoxystyrene (16.8 mL, 0.110 mol) and subsequently diiodomethane (23.0 mL, 0.286 mol). After the reaction mixture was stirred at rt for 5 hours, it was heated at reflux for 12 hours. The reaction was quenched with aqueous 2N HCl. The organic layer was separated and washed with brine, dried over Na2SO4, filtered, and the filtrate was concentrated under reduced pressure to afford the title compound as a brown oil (16.1 g, 83%).
Stage #1: diiodomethane With diethylzinc In hexane; dichloromethane at 0℃; for 1.25h; Inert atmosphere; Stage #2: With trichloroacetic acid In 1,2-dimethoxyethane; hexane; dichloromethane at 0℃; for 1.25h; Inert atmosphere; Stage #3: p-acetoxystyrene In 1,2-dimethoxyethane; hexane; dichloromethane at 22℃; for 20h; Inert atmosphere;
Stage #1: diiodomethane With diethylzinc In hexane; dichloromethane at 0℃; for 1.25h; Inert atmosphere; Stage #2: With 1,2-dimethoxyethane; trichloroacetic acid In hexane; dichloromethane at 0℃; for 1.25h; Inert atmosphere; Stage #3: p-acetoxystyrene In hexane; dichloromethane at 22℃; for 20h; Inert atmosphere;
  • 26
  • [ 108-24-7 ]
  • [ 2628-17-3 ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
86% In N,N-dimethyl acetamide for 0.5h; Heating / reflux; 6 Example 6; Preparation of P-Acetoxystyrene from N,N-Dimethyltyrosine N-Oxide in One Pot; To a 25 ml 3-neck flask equipped with water circulating distilling head and collecting flask, and under gentle nitrogen sweep, was added 0.52 g (0.0023 mole) of N,N-dimethyltyrosine N-oxide (prepared as described in Example 2) and 5 mL (4.685 g) DMAc. To the resulting solution was added 0.011 g (5 mole %) potassium acetate. The flask was lowered into a preheated oil bath at 123° C. The reaction was sampled and monitored by HPLC. A yield of 97% p-hydroxystyrene was determined after 2.4 h. To the solution was added 0.282 g, (2.76 mmol) acetic anhydride and the heating continued for 30 minutes. HPLC analysis using the method described in General Methods with a calibration curve for pAS showed the yield of p-acetoxystyrene to be 86%. The reaction mixture was allowed to cool to room temperature, then poured into 25 ml water. Extraction with ethylacetate, followed by removal of the solvent, gave a yellow oil. Distillation using an oil sublimator at 2 ee-5 torr gave the desired product, as a clear oil.
58.6% With 10H-phenothiazine; triethylamine In tert-butyl methyl ether at -5 - 20℃; for 1h; Green chemistry; 1 Comparative example 1 Add p-hydroxystyrene (120g) to a 2L four-neck bottle. triethylamine (106g), phenothiazine (1.2g), methyl tert-butyl ether (480 g) and a dry ice-ethanol bath were cooled to -5 to 0 °C. Start adding dropwise acetic anhydride (110g) with stirring. the internal temperature is controlled at -5 to 0 °C. After the completion of the dropwise addition, the temperature was raised at 10 to 20 °C to continue the reaction for 1 hour. Sampling analysis (central control 1, raw material Add water (300g) and stir for 30 minutes. The aqueous layer was separated to remove most of the acetic acid. The organic layer was again added with a 0.5% sodium hydrogen carbonate solution (100 g), stirred for 30 minutes, and the aqueous layer was separated to remove acetic acid. The organic layer was added with water (100 g), stirred for 30 minutes, and the aqueous layer was separated. HaveThe machine layer was dried over sodium sulfate (20 g) for 4 hours. After completion, phenothiazine (1.2 g) was added, and the reaction liquid was concentrated, and methyl tert-butyl ether (300 g) was collected to obtain 112 g of crude product.The crude product was distilled under reduced pressure to give the product p-acetoxystyrene (95 g).The yield is 58.6%.Sampling analysis (main content >99%).A total of 400 g of wastewater was produced, 100 g of salty wastewater, and 20 g of sodium sulfate.
24% With dmap; triethylamine In dichloromethane at 23℃; for 0.5h; Inert atmosphere;
24% With dmap; triethylamine In dichloromethane at 23℃; for 0.5h; Inert atmosphere; 1 4-Acetyistyrene (precursor 7). Precursor 6 (100 mg, 0.832 mmol) CH2C12(10 mL) was added to a mixture of triethylamine (1.16 mL), acetic anhydride (83 iL),and DMAP (100 mg) under an atmosphere of N2. The mixture was stirred at 23°C for30 minutes and then diluted with CH2C12 (20 mL). The organic layer was washed with water 3 times and then once with saturated NaHCO3 solution. The organic layer wasdried (MgSO4) and concentrated in vacuo. Purification by column chromatography gave the title compound: yield 24%. ‘H NMR (300 MHz, CDC13, ö): 7.42-7.40 (m, 2H), 7.07-7.02 (m, 2H), 6.71 (dd, J= 16, 9 Hz, 1H), 5.71 (d, J= 16Hz, 1H), 5.25 (d, J= 9 Hz, 1H), 2.28 (s, 3H).
80.20 g at 80℃; for 2h; 7; 8 Example 8 Synthesis of 4-acetoxystyrene 80 g of 4-hydroxybenzaldehyde and 102.3 g of malonic acid are dissolved in 240 g of pyridine, and 4.92 g of glycine is added to this solution.This solution is stirred at 80 ° C. under atmospheric pressure for 120 minutes. Thereafter, 66.3 g of triethylamine was added to the resulting solution and heated under reflux at 140 ° C. for 8 hours.100.3 g of acetic anhydride was added to the resulting solution, and the mixture was stirred at 80 ° C. under atmospheric pressure for 2 hours.When gas chromatography mass spectrometry is carried out, the conversion to 4-acetoxystyrene is 82%. After completion of the reaction,From the resultant solution, the solvent was distilled off under reduced pressure,240 g of hexane and 80 g of 2% by mass hydrochloric acid are added and stirred for several minutes.After washing the obtained organic layer with water, the solvent was distilled off under reduced pressure,By distillation under reduced pressure, 80.20 g of highly pure acetoxystyrene is obtained (yield 76%).

  • 27
  • [ 6773-29-1 ]
  • [ 2628-16-2 ]
  • [ 1034147-66-4 ]
YieldReaction ConditionsOperation in experiment
77% With dirhodium tetraacetate In dichloromethane at 20℃; for 15h;
67% Stage #1: dimethyl diazomalonate; p-acetoxystyrene In dichloromethane at 0 - 22℃; Inert atmosphere; Stage #2: With tetrakis(hydroxymethyl)phosphonium hydroxide In benzene at 60℃; for 12h;
62% With dirhodium tetraacetate In dichloromethane at 20℃; for 7h;
With dirhodium tetraacetate In dichloromethane at 20℃; for 15h;
With rhodium(II) acetate dimer In dichloromethane at 20℃; for 15h; General Procedure for the Preparation of DA-cyclopropanes (GP 1) General procedure: To a solution of the corresponding styrene (1.0 equiv), Rh2(OAc)4 (0.5 mol%) in dichloromethane wasadded dropwise diazomalonate (1.30 equiv) in dichloromethane over 15 h via syringe pump at ambienttemperature. The solvent was removed in vacuo and silica gel column chromatography gave the desiredproduct.1 All donor-acceptor cyclopropanes are known to literature and were prepared according toexisting procedures.

  • 28
  • [ 360068-17-3 ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
96% With gallium; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Ultrasonic irradiation; chemoselective reaction;
96% With bismuth(III) chloride; gallium In tetrahydrofuran at 20℃; for 0.5h;
94% With bismuth(III) chloride; indium In methanol at 20℃; for 0.5h; Sonication; chemoselective reaction;
93% With indium; cobalt(II) chloride hexahydrate In methanol at 20℃; for 0.5h;
93% With indium; niobium pentachloride In tetrahydrofuran at 20℃; for 0.166667h; Sonication; chemoselective reaction; A typical procedure for the debromination of vic-dibromides is as follows: General procedure: Indium powder (230 mg, 2.0 mmol) and NbCl5 (238 mg,1.0 mmol) are mixed in THF (4 mL). The resulting mixture is sonicated in an ultrasonic cleaner9 for 30 min and a solution of the low-valent niobium-indium complex is formed. 1,2-Dibromo-1,2-diphenylethane (170 mg, 0.5 mmol) is then added to this solution and the reaction mixture is stirred for 15 min at room temperature. The solvent is removed under reduced pressure and the residue is extracted with ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. The crude product is purified by silica gel column chromatography (hexane:ethyl acetate = 10:1) to afford trans-stilbene (85 mg, 94%).
93% at 20℃; for 0.0833333h; chemoselective reaction; General Procedure for the Reaction General procedure: A 10-mL round-bottomed flask was charged with indiumpowder (230 mg, 2.0 mmol), vanadium trichloride (157 mg,1.0 mmol) and THF (4 mL). The resulting mixture was stirred for 30 min under sonication producing a solution ofthe low-valent vanadium-indium complex. 1,2-Dibromo-1,2-diphenylethane (170 mg, 0.5 mmol) was then added tothis solution and the reaction mixture was stirred for 3 minat room temperature. The progress of the reaction was monitoredby TLC. After completion of the reaction, the solventwas removed under reduced pressure and the residuewas then extracted with ethyl acetate (3 × 10 mL). The combinedextract was washed with brine, dried over anhydrousNa2SO4 and concentrated. The crude product wasfurther purified by column chromatography on a silica gel(hexane:ethyl acetate = 10:1) to provide trans-stilbene (85 mg,94%). All the products were identified by comparison oftheir spectroscopic data with authentic compounds.
91% With indium; iron(III) chloride hexahydrate In methanol at 20℃; for 1.5h; chemoselective reaction;
91% With 1,1'-bis(trimethylsilyl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene In acetonitrile at 20℃; for 2h; Inert atmosphere;

  • 29
  • [ 623-17-6 ]
  • [ 2628-16-2 ]
  • [ 1187364-12-0 ]
  • 30
  • [ 2628-16-2 ]
  • [ 89487-91-2 ]
  • [ 1188366-13-3 ]
  • 31
  • [ 75-11-6 ]
  • [ 2628-16-2 ]
  • [ 10292-61-2 ]
YieldReaction ConditionsOperation in experiment
94% To a solution of diethylzinc (59 mL, 65.9 mmol) in toluene (80 mL) was added acetic acid 4-vinyl-phenyl ester (5 mL, 32.7 mmol) and diiodomethane (6.86 mL, 85 mmol). The resultant mixture was stirred at room temperature for 5 h, and then heated to reflux for 12 h. The reaction mixture was quenched with 2N HCl solution, the organic layer separated, washed with brine, dried over Na2SO4, and concentrated to afford a brown oil (4.5 g). The brown oil (4.5 g) was dissolved in MeOH/THF (20/20 mL), then treated with Na2CO3 (5.41 g, 51.1 mmol) at room temperature for 2 h. The reaction mixture was diluted with EtOAc, washed sequentially with saturated NH4Cl (aq) and H2O, and extracted with EtOAc (3×). The organic extracts were combined, dried over Na2SO4 and concentrated under reduced pressure to afford the title compound (3.2 g; 94% yield), which was used directly without further purification.
  • 32
  • [ 2628-16-2 ]
  • [ 89818-46-2 ]
  • [ 1289560-26-4 ]
YieldReaction ConditionsOperation in experiment
74% With silver(I) acetate; palladium diacetate In acetonitrile at 80℃; for 12h;
65% With oxygen; palladium diacetate In N,N-dimethyl-formamide at 80℃; for 13h; (E)-4-(2-(Pyridin-2-ylsulfinyl)styryl)phenyl Acetate (3ad); Typical Procedure for 2-Pyridyl Sulfoxide Directed Pd(II)-Catalyzed C-H Olefination of Arenes An oven-dried glass reaction tube with a septum was charged with 2-(phenylsulfinyl)pyridine (1a; 51 mg, 0.25 mmol) and Pd(OAc)2 (6 mg, 0.025 mmol, 0.1 equiv). The mixture was degassed with three vacuum-oxygen cycles before DMF (2.5 mL) and olefin 2d (81 mg, 0.5mmol, 2 equiv) were added at room temperature. Then the reaction mixture was purged with O2 using a balloon and the reaction tube was closed with a screw cap. Finally, the mixture was stirred on a preheated heating block at 80 °C for 13 h. The reaction mixture was quenched with H2O and extracted with ethyl acetate (3 × 10 mL). The organic layer was separated, dried over Na2SO4, and concentrated under vacuum. The crude residue was purified using column chromatography on silica gel (hexane/EtOAc, 4:1) to provide 3ad as a yellow solid; yield: 59 mg (65%).
49% With [bis(acetoxy)iodo]benzene; palladium diacetate In 1,2-dichloro-ethane at 110℃; for 20h; Inert atmosphere;
  • 33
  • [ 3939-23-9 ]
  • [ 2628-16-2 ]
  • [ 1256379-23-3 ]
  • 34
  • [ 3939-23-9 ]
  • [ 2628-16-2 ]
  • [ 1256379-27-7 ]
  • 35
  • N,N-DMF [ No CAS ]
  • [ 2628-16-2 ]
  • [ 6304-89-8 ]
  • [ 1236211-29-2 ]
YieldReaction ConditionsOperation in experiment
With N-ethylmorpholine;; thionyl chloride;palladium diacetate; In hexane; ethyl acetate; toluene; Example 15 (E)-3,4'-Diacetoxystilbene, [(E)-3-(4-acetoxystyryl)phenyl acetate] (15). A suspension of <strong>[6304-89-8]3-acetoxybenzoic acid</strong> in dry toluene, N,N-DMF and thionyl chloride was heated to 100 C. under an argon atmosphere and maintained for 3 hours. The solvents were removed by vacuum distillation and the resultant solid redissolved in dry toluene, then this solution was sonicated under vacuum for 20 minutes. 4-Acetoxystyrene, N-ethylmorpholine and palladium diacetate (2 mole %) were added and the mixture heated overnight at 120 C. under an argon gas atmosphere. Upon cooling to room temperature, ethyl acetate was added, which was subsequently washed three times with 0.1 M HCl and twice with water, then dried, filtered and rotary evaporated to give of a brown liquid. Purification by column chromatography (gradient elution starting with 4:1 hexane/EtOAc and finishing with 2:1 hexane/EtOAc) gave a white solid. 1H NMR showed this to be mostly (E)-3,4'-diacetoxystilbene and a small amount of unreacted 4-acetoxystyrene. Recrystallization from EtOAc/hexane gave (E)-3-(4-acetoxystyryl)phenyl acetate exclusively as white mica plates. Rf 0.32 (4:1 hexane/EtOAc), 0.59 (2:1 hexane/EtOAc); mp 124.5-125.0 C., 1H NMR (CDCl3): delta 2.28 (s, 3H, OAc), 2.29 (s, 3H, OAc), 6.93-7.09 (m, 5H, H-4, 2*Htrans, H-3', H-5'), 7.21-7.22 (m, 1H, H-2), 7.30-7.34 (m, 2H, H-5, H-6), 7.45-7.50 (m, 2H, H-2', H-6'); 13C JMOD NMR (CDCl3): delta 20.11 (2*OC(O)CH3), 118.27 (4), 119.74 (2), 120.86 (3',5'), 123.19 (6), 126.55 (2',6'), 126.96, 127.76 (2*Ctrans), 128.61 (5), 133.79 (1'), 137.92 (1), 149.32 (4'), 150.15 (3), 168.35 (2*C=O).
  • 36
  • [ 2628-16-2 ]
  • [ 35354-29-1 ]
  • [ 42206-94-0 ]
YieldReaction ConditionsOperation in experiment
With N-ethylmorpholine;; thionyl chloride;palladium diacetate; In ethyl acetate; N,N-dimethyl-formamide; toluene; (E)-3,4',5-Triacetoxystilbene 3,5-Diacetoxybenzoic acid (8.022 g, 33.706 mmol) suspended in a mixture of toluene (130 mL), DMF (500 muL) and thionyl chloride (16.00 mL, 220.6 mmol) was heated at 100 C. for three hours under an argon gas atmosphere. The solvents were removed by vacuum distillation and the residue re-suspended in toluene (85 mL) and sonicated under vacuum to remove dissolved gases. 4-Acetoxystyrene (5.74 mL, 37.5 mmol), N-ethylmorpholine (4.31 mL, 33.9 mmol) and palladium diacetate (35 mg, 0.16 mmol, 0.46 mole %) were added and the reaction heated to reflux for 2 hours. Further palladium diacetate (116 mg, 0.52 mmol, 1.54 mole %) was added and the reaction left to reflux overnight. On return to room temperature, ethyl acetate (500 mL) was added, the solution was washed with 0.1 M HCl (2*300 mL) and water (300 mL) and then dried and evaporated to return a brown solid. Purification with column chromatography (isocratically eluted with 2:1 Et2O/hexane) gave 7.888 g of a white solid, shown by 1H NMR to be predominantly the desired adduct. Further chromatography (gradient eluted starting with 4:1 hexane/EtOAc and finishing with 2:1 hexane/EtOAc) returned pure (E)-3,4',5-triacetoxystilbene (6.071 g, 51%) as a white solid. Rf 0.29 (2:1 hexane/EtOAc); mp 112.5-113.0 C. (lit mp 116 C.); (deltaC (CDCl3) 2.27 (s, 9H, 3*OAc), 6.80 (pseudo t, 1H, J 2.1, 4'-H), 6.93 (d, 1H, J 16.3, Htrans), 7.03 (d, 1H, J 16.3, Htrans), 7.04-7.09 (m, 4H, 3-H, 5-H, 2'-H, 6'-H) and 7.44-7.47 (m, 2H, 2-H, 6-H); deltaC(CDCl3) 20.07, 113.39, 115.88, 120.88, 126.19, 126.64, 128.64, 133.45, 138.53, 149.46, 150.34, 167.91 and 168.30; m/z (ESI) 377 (MNa+, 100%), 378 (21).
  • 37
  • [ 2628-16-2 ]
  • 3,5-diacetoxybenzoic acid, N,N-DMF and thionyl chloride [ No CAS ]
  • [ 42206-94-0 ]
YieldReaction ConditionsOperation in experiment
With N-ethylmorpholine;;palladium diacetate; In hexane; ethyl acetate; toluene; Example 25 (E)-3, 4',5-Triacetoxystilbene, (E)-5-(4-acetoxystyryl)-1,3-phenylene diacetate (25). A mixture of 3,5-diacetoxybenzoic acid, N,N-DMF and thionyl chloride in dry toluene was heated to 100 C. under an argon atmosphere for 3 hours. The solvents were removed by vacuum distillation and the solid white residue subsequently suspended in dry toluene and sonicated under vacuum. 4-acetoxystyrene, N-ethylmorpholine and palladium diacetate (2.0 mole %) were added and this mixture was heated overnight at 120 C. Upon cooling to room temperature, ethyl acetate was added and the solution washed three times with 0.1 M HCl, then, dried, filtered and rotary evaporated to give a brown solid. Purification by gradient elution column chromatography (2:1 hexane/EtOAc to 100% EtOAc) gave (E)-5-(4-acetoxystyryl)-1,3-phenylene diacetate as a white solid. Rf 0.29 (2:1 hexane/EtOAc); mp 112.5-113.0 C., 1H NMR (CDCl3): delta 2.27 (s, 9H, 3*OAc), 6.80 (pseudo t, 1H, J=2.1 Hz, 4'), 6.93 (d, 1H, J=16.3 Hz, Htrans), 7.03 (d, 1H, J=16.3 Hz, Htrans), 7.04-7.09 (m, 4H, 3,5,2',6'), 7.44-7.47 (m, 2H, 2,6); 13C JMOD NMR (CDCl3): delta 20.07 (3*CH3), 113.39 (4'), 115.88 (2',6'), 120.88 (3,5), 126.19, 126.64, 128.64 (2*Ctrans, 2, 6), 133.45 (1), 138.53 (1'), 149.46 (4), 150.34 (3', 5'), 167.91, 168.30 (3*C=O); LRESI positive ion mass spectrum; m/z 377 (MNa+, 100%), 378 (21%).
  • 38
  • [ 2628-16-2 ]
  • [ 55962-05-5 ]
  • N-(p-toluenesulfonyl)-2-(4-acetoxylphenyl)aziridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With iodine; tetra-(n-butyl)ammonium iodide In acetonitrile at 20℃; for 3h; Inert atmosphere;
77.3% With [Cu(N,N'-bis(4-hydroxysalicylidene)phenylene-1,2-diamine)] immobilized on modified multi-wall carbon nanotubes In acetonitrile at 25℃; for 4h; General procedure for aziridination of styrene General procedure: [Cu((OH)2-salophen)]MWNTs] (5.6 mol%), styrene (0.56 ml,5 mmol) and PhI = NTs (0.372 g, 1 mmol) were added to acetonitrile (3 ml) and the reaction mixture was stirred at room temperature.The reaction was monitored by disappearance of the PhI = NTs from the reaction mixture. After completion of the reaction, the catalyst was filtered and the filtrate was concentrated and purified by column chromatography (hexane/ethyl acetate, 95/5, v/v) to afford pure product as white solid
73% With [PhB{CH2P(p-CF3Ph)2}3]Cu(PPh3) In dichloromethane at 20℃; for 5h; Inert atmosphere; Schlenk technique;
60% With bis(acetylacetonate)copper(II) In acetonitrile at 20℃;
51% With Tp(CF3)2,BrCu(NCMe) In water at 20℃; for 4h; Schlenk technique; Inert atmosphere;
84 %Spectr. Stage #1: p-acetoxystyrene With {Cu[Ph2P(NSiMe3)2]2 In chloroform-d1 for 0.0166667h; Schlenk technique; Inert atmosphere; Stage #2: [N-(p-tolylsulfonyl)imino]phenyliodinane In chloroform-d1 at 25℃; for 12h; Schlenk technique; Inert atmosphere;
In dichloromethane at 25℃; Inert atmosphere;

  • 39
  • [ 2628-16-2 ]
  • [ 28917-44-4 ]
  • [ 1432450-00-4 ]
YieldReaction ConditionsOperation in experiment
88% With N-ethylmorpholine;; 1,3-bis-(1-adamantyl)imidazolinium tetrafluoroborate; palladium diacetate In para-xylene at 115 - 120℃; for 3h; Inert atmosphere; (E)-4-(3,5-bis(benzyloxy)styryl)phenyl acetate (9) A 50 mL round bottomflask was charged with p-xylene (20 mL), Pd(OAc)2 (22.5 mg, 0.1mmol), 1,3-bis-(1-adamantyl)imidazolium tetrafluoroborate (8) (42.6mg, 0.1 mmol), 3,5-bis(benzyloxy)benzoic chloride (6) (4.50 g, 10 mmol), 4-acetoxystyrene (7) (2.02 g, 12.5 mmol), and N-ethyl morpholine (1.58mL, 12.5 mmol). A condenser column was installed and the flask and column weredegassed three times with Ar. The mixture was heated at 115-120 °C for 3 hoursunder an Ar atmosphere. After the solution was cooled to rt it was poured into asilica gel column. Eluting solvent: 5-10% EtOAc/Hex. Flash chromatography gaveproduct (9) (3.15 g, 88%) as a white solid. Data are: 1HNMR (CDCl3, 500 MHz): δ 7.507(d, J = 8.5 Hz, 2H), 7.407 (m, 10H),7.094 (d, J = 8.5 Hz, 2H), 7.055 (d, J = 16 Hz, 1H), 6.977 (d, J = 16 Hz, 1H), 6.774 (d, J = 2 Hz, 2H), 6.569 (t, J = 2 Hz, 1H), 5.084 (s, 4H), 2.318 (s,3H); 13C NMR (CDCl3, 125 MHz): δ 169.460, 160.168, 150.145, 139.240,136.833, 134.930, 128.823, 128.625, 128.274, 128.041, 127.568, 127.511,121.820, 105.823, 101.628, 70.153, 21.163; HRMS found 451.1971 (M+H)+,calculated 451.19 for (C30H26O4+H)+.
  • 40
  • [ 2628-16-2 ]
  • [ 555-16-8 ]
  • [ 1022875-86-0 ]
YieldReaction ConditionsOperation in experiment
82% With N-Bromosuccinimide; oxygen; 3-benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazol-3-ium chloride; triethylamine In dimethyl sulfoxide at 25℃; for 23h; regioselective reaction;
82% With N-Bromosuccinimide; oxygen; 3-benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazol-3-ium chloride; triethylamine In dimethyl sulfoxide at 25℃; for 23h; 1 EXAMPLE 1 General procedure: To a solution of alkenes (IIIa-q) (1 equiv.) in DMSO (20 ml), N-Heterocyclic carbene (10 mol %), N-Bromo succinamide (1 equiv.), triethyl amine (1.2 equiv.) and aldehyde (IVa-f)were added under oxygen atmosphere. The reaction mixture was then stirred at 25°C. After completion (monitored by TLC), the reaction mixture was then concentrated, followed by the addition of H20 (50 mL). It was extracted with EtOAc (3 x 50 ml) and the combined organic layers dried over anhydrous Na2S04. Removal of solvent gave a-acyloxy carbonyls (Ia-v), which were purified by column chromatography over silica gel using pet ether/EtOAc (1/19) as eluent to obtain pure a-acyloxy carbonyls in high purity.
  • 41
  • [ 2628-16-2 ]
  • [ 69655-76-1 ]
  • C80H72O28Si8 [ No CAS ]
  • 42
  • [ 2628-16-2 ]
  • [ 25015-63-8 ]
  • [ 1600527-29-4 ]
YieldReaction ConditionsOperation in experiment
92% With [{CyPN(H)P}Co(CH2SiMe3)]-BArF4 In diethyl ether at 25℃; for 4h; Inert atmosphere; Glovebox; Schlenk technique;
90% With <SUP>Mes</SUP>BIPCoCl<SUB>2</SUB>; sodium t-butanolate at 25℃; for 1h;
90% With C20H22AlN2PSe In neat (no solvent) at 30℃; for 8h; Schlenk technique; Glovebox; Inert atmosphere; chemoselective reaction;
80% With (<SUP>iP</SUP><SUP>r</SUP>PNN)CoCl<SUB>2</SUB>; sodium triethylborohydride In tetrahydrofuran; toluene at 25℃; for 0.25h; Inert atmosphere; Glovebox; Schlenk technique; chemoselective reaction;
65% With fac-[Mn(1,2-bis(di-isopropylphosphino)ethane)(CO)3(CH2CH2CH3)] In tetrahydrofuran at 80℃; for 24h; Sealed tube; Inert atmosphere;
55% With sodium triethylborohydride; scandium tris(trifluoromethanesulfonate) In tetrahydrofuran; toluene at 100℃; for 24h; Microwave irradiation; Inert atmosphere; regioselective reaction;
50% With silver hexafluoroantimonate at 60℃; for 24h; Schlenk technique; Glovebox; Inert atmosphere;
36% With tropylium tetrafluoroborate In neat (no solvent) at 70℃; for 12h;
With C20H37CoN3OP2(1+)*BF4(1-) In benzene at 25℃; for 24h; Inert atmosphere;

  • 43
  • [ 2628-16-2 ]
  • [ 1605274-62-1 ]
  • (E)-4-acetoxy-4'-(pentafluorosulfanyl)stilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With palladium diacetate In ethanol; water at 20℃; for 24h; diastereoselective reaction;
64% With palladium diacetate In ethanol; water at 20℃; for 14h;
64% With palladium diacetate In ethanol; water at 20℃; for 14h; 12 (E)-4-Acetoxy-4_-(pentafluorosulfanyl)stilbene (2e) (E)-4-Acetoxy-4_-(pentafluorosulfanyl)stilbene (2e) Palladium(II) acetate (0.5 mg, 0.002 mmol) was added to a solution of 1 (11.6 mg, 0.0365 mmol) and 4-acetoxystyrene (11.5 mg, 0.0709 mmol) in 0.22 g of 95% aqueous ethanol. The reaction mixture was stirred at room temperature for 14 h, filtered through a pad of Celite 545 with CH2Cl2, and purified by SiO2 column chromatography (1:1 hexane/CH2Cl2) to give 2e (8.5 mg, 64% yield) as colorless crystals; m.p. 177.5-178.5° C. MS (GC, EI): m/z=364 [M+], 322 [M+-COCH2], 194, 165. IR (ATR): v=1759, 1593, 1508, 1373, 1223, 833 cm-1. 1H NMR (500 MHz, CDCl3): δ=7.73 (d, J=8.7 Hz, 2H), 7.55 (d, J=8.4 Hz, 2H), 7.54 (d, J=8.7 Hz, 2H), 7.16 (d, J=16.4 Hz, 1H), 7.12 (d, J=8.4 Hz, 2H), 7.04 (d, J=16.4 Hz, 1H), 2.32 (s, 3H) ppm. 13C NMR (125 MHz, CDCl3): δ=169.4 (C), 152.6 (C), 150.7 (C), 140.4 (C), 134.2 (C), 130.9 (CH), 127.8 (2CH), 126.6 (CH), 126.3 (4CH), 122.0 (2CH), 21.1 (CH3) ppm. 19F NMR (470 MHz, CDCl3): δ=84.9 (quint, J=150 Hz, 1 F), 63.1 (d, J=150 Hz, 4 F) ppm.
  • 44
  • [ 2628-16-2 ]
  • [ 1293389-28-2 ]
  • (E)-4-(2-(5,6-difluorobenzo[c][1,2,5]thiadiazol-4-yl)vinyl)phenyl acetate [ No CAS ]
  • C26H18F2N2O4S [ No CAS ]
  • 45
  • [ 2628-16-2 ]
  • [ 61654-67-9 ]
  • C17H16O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With palladium diacetate; tetra-(n-butyl)ammonium iodide; sodium carbonate In N,N-dimethyl-formamide at 20 - 100℃; for 10h; Inert atmosphere; Typical procedure for the Mizoroki-Heck reaction of 10 and 11 Toa stirred solution of 10 (116 mg, 0.53 mmol) in dry DMF (1.5 mL) kept at r.t. under argon were added dry Na2CO3 (169 mg, 1.60 mmol), tetrabutylammonium iodide (233 mg, 0.63 mmol), Pd(OAc)2 (5.9 mg,5 mol %) and 11 (172 mg, 1.06 mmol). The mixture was heated to 100°C for 10 h. Then EtOAc (20 mL), benzene (10 mL) and H2O(20 mL) were added. The organic layer was separated and washed with H2O (20 mL) and dried over Na2SO4. After filtration and evaporation, the residue was chromatographed on silica gel (hexane/EtOAc 2 : 1) to provide the 2,3-dihydrobenzofuran 13 as a brown solid.
  • 46
  • [ 2628-16-2 ]
  • [ 101-42-8 ]
  • 4-(1-(dimethylcarbamoyl)-1H-indol-2-yl)phenyl acetate [ No CAS ]
  • 47
  • [ 2628-16-2 ]
  • [ 5405-15-2 ]
  • 4-(6-methyl-2-phenylquinolin-4-yl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With trifluorormethanesulfonic acid; oxygen at 120℃; for 24h;
41% With oxygen; tris(p-bromophenylammoniumyl) hexachloroantimonate In acetonitrile at 60℃; for 24h;
  • 48
  • [ 2628-16-2 ]
  • Umemoto's reagent [ No CAS ]
  • 4-(1-chloro-3,3,3-trifluoropropyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With chloro-trimethyl-silane; tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate In chloroform at 20℃; for 2.5h; Irradiation; Inert atmosphere; Three-Component Photoredox-Mediated Chloro-, Bromo-, or Iodotrifluoromethylation of Alkenes; General Procedures General procedure: Procedure A: A test tube was charged with the corresponding styrene1 (0.1 mmol), Umemoto reagent 2a (40.8 mg, 0.12 mmol, 1.2 equiv), and Ru(bpy)3(PF6)2 (4a; 0.9 mg, 0.001 mmol, 0.01 equiv). The mixture was dissolved in distilled CHCl3 (2 mL), and TMSCl (38 μL, 0.3 mmol, 3 equiv) was added. The solution was then irradiated with blue LEDs at r.t. for 2.5 h. The solvent was removed in vacuo. The residue was purified by flash chromatography on silica gel (heptanes-EtOAc, from 100:0 to 90:10) to afford the corresponding pure trifluoromethylated product.
  • 49
  • [ 2628-16-2 ]
  • Umemoto's reagent [ No CAS ]
  • 4-(1-bromo-3,3,3-trifluoropropyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; caesium bromide In acetonitrile at 20℃; for 2.5h; Irradiation; Inert atmosphere; Three-Component Photoredox-Mediated Chloro-, Bromo-, or Iodotrifluoromethylation of Alkenes; General Procedures General procedure: Procedure C: A test tube was charged with the corresponding alkene (0.1 mmol), Umemoto reagent 2a (40.8 mg, 0.12 mmol, 1.2 equiv), and Ru(bpy)3(PF6)2 (4a; 0.9 mg, 0.001 mmol, 0.01 equiv). The mixture was dissolved in distilled MeCN (2 mL), and CsBr or CsI (0.3 mmol, 3 equiv) was added. The solution was then irradiated with blue LEDs at r.t. for 2.5 h. The solvent was removed in vacuo. The residue was purifiedby flash chromatography on silica gel (heptanes-EtOAc, from100:0 to 90:10) to afford the corresponding pure trifluoromethylated product.
  • 50
  • [ 2628-16-2 ]
  • 1-(4-acetic acid phenyl ester)-2-nitro-ethanone oxime [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With tert.-butylnitrite; water In N,N-dimethyl-formamide at 50℃; for 1.5h; Inert atmosphere; Schlenk technique; stereoselective reaction; Typical reaction procedure for the synthesis of 2a General procedure: 1a (0.25 mmol) and TBN (0.50 mmol) were respectively added to the solvent of DMSO and water (v : v = 20:1, 1.0 ml) or DMF and water (v : v = 20:1, 1.0 ml) in a Schlenk tube. The tube was vacuumized and degassed with nitrogen for several times. The mixture was then stirred at 50 °C for 1.5 h. When the reaction was finished, appropriate ethyl acetate was added to the mixture and DMSO or DMF were extracted by water. The obtained organic phase was evaporated to remove the solvent and the resulting residue was further purified by flash column chromatography using petroleum ether/ethyl acetate (v : v = 3:1) to afford the product 2a.
61% With tert.-butylnitrite In water; dimethyl sulfoxide at 20℃; for 12h; Experimental Section: General procedure: To a 25 mL round bottom flask charged with a magnetic stir-bar was added H2O (0.5 mL),Styrene (0.5 mmol), tert-butyl nitrite (1 mmol) and DMSO (1 mL).Then the reaction mixture wasstirred at room temperature for 12h. After the reaction was finished, the mixture was diluted withCH2Cl2, washed with brine and extracted with CH2Cl2. The combined organic extracts were driedover Na2SO4, concentrated in vacuum, and the resulting residue was purified by silica gel columnchromatography (petroleum ether/ethyl acetate=5:1) to afford the desired product. The Z/E ratioswere determined from the signals of CH2 groups connected to the nitro group.
  • 51
  • [ 2628-16-2 ]
  • 1-(p-toluenesulfonylamino)-pyridinium tetrafluoroborate [ No CAS ]
  • C17H19NO5S [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With tris[2-phenylpyridinato-C2,N]iridium(III) In water; acetone at 20℃; for 4h; Schlenk technique; Inert atmosphere; Irradiation;
86% With tris[2-phenylpyridinato-C2,N]iridium(III); water In acetone at 20℃; for 4h; Irradiation; Inert atmosphere; 5.4 Synthesis of N- (2-hydroxy-2- (4- (boronic pinacol ester) phenyl) ethyl) -4- methylbenzenesulfonamide According to the above general method, 4-acetoxystyrene (compound 2c) (64.8 mg, 0.400 mmol), 1-(P-toluenesulfonylamino) -pyridinium tetrafluoroborate (Compound 1a) (148.2 mG, 0.441 mmol), and fac- [Ir (ppy) 3] (2.6 mg, 3.97 μmol) using silica gel column chromatographyAfter purification by chromatography (hexane / EtOAc = 3: 1), compound 3ac was obtained as a colorless solid(118.8 mg, yield 86%, reaction time = 4 h).
  • 52
  • [ 2628-16-2 ]
  • [ 1402404-17-4 ]
  • 4-((1SR,2RS)-2-(4-acetyl-5-methylfuran-2-yl)-2-(trimethylsilyl)cyclopropyl)phenylacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With zinc(II) chloride In 1,2-dichloro-ethane at 50℃; for 22h; Inert atmosphere; Schlenk technique; (16) Representative Procedure: General procedure: To a solution of enynone 1 (0.30 mmol) and alkene 2 (1.8 mmol, 6.0 equiv) in 1,2-dichloroethane (3.0 mL, 0.10 M), ZnCl2 (4.0 mg, 10 mol%) was added at ambient temperature. The Schlenk flask was placed in a preheated oilbath at 50 °C and the reaction mixture was stirred until consumption of 1 (TLC analysis). After elimination of the solvent, purification by flash column chromatography (SiO2, hexane-EtOAc) afforded the corresponding cyclopropanes 3. Characterizationdata for compound 3a: 1H NMR (300 MHz, CDCl3): δ =7.05-7.23 (m, 3 H), 6.92-7.03 (m, 2 H), 5.86 (s, 1 H), 2.37 (s, 3H), 2.34 (dd, J = 7.9, 6.1 Hz, 1 H), 2.25 (s, 3 H), 1.63 (dd, J = 6.0,4.8 Hz, 1 H), 1.39 (dd, J = 7.8, 4.8 Hz, 1 H), 0.09 (s, 9 H). 13C NMR(75 MHz, CDCl3): δ = 194.4 (C), 156.6 (C), 153.9 (C), 138.3 (C),127.9 (CH), 127.6 (CH), 125.9 (CH), 121.6 (C), 107.5 (CH), 29.0(Me), 26.9 (CH), 17.7 (C), 15.1 (CH2), 14.2 (Me), -2.9 (Me). HRMS(ESI): m/z [M]+ calcd for C19H24O2Si: 312.1546; found: 312.1543.
  • 53
  • [ 156-60-5 ]
  • [ 2628-16-2 ]
  • (E)-4-(2-chlorovinyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With C56H65F5MoN2O In benzene at 22℃; diastereoselective reaction;
75% With C56H65F5MoN2O In benzene at 22℃; for 4h; Glovebox; Inert atmosphere; (£)-4-(2-Chlorovinyl)phenyl acetate (E2) [00337] (£)-4-(2-Chlorovinyl)phenyl acetate (E2): Following the general procedure, a solution of Mo-El in benzene (0.1 M, 24 μ,, 2.4 μηιο, 3 mol %) was transferred by syringe to an oven-dried vial containing E-l,2-dichloroethene (77.6 mg, 0.8 mmol, 10.0 equiv) and 4- acetoxystyrene (13.0 mg, 0.0800 mmol, 1.00 equiv). The resulting solution was allowed to stir for 4 hours at 22 °C. The reaction was quenched by addition of wet CDCI3 and analysis of the unpurified mixture revealed >98% consumption of 4-acetoxystyrene. The resulting orange oil was purified by silica gel chromatography (10: 1 hexanes/Et20) to afford E2 (11.8 mg, 0.0600 mmol, 75% yield) in >98:2 E:Z ratio as off-white solid. 1H NMR (400 MHz, CDC13): δ 7.30 (2H, d, J = 8.8 Hz), 7.06 (2H, d, J = 8.9 Hz), 6.81 (1H, d, J = 13.7 Hz), 6.60 (1H, dd, J = 13.7 Hz), 2.30 (4H, s).
  • 54
  • [ 2628-16-2 ]
  • [ 13031-41-9 ]
YieldReaction ConditionsOperation in experiment
88% With formic acid; sodium nitrite In acetonitrile at 70℃; for 4h; Schlenk technique; 2. Typical procedure for the synthesis of nitriles from olefins General procedure: A Schlenk tube was charged with olefins 1 (0.4 mmol), NaNO2 (138 mg, 2 mmol), HCOOH (0.5 mL, 10 mmol), and CH3CN(4.5mL). The reaction mixture was stirred at 70 °C under air atmosphere for 4 h. After cooling to room temperature, the solution was filtered to remove the solid by-product then was washed with ethyl acetate (3×10 mL). The solution was concentrated under vacuum and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to obtain the desired product 2.
88.9% With formic acid; 5,10,15,20‐tetrakis‐(4‐sulfonatophenyl)‐porphyrin‐iron(III) chloride; sodium nitrite In acetonitrile at 70℃; for 4.5h; 18 Synthesis of p-acetoxybenzonitrile To the reaction tube was added 0.4 mmol of p-acetoxybenzene styrene, 2 mmol of sodium nitrite,3 mg of metallic iron (III) porphyrin and 4.5 ml of acetonitrile solvent were added, heated and stirred at 70 ° C in an air atmosphere,0.5 ml of formic acid was added dropwise within the first 0.5 hours, and after 4 hours of reaction, heating and stirring were stopped, and the mixture was cooled to room temperature,The crude product was obtained by rotary evaporator, and then purified by column chromatography to give the desired product,The column eluant used was a mixed solvent of petroleum ether and ethyl acetate.Acetoxybenzonitrile has the following structure:The compound is a white solid with a yield of 88.9% and its nuclear magnetic data is as follows:
  • 55
  • [ 2628-16-2 ]
  • [ 434-90-2 ]
  • C28H14F8O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
94.2% With water; potassium hydroxide; In diethylene glycol dimethyl ether; at 45℃; for 15h;Inert atmosphere; Example 2 Synthesis of Fluorinated Aromatic Compound (A-1) Into a 200 mL three-necked flask equipped with a three-way cock for introducing nitrogen, and a thermocouple thermometer, 10.0 g of <strong>[434-90-2]perfluorobiphenyl</strong> and 12.2 g of p-acetoxystyrene were put and dissolved in 60 g of diglyme. Then, 20.6 g of a 48% potassium hydroxide aqueous solution was added and stirred for a reaction. The temperature of the reaction solution was controlled at 45 C., and the reaction was conducted for 15 hours. Then, the reaction crude liquid was dropped into 312 g of 0.5N hydrochloric acid, whereby a white solid precipitated. The obtained solid was collected by filtration and washed twice with ion-exchanged water, to obtain 15.1 g (yield: 94.2%) of the fluorinated aromatic compound (A-1) as white solid. With respect to the obtained fluorinated aromatic compound (A-1), analyses by NMR were conducted, whereby results similar to those in Example 1 were obtained. Tg=0.1 C., Tm1=81.6 C., Tm2=108.9 C. The reason as to why Tg and Tm are different from Example 1 is considered to be error due to the data analysis.
94.2% With potassium hydroxide; In diethylene glycol dimethyl ether; N,N-dimethyl acetamide; water; at 45℃; for 15h;Inert atmosphere; For introducing nitrogen in a three-way piston, of the thermocouple thermometer 200 ml of the 3 input mouth flask in 10.0g <strong>[434-90-2]perfluorobiphenyl</strong>, 12.2g the acetoxy styrene, the dissolved in 60g after diethylene glycol dimethyl ether, added 48% aqueous solution of potassium hydroxide of 20.6g, to enable its reaction stirring. Controlling the temperature of the reaction liquid 45 C, for 15 hours reaction. Furthermore, to the reaction thick bubble 312g0.5N when the hydrochloric acid, with the white solid precipitated. The solid obtained by separation by filtration, ion-exchange water for 2 times of cleaning, as a white solid of the fluorine-containing aromatic compound (A-1) 15.1g (yield 94.2%).
  • 56
  • [ 2628-16-2 ]
  • [ 434-64-0 ]
  • C31H21F5O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With water; potassium hydroxide In diethylene glycol dimethyl ether at 45℃; for 15h; Inert atmosphere; 7 Example 3 Synthesis of Fluorinated Aromatic Compound (A-2) Example 7 Synthesis of Fluorinated Aromatic Compound (A-2) Into a 1 L four-necked flask equipped with a three-way cock for introducing nitrogen and a thermocouple thermometer, 20.1 g of perfluorotoluene and 51.4 g of p-acetoxystyrene were put and dissolved in 143.3 g of diglyme. Then, 73.4 g of a 48% sodium hydroxide aqueous solution was added and stirred for a reaction. The temperature of the reaction solution was controlled at 45° C., and the reaction was conducted for 15 hours. Then, the reaction crude liquid was dropped in 497.7 g of 0.1 N hydrochloric acid, whereby a white solid precipitated. The obtained solid was collected by filtration and washed twice with ion-exchanged water, to obtain 39.4 g (yield: 86.0%) of the fluorinated aromatic compound (A-2) as white solid. With respect to the obtained fluorinated aromatic compound (A-2), analyses by NMR were conducted, whereby results similar to those in Example 3 were obtained. Tg=-0.1° C., Tm1=122.7° C., Tm2=130.6° C. The reason as to why Tg and Tm are different from Example 3 is considered to be error due to the data analysis.
86% With sodium hydroxide In diethylene glycol dimethyl ether at 60℃; for 6h; Inert atmosphere; 7 Embodiment 7: fluorine-containing aromatic compound (A-2) synthetic For introducing nitrogen in a three-way piston, thermocouple thermometer of the 1L the 4 input mouth flask in 20.1g perfluorinated toluene, 51.4g the acetoxy styrene, the dissolved in 143.3g after diethylene glycol dimethyl ether, by adding 48% sodium hydroxide aqueous solution of 73.4g, to enable its reaction stirring. The temperature control of the reaction liquid in the 45 °C, to enable its reaction 15 hours. Furthermore, to the reaction thick bubble 497.7g0 . 1N when the hydrochloric acid, with the white solid precipitated. The solid obtained by separation by filtration, ion-exchange water for 2 times of cleaning, as a white solid of the fluorine-containing aromatic compound (A-2) 39.4g (yield 86.0%).
  • 57
  • [ 2628-17-3 ]
  • [ 75-36-5 ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
87.7% With 10H-phenothiazine; triethylamine In tert-butyl methyl ether at -5 - 20℃; for 1h; Green chemistry; 1; 3; 4 Example 1 Add p-hydroxystyrene (120g) to a 2L four-neck bottle. triethylamine(106g), phenothiazine (1.2g), Methyl tert-butyl ether (480 g), Dry ice-ethanol bath to -5 to 0 °C, acetyl chloride (86g) was added dropwise with stirring. The internal temperature is controlled at -5 to 0 °C. After the completion of the dropwise addition, the temperature was raised at 10 to 20 °C to continue the reaction for 1 hour. Sampling analysis (central control 1, raw material After completion of the reaction, the mixture was filtered, and the cake was washed with methyl t-butyl ether (50 g × 3). The filtrate was quenched by the addition of 4 g of methanol, and the reaction was stirred for 10 minutes. After completion, phenothiazine (1.2 g) was added and the reaction mixture was concentrated.Methyl tert-butyl ether (580 g) was recovered to give a crude product (160 g).The crude product was distilled under reduced pressure to give the product, p-acetoxy styrene (142 g), yield 87.7%, and sampled for analysis (main content >99%).
72% With triethylamine In dichloromethane at 0 - 20℃; for 24h;
69% With triethylamine In dichloromethane at 0℃; for 3h;
With triethylamine In dichloromethane at 20℃;

  • 58
  • [ 617-86-7 ]
  • [ 2628-16-2 ]
  • (E)-4-(2-(triethylsilyl)vinyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With dimanganese decacarbonyl; N,N-bis(diphenylphosphino)isopropylamine at 140℃; for 24h; Sealed tube; 3 Embodiment 3 Add decacarbonyl dimanganese (19 mg, 0.05 mmol), ligand 1 (43 mg, 0.10 mmol) and trifluorotoluene (0.2 mL) to the dried sealed tube and stir at 80 ° C for 1 h.Then (162 mg, 1.00 mmol) and HSiEt3 (116 mg, 1.00 mmol) were added. The reaction system continued to react at 140 ° C for 24 h. After the reaction was completed, it was cooled to room temperature.The reaction solution was concentrated, and column chromatography yielded 233 mg of the product (eluent: petroleum ether: ethyl acetate = 20: 1) in a yield of 84%.
84% With dimanganese decacarbonyl; N,N-bis(diphenylphosphino)isopropylamine at 140℃; for 24h; Sealed tube; General procedure for the dehydrosilylation reaction of non-gaseous alkenes General procedure: To an oven-dried 10-ml sealed tube, [Mn2(CO)10] (5 mol%), iPrPNP ligand (L12; 10 mol%, 0.1 mmol) and PhCF3 (0.2 ml) were added under air conditions and the mixture was stirred at 80 °C for 50 min to 1 h to become a deeply red homogeneous solution. Alkene (1.0 mmol) and silane (1.0 mmol) were then rapidly added, successively, into the sealed tubes with a liquid-transferring gun. The resulting yellow reaction mixture was rigorously stirred at 140 °C for 24 h. Once the reaction was finished, the solvent was removed under vacuum and the resulting residue was purified by column chromatography on silica gel to afford the products.
81% With norborn-2-ene; chloro(1,5-cyclooctadiene)rhodium(I) dimer; triphenylphosphine In tetrahydrofuran at 100℃; for 2h; Schlenk technique; Inert atmosphere; Sealed tube;
45% With di-tert-butyl peroxide; copper diacetate In <i>tert</i>-butyl alcohol at 110℃; for 24h; Inert atmosphere; stereoselective reaction;

  • 59
  • [ 2628-16-2 ]
  • [ 1666-13-3 ]
  • 4-[1-hydroxy-2-(phenylselanyl)ethyl]phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With iodosylbenzene; water In acetonitrile at 20℃; for 20h; diastereoselective reaction;
79% With water; iodine In ethyl acetate at 20℃; for 12h; regioselective reaction; Typical Procedure for the I2-mediated hydroxyselenenylation of alkenes General procedure: Alkenes 1 (0.24 mmol), diselenides 2 (0.10 mmol) and I2 (0.10 mmol) were added successively to MeCN/H2O (v/v, 1/1) (3 mL). The mixture was vigorously stirred at r. t. for 12 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL),sat. aq. Na2CO3 (2 mL) and H2O (5 mL), respectively. The mixture was extracted with CH2Cl2 (3×5 mL) and the combined organic phase was dried over anhydrous Na2SO4,filtered, and concentrated under reduced pressure. The residue was then purified on a silica gel plate (4:1 petroleum ether-ethyl acetate) to furnish products 3.
68% With ammonium iodide; water; 3-chloro-benzenecarboperoxoic acid In ethyl acetate at 20℃; for 3h; regiospecific reaction;
With dihydrogen peroxide In water; acetonitrile at 60℃; for 10h; Sealed tube;

  • 60
  • [ 524-38-9 ]
  • [ 2628-16-2 ]
  • 4-(2-((1,3-dioxoisoindolin-2-yl)oxy)-1-hydroxyethyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With tert.-butylhydroperoxide; oxygen In decane; 1,2-dichloro-ethane at 20℃; for 48h; 1 Typical procedure for the synthesis of product 3 General procedure: To a solution of N-hydroxyphthalimide (2, 0.3 mmol, 48.9 mg) in DCE (3.0 mL) was added styrene (1a, 0.6 mmol), 10% TBHP (5-6 M in decane). The flask was evacuated and back filled with O2 for three times. The reaction mixture was then stirred for 24 h at room temperature. After the reaction, the resulting mixture was quenched with water and extracted twice with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4 and concentrated. Purification of the crude product by flash column chromatography afforded the product 3a (petroleum ether/ethyl acetate as eluent (6:1)).
50% With cobalt(II) chloride hexahydrate; oxygen In 1,2-dichloro-ethane at 40℃; for 12h; Sealed tube;
  • 61
  • [ 878-00-2 ]
  • [ 1779-49-3 ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
60.91% With potassium carbonate In tetrahydrofuran at 70℃; for 24h; 1.2 (2) Synthesis of 3 4-acetoxybenzaldehyde (2.0 g, 12.18 mmol) was added to a 100 mL round bottom flask, then dissolved in 50 mL of tetrahydrofuran, then potassium carbonate (1.9 g, 13.75 mmol) was added, and finally methyltriphenyl was added. Phosphine bromide(4.8 g, 13.44 mmol), heated at 70 ° C (degrees Celsius), after 24 h, detected by TLC, the reaction was completed. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with ethyl acetate (50 mL×3). The organic phase was combined, washed with brine (100 mL×3), and dried over anhydrous sodium sulfate. Chromatography (ethyl acetate: petroleum ether = 1 : 100, 1L) eluted toield of pale yellow oily material: 4- acetoxy styrene (3) 1.2 g, yield 60.91%.
With potassium carbonate In 1,4-dioxane for 16h; Reflux;
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: 4-formylphenyl acetate In tetrahydrofuran at 0 - 20℃; for 10h; Inert atmosphere;
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: 4-formylphenyl acetate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; Stage #2: 4-formylphenyl acetate In tetrahydrofuran at 0 - 20℃; General procedure for the preparation of substituted olefin: General procedure: An oven-dried round-bottom flask was charged with CH3PPh3Br (1.5 equiv.) or CH3CH2PPh3Br (1.5equiv.) and THF (carbonyl substrate concentration = 0.2 M). tBuOK (1.5 equiv.) was added to thesuspension at 0 °C. The resulting mixture was allowed to warm up to room temperature and stirred for 1h. The yellow suspension was cooled to 0 °C again followed by portion-wise addition of the carbonylsubstrate (1 equiv.). Subsequently, the mixture was further stirred at room temperature for 1-12 hours.After the completion of the reaction, the solvent was removed by evaporation, the resulting mixture wasdiluted with water (30 mL) and extract with dichloromethane (3 x 20 mL), and the combined organiclayer was dried with anhydrous Na2SO4. Concentration in vacuo followed by silica gel columnpurification with petroleum ether/ethyl acetate eluent gave the desired product in yields range from 50-95%.

  • 62
  • [ 2628-16-2 ]
  • [ 624-38-4 ]
  • 1,4-bis[(E)-2-(4-acethoxyphenyl)ethenyl]benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With triphenyl phosphite; triethylamine; bis(dibenzylideneacetone)-palladium(0) In N,N-dimethyl-formamide at 110℃; for 48h; Sealed tube; Inert atmosphere; 2.4. Synthesis of oligo(phenylene vinylene)s 1a-i and 2a-g General procedure: according to the Mizoroki-Heck reaction (Scheme 1). First; by thecoupling between 4-substituted styrenes and dibromo or diiodobenzenes(Method A, Scheme 1), and second; the reaction between4-substituted bromo or iodobenzenes with 1,4-divinylbenzene(Method B, Scheme 1).The general procedure is as follows: 2.05 equivalents of thecorresponding styrene and 1 equivalent of 1,4-dibromo or 1,4-diiodobenzene (Method A, to OPVs 1a-d and 2a-f) or 2.05 equivalentsof the appropriate aryl halide and 1 equivalent of 1,4-divinylbenzene (Method B, to OPVs 1e-h), were placed in a 10 mLheadspace crimp vial equipped with a magnetic stir bar. Then, forboth methods, it was added 0.01 equivalents (1 mol%) of Pd(dba)2,0.1 equivalents (10 mol%) of P(OPh)3 and 5 equivalents of TEA. Thevial was sealed with a PTFE/silicone septum with aluminum capand purged-saturated with N2, then 2 mL of solvent was injected(dry DMF for OPVs-series 1 and 1,4-dioxane for OPVs-series 2,Scheme 1) and the system was purged once again with N2. Thereaction mixture was vigorously stirred at 110 C during 48 h forOPVs-series 1 and 24 h for OPVs-series 2. After finished, highlyfluorescent solid products were obtained.
  • 63
  • [ 2628-16-2 ]
  • [ 133745-75-2 ]
  • N,N'-(1-(4-acetoxyphenyl)ethane-1,2-diyl)bis(N-(phenylsulfonyl)benzenesulfonamide) [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With (N,N'-bis(3,5-di-tert-butylsalicylidine)-1,2-benzenediamine(-2H))cobalt(II); triphenylphosphine In ethyl acetate at 60℃; for 10h; Schlenk technique; Inert atmosphere;
74% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 2,2,6,6-tetramethylheptane-3,5-dione; 1,1,1,2,2,2-hexamethyldisilane; tetrabutyl-ammonium chloride; copper(l) chloride In acetonitrile at 70℃; for 2h; Schlenk technique; Inert atmosphere; Representative procedure for the diamination of alkenes : (Table 2) General procedure: An oven-dried, 5 mL Schlenk flask equipped with a stir bar was place under an atmosphere of N2. CuCl (2.45 mg, 0.025 mmol%, 5 mol%) and dissolved in 0.5 mL fresh distilled CH3CN. 2,2,6,6-Tetramethyl-5-heptanedione (TMHD, 4.7 mg, 5.7μL, 0.025 mmol%, 5 mol%), 2,2,6,6-tetramethyl piperidine N-oxy radical (TEMPO, 11.7 mg, 0.075 mmol, 15 mol%) and hexamethyldisilane (150 mg, 154 μL, 0.75 mmol%, 1.5 equiv) were sequentially added to the above solution and stirred for 20 min. N-Fluorobenzenesulfonimide (472 mg, 1.5 mmol, 3.0 equiv) and styrene (57 μL, 0.5 mmol, 1.0 equiv) were dissolved in 0.5 mL fresh distilled CH3CN and added to the flask via a syringe at room temperature under nitrogen atmosphere. The resulting mixture was heated to 70 °C on a preheated oil spot, and the reaction progress was monitored by TLC analysis. After completion of the reaction, the mixture was cooled to 0°C, and quenched with 2 mL ofice-cold sat. NaHCO3 (aq). The remaining material was extracted three times with ethyl acetate (10mL) and the organic layer was dried with Na2SO4, and filtrated. Evaporation of the organic solvent and the resulting mixture was purified by column chromatography on silica gel (hexane-AcOEt 7:1) to afford the aminoalcohol 1a (247 mg, 71% yield) as a white solid.
  • 64
  • [ 2628-16-2 ]
  • [ 360068-17-3 ]
YieldReaction ConditionsOperation in experiment
93% With acetic acid; lithium bromide at 25℃; for 2h; Green chemistry; 8 Example 8 2 mmol (0.324 g) 4-acetoxystyrene, 4.0 mmol (0.347 g) lithium bromide was added to a 50 mL three-necked flask,12 mL of acetic acid was added as a solvent, and then 1.2 g of Zn-Al hydrotalcite ZnAl-BrO3--LDHs intercalated with bromate was added and magnetically stirred at 25° C. for 2 hours, and the reaction was complete by TLC.After the reaction is completed, the obtained reaction solution is centrifuged at 6500 r/min to remove zinc aluminum hydrotalcite solids, and the resulting liquid is placed in a separatory funnel, and methylene chloride and deionized water are added.The organic material should be extracted into the dichloromethane phase. The resulting solution is loaded with column chromatography silica gel, and the solvent is removed by distillation under reduced pressure.The remaining mixture was separated by column chromatography and collected with a mixture of petroleum ether and ethyl acetate in a volume ratio of 10:1 as eluent.The eluent containing the product, the eluent was evaporated to give the pure product. This material was found to have a yield of 93%.
With urea hydrogen peroxide adduct; trifluoroacetic acid; lithium bromide In acetonitrile at 80℃; for 1h;
With bromine In tetrachloromethane at 0 - 20℃; for 12.1667h;
With bromine In tetrachloromethane at 15 - 20℃; for 2h;

  • 65
  • [ 2628-16-2 ]
  • [ 80-17-1 ]
  • C16H14O5S [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With tert.-butylhydroperoxide; tetrabutylammomium bromide; oxygen In acetonitrile at 60℃; Schlenk technique; Green chemistry; General procedure: n-Bu4NBr (16.1 mg, 0.1 mmol) and TBHP (tert-butylhydroperoxide,46.0 mg, 1.0 mmol) were added to a solutionof styrene (1a, 52.0 mg, 0.5 mmol) and benzenesulfonohydrazide(2a, 94.6 mg, 0.55 mmol) in acetonitrile (2.0mL). The mixture was stirred at 60 °C for 8.0 h in a Schlenktube and a balloon filled with O2 was attached to the sidearm. The reaction was monitored by TLC before it wasquenched with water (10 mL) and extracted with dichloromethane(5×3 mL). The extracted organics were dried overanhydrous sodium sulfate and the solvent was removed underreduced pressure. The residue was purified by flash silicagel column chromatography using ethyl acetate/petroleumether (1:6) as eluent to give the desired compound 3aas a white solid (252.0 mg, 84%).
  • 66
  • [ 2628-16-2 ]
  • [ 5460-32-2 ]
  • [ 880354-47-2 ]
YieldReaction ConditionsOperation in experiment
With tetrabutylammomium bromide; potassium acetate; palladium diacetate; In N,N-dimethyl-formamide; at 80℃; for 5h;Inert atmosphere; Sealed tube; General procedure: To a solution of tetrabutylammonium bromide (1.100 g, 3.33 mmol), potassium acetate (0.586 g, 3.57 mmol), and palladium acetate (0.025 g, 0.11 mmol) in DMF (20 mL) were added substituted iodobenzene (2.21 mmol) and 4-acetyloxystyrene (2.44 mmol). The reaction mixture was recharged with Argon and stirred at 80C for 5 h in a sealed tube. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10:3) to afford the intermediate substituted (E)-4-styrylphenyl acetate. To a solution of triethylamine (2.0 mL) in MeOH (5 mL) was added substituted (E)-4-styrylphenyl acetate (1.36 mmol). The reaction mixture was stirred at reflux temperaturefor 3 h. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (dichloromethane/methanol, 10:0.3) to afford pure product.
  • 67
  • [ 2628-16-2 ]
  • [ 198206-33-6 ]
  • (E)-4-(3-(trifluoromethoxy)styryl)phenol [ No CAS ]
  • 68
  • [ 2628-16-2 ]
  • [ 198206-33-6 ]
  • C17H13F3O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrabutylammomium bromide; potassium acetate; palladium diacetate; In N,N-dimethyl-formamide; at 80℃; for 5h;Inert atmosphere; Sealed tube; General procedure: To a solution of tetrabutylammonium bromide (1.100 g, 3.33 mmol), potassium acetate (0.586 g, 3.57 mmol), and palladium acetate (0.025 g, 0.11 mmol) in DMF (20 mL) were added substituted iodobenzene (2.21 mmol) and 4-acetyloxystyrene (2.44 mmol). The reaction mixture was recharged with Argon and stirred at 80C for 5 h in a sealed tube. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10:3) to afford the intermediate substituted (E)-4-styrylphenyl acetate. To a solution of triethylamine (2.0 mL) in MeOH (5 mL) was added substituted (E)-4-styrylphenyl acetate (1.36 mmol). The reaction mixture was stirred at reflux temperaturefor 3 h. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (dichloromethane/methanol, 10:0.3) to afford pure product.
  • 69
  • [ 2628-16-2 ]
  • [ 5876-51-7 ]
  • [ 1637752-58-9 ]
YieldReaction ConditionsOperation in experiment
81.9% With tetrabutylammomium bromide; potassium acetate; palladium diacetate; In N,N-dimethyl-formamide; at 80℃; for 5h;Inert atmosphere; Sealed tube; General procedure: To a solution of tetrabutylammonium bromide (1.100 g, 3.33mmol), potassium acetate (0.586 g, 3.57 mmol), and palladium acetate (0.025 g, 0.11mmol) in DMF (20 mL) were added substituted iodobenzene (2.21mmol) and substituted styrene (2.44 mmol). The reaction mixture was recharged with argon and stirred at 80C for 5 h in a sealed tube. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10:3) to afford pure product.
  • 70
  • [ 2628-16-2 ]
  • [ 25245-27-6 ]
  • (E)-1-(4'-acetoxyphenyl)-2-(3,5-dimethoxyphenyl)ethene [ No CAS ]
YieldReaction ConditionsOperation in experiment
93.7% With tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl-formamide at 80℃; for 5h; Inert atmosphere; Sealed tube; General Procedure for Synthesis of the Compounds as Shown in the Scheme S1 General procedure: To a solution of tetrabutylammonium bromide (1.100 g, 3.33mmol), potassium acetate (0.586 g, 3.57 mmol), and palladium acetate (0.025 g, 0.11mmol) in DMF (20 mL) were added substituted iodobenzene (2.21mmol) and substituted styrene (2.44 mmol). The reaction mixture was recharged with argon and stirred at 80°C for 5 h in a sealed tube. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10:3) to afford pure product.
82% With triethylamine In toluene Reflux; 55 Carbon-Carbon Bond forming Reaction using Polymer-Supported Metal Catalyst A toluene (PhMe) solution containing 1.0 mmol of iodobenzene (A), 1.1 mmol of acrylic acid (B) and 1.5 mmol of triethylamine (NEt3) is prepared and 0.05 mmol of a palladium catalyst is added to be stirred in heating reflux conditions for several hours. Dichloromethane is then added, and the palladium catalyst is removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain transcinnamic acid (C), which is a corresponding coupling body, in a white solid. Results are shown in Examples 51 to 54 Table 3. As shown in Example 55, instead of iodobenzene and acrylic acid, 1.5 mmol of 3,5-dimethoxy iodobenzene (D) and 3.0 mmol of 4-acetoxystyrene (E) are used respectively to obtain trans-4-acetoxy-3’-S’-dimethoxy stilbene (F) in a white solid.
74% With 3-(anthracen-9-ylmethyl)-1-(3-(3,6-dichloro-9H-carbazol-9-yl)-2-hydroxypropyl)-1H-imidazol-3-ium chloride; palladium diacetate; triethylamine In acetonitrile at 120℃; for 24h; Schlenk technique; Inert atmosphere; chemoselective reaction;
  • 71
  • [ 2628-16-2 ]
  • [ 2265-91-0 ]
  • (E)-1-hydroxy-4-(3,5-difluoro)styrylbenzene [ No CAS ]
  • 72
  • [ 2628-16-2 ]
  • [ 2265-91-0 ]
  • (E)-3,5-difluoro-4'-acetoxystilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrabutylammomium bromide; potassium acetate; palladium diacetate; In N,N-dimethyl-formamide; at 80℃; for 5h;Inert atmosphere; Sealed tube; General procedure: To a solution of tetrabutylammonium bromide (1.100 g, 3.33 mmol), potassium acetate (0.586 g, 3.57 mmol), and palladium acetate (0.025 g, 0.11 mmol) in DMF (20 mL) were added substituted iodobenzene (2.21 mmol) and 4-acetyloxystyrene (2.44 mmol). The reaction mixture was recharged with Argon and stirred at 80C for 5 h in a sealed tube. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10:3) to afford the intermediate substituted (E)-4-styrylphenyl acetate. To a solution of triethylamine (2.0 mL) in MeOH (5 mL) was added substituted (E)-4-styrylphenyl acetate (1.36 mmol). The reaction mixture was stirred at reflux temperaturefor 3 h. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl and concentrated in vacuo. The residue was purified by column chromatography on silica gel (dichloromethane/methanol, 10:0.3) to afford pure product.
  • 73
  • [ 2628-16-2 ]
  • C10H10N6O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With tert-Butyl peroxybenzoate; trimethylsilylazide; manganese triacetate In dichloromethane for 12h; Inert atmosphere; 3 Example 3: 15 ml of the reaction tube was added to the catalyst manganese acetate(Mn (OAc) 3 • 2H2O, 4.0 mg, 0.015 mmol, 5% mol)Pump pump vacuum,Filled with nitrogen,Repeated pumping gas 2 times,To the reaction tube was added 2 ml of dichloromethane,Plus 4-acetoxystyrene (48.7 mg, 0.3 mmol, 1.0 equiv)Plus t-butyl peroxybenzoate (84.0 [mu] L, 0.45 mmol, 1.5 eq)Plus azide trimethylsilane(TMSN3, 118 μl, 0.9 mmol, 3.0 equiv)The mixture was stirred under a nitrogen atmosphere for 12 hours,Add 2 ml of saturated sodium bicarbonate solution,Stir for 30 minutes to remove benzoic acid,After extraction with methylene chloride, the mixture was dried, evaporated to dryness of the solvent and methylene chloride. The solvent was evaporated to dryness. The residue was purified by column chromatography ()To give the product 65.1 mg,The total yield was 88%.
76% With copper(l) iodide; tert-Butyl peroxybenzoate; trimethylsilylazide In acetonitrile at 50℃; for 6h; Schlenk technique; Inert atmosphere; Green chemistry; 1.A1; 1.B1; 7 Method B1: General procedure: Adding a compound containing carbon-carbon double bonds (1 equivalent) to the Schlenk tube, CuI (10 mol%),TMSN3 (212 mg, 1.75 mmol, 3.5 equivalents), TBPB (149 mg, 0.75 mmol, 1.5 eq.) and CH3CN (2 mL) were stirred under nitrogen atmosphere at 50 ° C for 6 hours and then cooled to room temperature. The mixture was extracted with a saturated NaHCO3 solution and ethyl acetate. The organic phase was evaporated on a rotary evaporator, and the silica gel was passed through a column to obtain a diazide compound.
  • 74
  • [ 2628-16-2 ]
  • [ 20469-65-2 ]
  • [ 537-42-8 ]
YieldReaction ConditionsOperation in experiment
52%Chromat. With potassium carbonate; In ethanol; water; at 150℃; for 0.5h;Microwave irradiation; Sealed tube; Green chemistry; General procedure: The experimental procedure for MW-assisted Mizoroki-Heckcoupling reactions was carried out analogously to the procedure previously reported [47]. Into a 10 mL MW tube equippedwith a magnetic stirring bar, aryl halide 1a-h (0.25 mmol),K2CO3 (0.5 mmol), olefin 2a-d (0.3 mmol), ethanol (0.5 mL)and water (to obtain a total volume of 2 mL taking into accountthe volume of Pd NPs solution) were added. Finally, the required volume of the Pd NPs dispersion was added. Then, thereaction tube was sealed with a rubber cap and heated at130-150 C for 5-30 minutes under MW irradiation (fixed temperature method) using air cooling. After that, the reaction mixture was cooled to room temperature, extracted three times withethyl acetate (15 mL each) and dried with anhydrous Na2SO4.The stilbene products 3-15 were purified by silica gel columnchromatography. The products were characterized by 1H NMR,13C NMR, and GC-MS. All spectroscopic data were in agreement with those previously reported for the following compounds: (E)-1-(4-styrylphenyl)ethanone (3) [64], (E)-phenyl(4-styrylphenyl)methanone (4) [64], (E)-3-styrylquinoline (5) [55],(E)-1,3-dimethoxy-5-styrylbenzene (6) [64], (E)-1-methoxy-4-styrylbenzene (7) [64], (E)-1-methyl-4-styrylbenzene (8) [65],(E)-1-methyl-2-styrylbenzene (9) [65], (E)-4-styrylphenol (10)[66], (E)-4-(3,5-dimethoxystyryl)pyridine (14) [67], 1-(4-(2,2-diphenylvinyl)phenyl)ethanone (15) [56], and (E)-4-(3,5-dimethoxystyryl)phenol or pterostilbene (19) [60].
  • 75
  • [ 935-04-6 ]
  • [ 2628-16-2 ]
  • 2,2,2-trifluoroethyl ((4-(trifluoromethyl)benzoyl)oxy)carbamate [ No CAS ]
  • 4-(3-(benzyloxy)-4-(((2,2,2-trifluoroethoxy)carbonyl)amino)butanoyl)phenyl acetate [ No CAS ]
  • 76
  • [ 2628-16-2 ]
  • [ 133745-75-2 ]
  • N-[2-chloro-2-(4-acetoxyphenyl)ethyl]-N-(phenylsulfonyl)benzenesulfonamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With chloro-trimethyl-silane; dimethylsulfide; copper(II) acetylacetonate In dichloromethane at 120℃; for 1h; Inert atmosphere; Sealed tube; Microwave irradiation; regioselective reaction; A typical procedure for copper-catalyzed chloroamination of alkenes with chlorotrimethylsilane and N-fluorobenzenesulfonimide: Synthesis of N-(2-chloro-2-phenylethyl)-N-(phenylsulfonyl)benzenesulfonamide (2a) General procedure: Copper(II) acetylacetonate (10.5 mg, 0.04 mmol) and N-fluorobenzenesulfonimide (504.5 mg, 1.6 mmol) were placed in a 5-mL glass pressure vial. The vial was flushed with argon and sealed with a PTFE-silicone septum. Dichloromethane (2 mL), dimethyl sulfide (1.5 mL, 0.02 mmol), chlorotrimethylsilane (0.20 mL, 1.6 mmol), and styrene (41.6 mg, 0.4 mmol) were added. The mixture was heated at 120 °C with stirring for 1 h in the microwave reactor. The mixture was then cooled to room temperature. Water (3 mL) was added, and the product was extracted with ethyl acetate (5 mL) three times. The combined organic layers were washed with brine (5 mL) and dried over anhydrous sodium sulfate. After the volatiles were evaporated, the resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate = 5/1) to provide 2a as white solid (154.9 mg, 0.355 mmol, 89
55% With chloro-trimethyl-silane; 2.9-dimethyl-1,10-phenanthroline; saccharin sodium salt; copper(l) chloride In 1,2-dichloro-ethane at 70℃; for 16h; Sealed tube; regioselective reaction; 1.2 General procedure for the aminochlorination of alkenes General procedure: In a 10 ml vial fitted with a magnetic stirbar, CuCl (10 mg, 0.1 mmol), neocuproine (21 mg, 0.1 mmol) and 1,2-dichloroethane (4.0 mL) were stirred for 5 min. NFSI (316 mg, 1.0 mmol) and NaSac (206 mg, 1.0 mmol) were then added. The mixture was heated to 70 °C and, in that order, TMSCl (133 µL, 1.0 mL) and styrene (115 µL) were then added. The vial was sealed and the reaction mixture was stirred for 16 h. After this time, the solvent is evaporated under reduced pressure and the crude product is purified by chromatography (silica gel, petroleum ether/ ethyl acetate, 4/1, v/v) to afford 379 mg of product as a colorless oil (87% yield).
  • 78
  • [ 175676-42-3 ]
  • [ 2628-16-2 ]
  • 4-(2-azido-1-(trifluoromethoxy)ethyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
69% With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; silver fluoride; 1-azido-1λ3-benzo[d][1,2]iodaoxol-3(1H)-one; 4,4',4-tri-tert-butyl-2,2':6',2-terpyridine In acetonitrile at 10℃; for 4h; Inert atmosphere; Glovebox; Sealed tube; Irradiation;
69% With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; silver fluoride; 1-azido-1λ3-benzo[d][1,2]iodaoxol-3(1H)-one; 4,4',4-tri-tert-butyl-2,2':6',2-terpyridine In acetonitrile at 20℃; for 4h; Inert atmosphere; Sealed tube; Irradiation; 57 Example 6 1-(2-azido-1-(trifluoromethoxy)ethyl)-2,4,6-trimethylbenzene (4a) General procedure: Under the protection of N2, Ru(bpy)3(PF6)2 (2.4 mg, 0.00300 mmol, 1.0 mol%), AgF (19.2 mg, 0.150 mmol, 50.0 mol%) was added to the sealed tube. 4,4',4"-tri-tert-butyl-2,2':6',2"-terpyridine (tbtpy, 36.0 mg, 0.0900 mmol, 30.0 mol%),1-azido-1,3 benzo[d][1,2]iodohydroxy-3(1H)-one (3) (173.4 mg, 0.600 mmol, 2.00 eq.), then acetonitrile solvent (2.40 mL) ,4-phenylstyrene (1a) (43.9 mg, 0.300 mmol, 1.00 equiv), trifluoromethyl 4-methylbenzenesulfonate (2) (169 μL, 0.9 mmol, 3.00 equiv) was added to the reaction. The resulting mixture was then allowed to stand at room temperature and stirred under irradiation with a 14 W blue LED for 4 hours.After that, the reaction mixture was concentrated in vacuo and purified by silica gel chromatography.Elution with petroleum ether / ethyl acetate 100:1 (v / v) gave the corresponding product (4a), 65.5mg.
  • 79
  • [ 6935-29-1 ]
  • [ 2628-16-2 ]
  • (E)-2-(4-acetoxystyryl)quinoxaline 1-oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With Fmoc-Val-OH; palladium diacetate; silver carbonate In 1,4-dioxane at 120℃; for 12h; Inert atmosphere; Sealed tube; Alkenylation reaction: General procedure: Pd(OAc)2 (1.9 mg, 0.0085mmol, 10 mol%) Ag2CO3 (35.3 mg, 0.128 mmol, 1.5 equiv.), quinoxaline N-oxide (50 mg, 0.342 mmol, 4 equiv) and Fmoc-Val-OH (0.0138, 0.0855 mmol, 1 equiv) were added to 1 mL amber screw-capped vial, equipped with a stirring bar. Following addition of solid compounds, the vial was hermetically sealed with Teflon-lined cap, and the reaction medium was purged with nitrogen. Previously dried 1,4-dioxane (0.5 mL) and the alkene (0.0855 mmol) were added into solid mixture, with syringe assistance. The reaction mixture was stirred at 120 °C for 12 hours. The reaction was cooled until room temperature, filtered by assistance of a plug of celite, washed with ethyl acetate (30 mL), the solvent was removed under reduced pressure.
  • 80
  • [ 3017-70-7 ]
  • [ 2628-16-2 ]
  • [ 23665-09-0 ]
  • 4-(3,4-dimethyl-1-phenylpent-3-en-1-yl)phenyl acetate [ No CAS ]
  • 81
  • [ 7150-72-3 ]
  • [ 2628-16-2 ]
  • 2,2,2-trifluoroethyl ((4-(trifluoromethyl)benzoyl)oxy)carbamate [ No CAS ]
  • 4-(3-[(tert-butoxycarbonyl)amino]-4-[(2,2,2-trifluoroethoxy)carbonyl]amino}butanoyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
48% With tris[2-phenylpyridinato-C2,N]iridium(III); In dimethyl sulfoxide; at 20℃; for 6h;Inert atmosphere; Irradiation; General procedure: A 10 mL round-bottomed flask equipped with a rubber septum and a magnetic stir bar was charged with 1 (1.0 equiv), 2 (2.5 equiv), 3 (2.0 equiv), and fac-Ir(ppy)3 (0.01 equiv). The flask was evacuated and backfilled 3 times with N2. DMSO was then added with syringe under N2. The mixture was then irradiated by white LED strips. After completion of the reaction (6 h, as judged by TLC analysis), the mixture was poured into a separatory funnel containing sat. aq NaHCO3 (20mL) and EtOAc (20 mL). After extraction with EtOAc, the organic layer was separated, dried (Na2SO4), and concentrated under reduced pressure after filtration. The crude product was purified by flash chromatography on silica gel to afford the desired product 4.
  • 82
  • [ 421-83-0 ]
  • [ 2628-16-2 ]
  • 4-(1-chloro-3,3,3-trifluoropropyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With pyridine; copper dichloride In 1,4-dioxane at 100℃; for 1h; Inert atmosphere; Schlenk technique; 4.2 General procedure for chlorotrifluoromethylation of alkenes General procedure: CuCl2 (7 mg, 10 mol%), alkene (0.5 mmol), 1,4-dioxane (2 mL), CF3SO2Cl (152 mg, 1.8 eq.) and pyridine (4 mg, 10 mol%) were added into a Schlenk tube under a N2 atmosphere. The reaction mixture was stirred at 100 °C for 1 h. After being cooled to room temperature, the solid was removed by filtration and washed with DCM (30 mL). The combined organic solution was evaporated, and the resulting crude product was purified by flash column chromatography to give the products 3 or 4.
With C59H52CuN2OP2(1+)*F6P(1-); potassium carbonate In dichloromethane at 40℃; for 5h; Inert atmosphere; Schlenk technique; Glovebox; Irradiation;
  • 83
  • [ 354-58-5 ]
  • [ 2628-16-2 ]
  • 2,2,7,7-tetrachloro-1,1,1,8,8,8-hexafluoro-4,5-di(4-acetoxylphenyl)octane [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With potassium phosphate; fac-tris(2-phenylpyridinato-N,C2')iridium(III); water; triphenylphosphine; zinc(II) iodide In tetrahydrofuran at 20℃; for 12h; Schlenk technique; Inert atmosphere; Irradiation; General procedure for chloroalkylation and dimerization of styrenes General procedure: To a flame-dried Schlenk tube with a magnetic stirring bar were charged fac-[Ir(PPy)3] (3.9mg, 0.006 mmol), PPh3 (524.6mg, 2.0 mmol for products 2, 209.6mg, 0.8 mmol for products 3), K3PO4 (212.2mg, 1.0mmol), H2O (36.0mg, 2.0mmol), substrate 1 (0.2mmol), ZnI2 (319.2mg, 1.0mmol) and CF3CCl3 (187.4mg, 1.0mmol) or CCl4 (61.6mg, 0.4mmol) in THF (2mL). The flask was placed at a distance of 2 cm from the blue LEDs. The mixture was stirred under a nitrogen atmosphere and irradiated by blue LEDs for 12h. After the reaction was completed, H2O2 was added into the flask dropwise until solution become purple. Then, the mixture was poured into ethyl acetate, which was washed with saturated Na2S2O3 (2x15mL) and brine (1x15mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum. The residue was purified by flash column chromatography (petroleum ether/ethyl acetate, v/v) to afford the desired product.
With potassium phosphate; fac-tris(2-phenylpyridinato-N,C2')iridium(III); triphenylphosphine; zinc(II) iodide In tetrahydrofuran; water at 25℃; for 12h; Irradiation; Inert atmosphere; 8 Specific embodiment 8: 0.2 mmol of 4-acetoxystyrene under visible light irradiation1.0 mmol of trifluorotrichloroethane, 0.006 mmol of photo-oxidation reduction catalyst fac-[Ir(ppy)3], 2.0 mmol of deionized water,2.0 mmol of triphenylphosphine, 1.0 mmol of zinc iodide,1.0 mmol of potassium phosphate was added to 2.0 ml of tetrahydrofuran to carry out a reaction.The mixture was stirred under a nitrogen atmosphere at a temperature of 25 ° C for 12 hours.After the reaction was completed, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture.Wash with saturated sodium thiosulfate and brine. After extracting the aqueous layer with ethyl acetateThe combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo.The residue was purified by flash column chromatography.11.9 mg white solid2,2,7,7-tetrachloro-1,1,1,8,8,8 hexafluoro-4,5-bis(4-acetoxyphenyl)Octane, yield 19%.
  • 84
  • [ 887144-97-0 ]
  • [ 39965-81-6 ]
  • [ 2628-16-2 ]
  • C18H18F3NO2 [ No CAS ]
  • 85
  • [ 887144-97-0 ]
  • [ 29181-50-8 ]
  • [ 2628-16-2 ]
  • C17H13F3N2O2 [ No CAS ]
  • 86
  • [ 887144-97-0 ]
  • [ 7584-05-6 ]
  • [ 2628-16-2 ]
  • C17H16F3NO2 [ No CAS ]
  • 87
  • [ 887144-97-0 ]
  • [ 2628-16-2 ]
  • [ 68325-15-5 ]
  • C16H13ClF3NO2 [ No CAS ]
  • 88
  • [ 887144-97-0 ]
  • [ 2628-16-2 ]
  • [ 13958-98-0 ]
  • C16H13BrF3NO2 [ No CAS ]
  • 89
  • [ 2628-16-2 ]
  • [ 6971-74-0 ]
  • (E)-N-Ts-3-(4-acetoxybenzylidene)isoindolin-1-one [ No CAS ]
  • 90
  • [ 2628-16-2 ]
  • [ 21120-91-2 ]
  • 1-(4-vinylphenoxy)benzocyclobutene [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% In a 250 ml three necked round bottom flask equipped with a polytetraflouroethylene (Teflon polymer, Dupont, Wilmington, Del.) coated magnetic stir bar, potassium hydroxide (1.38 g, 1 eq) was dissolved in water (6.83 g). Then 4-acetoxy styrene (4 g, 1 eq) was added dropwise at room temperature, and the solution turned from colorless to pale orange. Potassium carbonate (6.82 g, 2 eq) was added portionwise, and the solution was stirred for one hour. The flask was equipped with a reflux condenser, then <strong>[21120-91-2]1-bromobenzocyclobutene</strong> (4.06 g, 1 eq) was added dropwise in DMF (41 ml). The solution was then heated to 70 C. and allowed to reflux overnight. To the reaction was added water (50 ml) and ethyl acetate (50 ml). The aqueous residue was extracted four times with ethyl acetate (100 ml). The combined organics were extracted with sodium bicarbonate solution (1×100 ml), lithium chloride aqueous solution (1×100 ml) and brine (2×100 ml). The organics were dried over sodium sulfate, filtered and concentrated in vacuo to give the product as a of white solid (3.36 g, 68% yield). Melting point 54-60 C. 1H NMR (600 MHz, Chloroform-d) delta 7.39 (d, J=8.6 Hz, 2H), 7.34 (td, J=7.3, 1.5 Hiz, 1H), 7.31-7.24 (m, 2H), 7.21-7.18 (m, 1H), 6.98 (d, J=8.6 Hz, 2H), 6.69 (dd, J=17.6, 10.9 Hz, 1H), 5.70 (dd, J=4.3, 1.9 Hz, 1H), 5.64 (dd, J=17.6, 0.9 Hz, 1H), 5.15 (dd, J=10.9, 0.9 Hz, 1H), 3.73 (dd, J=14.2, 4.3 Hz, 1H), 3.31 (d, J=14.2 Hz, 1H). 13C NMR (151 MHz, Chloroform-d) delta 157.79, 144.62, 142.57, 136.20, 130.87, 129.93, 127.50, 127.43, 123.48, 123.04, 115.06, 111.80, 74.28, 39.45. Yield from the above example was good and the resulting monomer was a stable solid which has a desirable ring opening cure temperature of 184 C.
  • 91
  • C10H10O2S [ No CAS ]
  • [ 2628-16-2 ]
YieldReaction ConditionsOperation in experiment
92% With molybdenum hexacarbonyl In toluene for 2h; Reflux; chemoselective reaction; 4.2. General procedure General procedure: A equimolar mixture of 4-chlorostyrene thiirane (171 mg, 1.0 mmol) and Mo(CO)6(264 mg, 1.0 mmol) were stirred in toluene (5 mL) at reflux for 1 hr. The progress of thereaction was followed by TLC. After completion, the reaction mixture was concentrated ona rotary evaporator, extracted successively with ethyl acetate, washed with water and brine.The organic layer was separated and dried over anhydrous Na2SO4. The crude product waspurified by column chromatography on a silica gel (hexane: ethyl acetate = 10:1) to afford4-chlorostyrene (132 mg, 95%). All products are known compounds and were identifiedby comparison of their spectroscopic data with those of authentic samples [25].
92% With molybdenum(V) chloride; zinc In tetrahydrofuran at 20℃; for 1.5h; 4.2. General procedure General procedure: Zinc powder (131mg 2.0mmol) and molybdenum(V) chloride (238mg, 1.0mmol) weremixed in THF (5 mL). The resulting mixture was stirred to produce a solution of the lowvalentmolybdenum-zinc complex. 4-Chlorostyrene thiirane (171mg, 1.0mmol) was thenadded to this solution and the reaction mixture was stirred for 0.5 h at room temperature.The progress of the reaction was followed by TLC. On completion, the solvent wasremoved under reduced pressure and the residue was extracted successively with ethylacetate, washed with water and brine. The organic fractions were separated and dried overanhydrous Na2SO4. The crude product was subjected to flash column chromatography onsilica gel (hexane:ethyl acetate = 10:1) to afford 4-chlorostyrene (132mg, 95%). All of theproducts are known compounds and their identification was based on spectral comparison with authentic samples [26].
  • 92
  • [ 7648-30-8 ]
  • [ 2628-16-2 ]
  • (E)-ethyl 4-(4-acetoxyphenyl)-2,2-difluoro-3-butenoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With potassium acetate In N,N-dimethyl acetamide at 20℃; for 16h; Schlenk technique; Inert atmosphere; UV-irradiation; General procedure for visible-light promoted atom transfer radicaladdition-elimination (ATRE) reaction for the synthesis of fluoroalkylatedalkenes using DMA as electron-donor General procedure: To a 25 mL of Schlenk tube equipped with a Teflon septum were added KOAc (0.6 mmol, 2.0 equiv.) under Ar, followed by DMA(2 mL). Then, alkene (1) (0.3 mmol, 1.0 equiv.), and IRF (2) (0.45 mmol, 1.5 equiv.)were added subsequently. After stirring under purple light for 16 hours, the residuewas diluted with ethyl acetate, washed with H2O and brine, dried over Na2SO4,filtered and concentrated. The residue was purified with silica gel chromatography to provide pure product.
77% With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; bis-diphenylphosphinomethane In N,N-dimethyl-formamide at 90℃; for 20h; Inert atmosphere; Schlenk technique;
  • 93
  • [ 2628-16-2 ]
  • 1-(methylsulfonyl)-2-(4-methoxyphenyl)diazene [ No CAS ]
  • 4-(2-(methylsulfonyl)acetyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With air In 1,4-dioxane; water at 25℃; for 24h; Irradiation; 13 Example 13: In a 15 mL reaction tube, p-acetoxystyrene 1i (0.2 mmol) and p-methoxybenzoazosulfone 2a (0.5 mmol) were added in this order.2 mL of 1,4-dioxane and 1 mL of water were mixed uniformly, and then the reaction was stirred at 25 ° C for 24 hours under the irradiation of a 3W blue LED lamp.After the reaction was detected by TLC, ethyl acetate was added for extraction, 3 mL each time, and the extraction was combined three times.After the extract was dried over anhydrous sodium sulfate, the extract was concentrated under reduced pressure under vacuum (0.08Mpa) to no solvent to obtain a crude product.Then it was washed with a mixed eluent of petroleum ether and ethyl acetate in a volume ratio of 5: 1, and subjected to flash column chromatography on a silica gel column.The β-carbonylsulfone product 3i of this example was obtained as a yellow oily solid with a yield of 65%.
47% With air In 1,4-dioxane; water at 20℃; for 16h; Irradiation;
  • 94
  • [ 623-73-4 ]
  • [ 2628-16-2 ]
  • ethyl 5-(4-acetoxyphenyl)-4,5-dihydroisoxazole-3-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tert.-butylnitrite; 1,1,1,3',3',3'-hexafluoro-propanol; tetrabutylammonium tetrafluoroborate In dichloromethane at 20 - 25℃; for 1h; Inert atmosphere; Electrolysis;
75% With tert.-butylnitrite; boron trifluoride diethyl etherate In acetonitrile at 25℃; for 12h; 7 Add acetonitrile (2.0mL), compound 1g (0.5mmol, 81.1mg), compound 2a (1.0mmol, 108μL), compound 3 (1.0mmol, 121μL), and catalyst boron trifluoride ether (0.05mmol) to the reaction test tube. ,14μL); then react for 12 hours at 25°C in the air; after the reaction, quench with saturated sodium chloride solution, then extract with ethyl acetate, use a rotary evaporator to remove the solvent, silica gel adsorption, and finally use The mixed solvent of ethyl acetate and petroleum ether was subjected to column chromatography to obtain 4 g of the product with a yield of 75%. The main test data of the prepared product are as follows. Through analysis, it can be known that the actual synthesized product is consistent with the theoretical analysis
75% With tert.-butylnitrite; boron trifluoride diethyl etherate In acetonitrile at 25℃; for 12h;
  • 95
  • [ 2628-16-2 ]
  • 4-(1,2-dichloroethyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With copper dichloride In acetonitrile at 20℃; for 72h; Inert atmosphere; Irradiation; 6 Example Six 3f (0.2mmol, 32.4mg), CuCl2 (0.8mmol, 107.6mg), acetonitrile MeCN (5mL) were added to the gas protection tube at one time. Then the system was stirred with 38W white LED under a nitrogen atmosphere at room temperature for 72 hours. The reaction system was quenched with saturated sodium sulfite solution, extracted three times with ethyl acetate, and the organic layers were combined, dried over anhydrous sodium sulfate, and rotated The solvent is removed by the evaporator and adsorbed on silica gel. The product 4f can be obtained by simple column chromatography with a yield of 80%.
80% With copper dichloride In acetonitrile at 20℃; for 72h; Schlenk technique; Inert atmosphere; Irradiation;
  • 96
  • [ 166328-14-9 ]
  • [ 2628-16-2 ]
  • 1,3-dioxoisoindolin-2-yl 1-methylcyclohexane-1-carboxylate [ No CAS ]
  • C21H26O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With fac-tris(2-phenylpyridinato-N,C2')iridium(III) In acetonitrile at 20℃; for 24h; Irradiation; regioselective reaction;
  • 97
  • [ 6479-18-1 ]
  • [ 2628-16-2 ]
  • [ 618-41-7 ]
  • 4-(1-(4-methyl-3-oxo-3,4-dihydroquinoxalin-2-yl)-2-(phenylsulfonyl)ethyl)phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile In 1,2-dichloro-ethane at 20℃; for 6h; Irradiation; 3. General procedure for visible-light-induced multi-component reaction of quinoxalin-2(1H)-ones, alkenes and sulfinic acids. General procedure: To a solution of quinoxalin-2(H)-one 1 (0.1 mmol), arylsulfinic acid 3 (0.2 mmol), 4CzIPN (0.001 mmol, 2 mol %), DCE ( 2 mL) was added alkene 2 (0.2 mmol). The reaction mixture was open to the air and stirred under the irradiation of 3 W blue LEDs at room temperature for 6 h. After completion of the reaction, the solution was concentrated in vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired product 4 or 5.
  • 98
  • [ 75-91-2 ]
  • [ 75-63-8 ]
  • [ 2628-16-2 ]
  • 4-[1-(tert-butylperoxy)-3,3,3-trifluoropropyl]phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With N-ethyl-N,N-diisopropylamine; cobalt(II) 2,4-pentanedionate In water monomer; acetonitrile at 65℃; for 4h; Inert atmosphere; Schlenk technique; 3-(tert-Butylperoxy)-1,1,1-trifluoroalkanes 2 and 3-(tert-Butylperoxy)-1-chloro-1,1-difluoroalkanes 4; General Procedure General procedure: To a 50-mL Schlenk flask was added Co(acac)2 (0.1 mmol, 10 mol%). The flask was sealed and evacuated for 30 s and purged with N2 (3 ×). After further evacuating for 30 s, CF3Br (3.1 mmol in a 50-mL Schlenk flask based on our previous report 4g) or CF2ClBr (4.1 mmol, see below) was backfilled. Then the flask was equipped with a N2 balloon and CH3CN (4 mL), alkene (1 mmol), amine (4 mmol, 4 equiv), and TBHP (4 mmol, 4 equiv, 70% solution in H2O) were added sequentially. After stirring for 4 h at 65 °C, the mixture was filtered through a pad of Celite. The filtrate was concentrated, and the residue was purified by chromatography (silica gel).
  • 99
  • [ 75-91-2 ]
  • [ 353-59-3 ]
  • [ 2628-16-2 ]
  • 4-[1-(tert-butylperoxy)-3-chloro-3,3-difluoropropyl]phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With N-ethyl-N,N-diisopropylamine; cobalt(II) 2,4-pentanedionate In water monomer; acetonitrile at 65℃; for 4h; Inert atmosphere; Schlenk technique; 3-(tert-Butylperoxy)-1,1,1-trifluoroalkanes 2 and 3-(tert-Butylperoxy)-1-chloro-1,1-difluoroalkanes 4; General Procedure General procedure: To a 50-mL Schlenk flask was added Co(acac)2 (0.1 mmol, 10 mol%). The flask was sealed and evacuated for 30 s and purged with N2 (3 ×). After further evacuating for 30 s, CF3Br (3.1 mmol in a 50-mL Schlenk flask based on our previous report 4g) or CF2ClBr (4.1 mmol, see below) was backfilled. Then the flask was equipped with a N2 balloon and CH3CN (4 mL), alkene (1 mmol), amine (4 mmol, 4 equiv), and TBHP (4 mmol, 4 equiv, 70% solution in H2O) were added sequentially. After stirring for 4 h at 65 °C, the mixture was filtered through a pad of Celite. The filtrate was concentrated, and the residue was purified by chromatography (silica gel).
  • 100
  • [ 75-91-2 ]
  • [ 75-61-6 ]
  • [ 2628-16-2 ]
  • 4-[3-bromo-1-(tert-butylperoxy)-3,3-difluoropropyl]phenyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With N-ethyl-N,N-diisopropylamine; cobalt(II) 2,4-pentanedionate In water monomer; acetonitrile at 65℃; for 4h; Inert atmosphere; Schlenk technique; 1-Bromo-3-(tert-butylperoxy)-1,1-difluoroalkanes 5; General Procedure General procedure: To a 50-mL Schlenk flask was added Co(acac)2 (0.1 mmol, 10 mol%). The flask was sealed and evacuated for 30 s and purged with N2 (3 ×).Then the flask was equipped with a N2 balloon and CH3CN (4 mL), alkene (1 mmol), CF2Br2 (3 mmol, 3 equiv), amine (4 mmol, 4 equiv), and TBHP (4 mmol, 4 equiv, 70% solution in H2O) were added sequentially. After stirring for 4 h at 65 °C, the mixture was filtered through a pad of Celite. The filtrate was concentrated, and the residue was purified by chromatography (silica gel).
  • 101
  • [ 2628-16-2 ]
  • [ 106871-53-8 ]
  • C18H18O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With ϖ-allylpalladium (II) chloride dimer; 2-(diphenylphosphino)pyridine In 1,2-dichloro-ethane at 80℃; for 18h; Schlenk technique; Inert atmosphere; regioselective reaction; General Procedure A: General procedure: Oxalic acid monothioesters (1.5 equiv, 0.3 mmol) (if solid), olefins (1.0 equiv, 0.2mmol) (if solid), [Pd(allyl)Cl]2 (2 mol %, 1.5 mg) and (2-py)PPh2 (8 mol %, 4.3 mg)2were placed in a transparent Schlenk tube equipped with a stirring bar. The tube wasevacuated and filled with argon (three times). To these solids, oxalic acidmonothioester (1.5 equiv, 0.3 mmol) (if liquid), olefins (1.0 equiv, 0.2 mmol) (ifliquid) and DCE (2.0 mL) were added via a gastight syringe under argon atmosphere.The mixture was stirred at 80 oC for 18 h. The mixture was quenched with brine andextracted with ethyl acetate (3 × 10 mL). The organic layers were combined andconcentrated under vacuo. The product was purified by flash column chromatographyon silica (petroleum ether or petroleum ether/ethyl acetate= 200:1~20:1).
Recommend Products
Same Skeleton Products
Historical Records

Related Functional Groups of
[ 2628-16-2 ]

Alkenes

Chemical Structure| 63449-52-5

[ 63449-52-5 ]

Ethene-1,2-diylbis(4,1-phenylene) diacetate

Similarity: 0.95

Chemical Structure| 93022-30-1

[ 93022-30-1 ]

4-Styrylphenyl acetate

Similarity: 0.95

Chemical Structure| 155222-48-3

[ 155222-48-3 ]

5-Vinyl-1,3-phenylene diacetate

Similarity: 0.95

Chemical Structure| 89148-30-1

[ 89148-30-1 ]

Buta-1,3-diene-1,4-diylbis(4,1-phenylene) diacetate

Similarity: 0.90

Chemical Structure| 63366-83-6

[ 63366-83-6 ]

(E)-4-(3,5-Dimethoxystyryl)phenyl acetate

Similarity: 0.90