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CAS No. : | 585-07-9 | MDL No. : | MFCD00048245 |
Formula : | C8H14O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SJMYWORNLPSJQO-UHFFFAOYSA-N |
M.W : | 142.20 | Pubchem ID : | 11448 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.62 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 41.42 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.36 cm/s |
Log Po/w (iLOGP) : | 2.48 |
Log Po/w (XLOGP3) : | 2.54 |
Log Po/w (WLOGP) : | 1.9 |
Log Po/w (MLOGP) : | 1.85 |
Log Po/w (SILICOS-IT) : | 1.43 |
Consensus Log Po/w : | 2.04 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.12 |
Solubility : | 1.07 mg/ml ; 0.00752 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.74 |
Solubility : | 0.259 mg/ml ; 0.00182 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.59 |
Solubility : | 3.67 mg/ml ; 0.0258 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.47 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P210-P280 | UN#: | 3272 |
Hazard Statements: | H225-H315 | Packing Group: | Ⅲ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54.81 %Chromat. | at 20℃; for 5 h; | The transesterification reactions were set up in the same manner described in EXAMPLE 1. However, in place of tert-butyl acetate, an alternative tert-butyl compound was added to the starting material (Z-L-Asp). The tert-butyl compounds tested were in the form of solvents. Each reaction was run at room temperature for about 4.5 to 5 hours. At the end of the reaction time, each mixture was analyzed using the UPLC technique, as described in EXAMPLE 1. The results in TABLE II show that the transesterification reactions in the presence of certain tert-butyl compounds, namely, tert-butyl benzoate, tert-butyl methacrylate, tert butyl propionate, and tert-butyl bromoacetate, yielded significant amounts of Z-Asp(OtBu)2. In contrary, methyl-tert butyl ether (MTBE), and tert-butyl formate were not as effective for producing Z-Asp(OtBu)2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetraphenylporphinatoaluminium ethyl In octane; benzene at 30℃; for 20h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With n-butyllithium; <i>tert</i>-butyl alcohol In tetrahydrofuran; hexane at -78℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With carbon monoxide; hydrogen In toluene at 100℃; for 25h; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With triethylamine for 0.5h; Ambient temperature; | |
84% | With sodium bicarbonate; triethylamine; citric acid In water | R.40 6,7-dihydroxy-2-methyl-4-thiaheptanoic acid t-butyl ester REFERENCE EXAMPLE 40 6,7-dihydroxy-2-methyl-4-thiaheptanoic acid t-butyl ester To thioglycerol (0.835 mI), t-butyl methacrylate (10 ml) and triethylamine (1 ml) were added, followed by stirring at 60° C. for 48 hours. After cooling and addition of water, the reaction mixture was extracted with chloroform. The extract was washed with a 5% aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and dried over anhydrous sodium sulfate, and the solvent was distilled off, to yield the title compound (2.11 g, yield 84%) as a colorless oily substance. IRυmaxneat cm-1: 3400, 1720 1 H-NMR (CDCl3)δ:1.21 (3H, d, J=6.6 Hz), 1.47 (9H, s), 2.50-2.90 (5H, m), 3.50-3.63 (1H, m), 3.68-3.88 (2H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 25℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 69% 2: 12% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 5.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With [MgBr](1+*[n-Bu2SnBrIH](1-) In tetrahydrofuran at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: tert-Butyl methacrylate; pentan-3-one With potassium <i>tert</i>-butylate In tetrahydrofuran at 25℃; for 0.5h; Stage #2: methyl iodide In tetrahydrofuran at 50℃; for 3h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.3% | Stage #1: butanone With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.0833333h; Stage #2: tert-Butyl methacrylate In tetrahydrofuran at 20℃; for 24h; | 2 Preparation of Int-6 To a solution of butan-2-one (1.06 g, 14.76 mmol, 1.31 mL, 1.2 equiv.) in THF (120.00 mL, 0.12 M) was added potassium tert-butoxide (1.66 g, 14.76 mmol, 1.2 equiv.) at 0° C. After 5 mins, tert-butyl 2-methylprop-2-enoate (1.75 g, 12.30 mmol, 1.99 mL, 1.0 equiv.) was added dropwise. The reaction mixture was warm to room temperature and stirred for 24 hours. The reaction mixture was quenched by the addition of 1.0 M aqueous HCl to pH=4. The resulting biphasic mixture was separated. The organic layers were washed with 10 mL of saturated NaHCO3 solution, followed by 10 mL of brine. The combined aqueous phases were extracted with a mixture of chloroform/2-propanol (ratio=9:1, 5 times). The combined organic phases were dried over Na2SO4, filtered and dried. The crude material was purified by column chromatography (eluent: 0-20% EtOAc in heptane) to provide int-6 (1.35 g, 9.63 mmol, 78.30% yield) as a pale yellow solid. Int-6 was a cis-enriched isomer according to the reference (JOC 2001, 66, 8000).1H NMR (500 MHz, methanol-d4) δ ppm 3.38-3.51 (m, 2H), 2.65-2.73 (m, 2H), 2.16 (dt, J=14.0, 5.5 Hz, 1H), 1.17 (d, J=6.7 Hz, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With sodium hydroxide; cyclo-octa-1,5-diene In 1,4-dioxane at 90℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 2-[2-[(tert-butyldimethylsilyl)oxy]ethoxy]ethyl methacrylate With diethylzinc; (diphenylmethyl)potassium In tetrahydrofuran at -78℃; for 2h; Stage #2: tert-Butyl methacrylate In tetrahydrofuran at -78℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 2-[2-[2-[(tert-butyldimethylsilyl)oxy]ethoxy]ethoxy]ethyl methacrylate With diethylzinc; (diphenylmethyl)potassium In tetrahydrofuran at -78℃; for 3h; Stage #2: tert-Butyl methacrylate In tetrahydrofuran at -78℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With Methyl 2-bromopropionate; N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper(I) bromide In acetone at 60℃; for 1.33333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: tert-Butyl methacrylate With Methyl 2-bromopropionate; N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper(I) bromide In acetone at 60℃; for 1.33333h; Stage #2: methacrylic acid methyl ester With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper(l) chloride In diphenylether; toluene at 90℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tris(2,4-di-tert-butylphenyl)phosphite; hydrogen In toluene at 40℃; for 30h; | ||
With hydrogen; 2.2'-Biphenylylenphosphorsaeure-methylester; bis-2,6-(2,4-dimethylphenyl)-4-phenylphosphabenzene In toluene at 50℃; for 22h; | ||
With hydrogen In toluene at 50℃; for 70h; |
With hydrogen In toluene at 100℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 81% 2: 15% | With oxygen; sodium carbonate In N,N-dimethyl acetamide at 23℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: tert-Butyl methacrylate With (diphenylmethyl)potassium In tetrahydrofuran Stage #2: poly(methyl methacrylate), 1,1-bis[3-(bromomethyl)phenyl]ethyl-terminated, Mn 1.23E4 Da by SEC, Mn 1.35E4 Da by osmometry, Mw/Mn 1.04; monomer(s): methyl methacrylate; 1,1-bis[3-(tert-butyldimethylsilyloxymethyl)phenyl]ethylene In tetrahydrofuran at -78℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: tert-Butyl methacrylate With (diphenylmethyl)potassium In tetrahydrofuran Stage #2: poly(methyl methacrylate), with 3,97 3-(bromomethyl)phenyl end groups, Mn 1.24E4 Da by SEC, Mn 1.32E4 by osmometry, Mn 1.36E4 Da by NMR, Mw/Mn 1.03; monomer(s): methyl methacrylate; 1,1-bis[3-(tert-butyldimethylsilyloxymethyl)phenyl]ethylene In tetrahydrofuran at -78℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With N,N,N',N'',N'''-pentamethyldiethylenetriamine; Ethyl 2-bromopropionate at 85℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With N,N,N',N'',N'''-pentamethyldiethylenetriamine; Ethyl 2-bromopropionate at 85℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With N,N,N',N'',N'''-pentamethyldiethylenetriamine; Ethyl 2-bromopropionate at 85℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With ethyl 2-bromoisobutyrate In toluene at 35℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethyl 2-bromoisobutyrate; copper(I) bromide; 4,4'-di-(5-nonyl)-2,2'-bipyridine In o-xylene at 100℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: tert-Butyl methacrylate With bromine In tetrachloromethane at 25℃; for 2h; Stage #2: With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrachloromethane at 25℃; for 5h; | |
Multi-step reaction with 2 steps 1: bromine / tetrachloromethane / 0 - 20 °C / Inert atmosphere 2: 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethyl 2-bromoisobutyrate; copper(ll) bromide; 4,4'-di-(5-nonyl)-2,2'-bipyridine In o-xylene at 60℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium <i>tert</i>-butylate; triisobutylaluminum In hexane; toluene at 0 - 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With oxygen In N,N-dimethyl acetamide at 50℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2.9-dimethyl-1,10-phenanthroline; oxygen In N,N-dimethyl-formamide at 20℃; for 12h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With tris(dibenzylideneacetone)dipalladium (0); N-Methyldicyclohexylamine; johnphos In 1,4-dioxane at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.2% | Example 17; 2-a-Chloro-5-{rf2S)-3-f5-chloro-l eta,3H-Sirori-benzofuran-2A'-pweridinl-r-yl)'2- hvdroxypropylloxy}-4~r(nethylamino)carbonyllphenoxy}-2-methylpropanoic acid.; Step 1. ^(l-tert-butoxycarbonyl-l-methylethoxy^S-chloro^-hydroxybenzoic acid methyl ester; To a solution of 5-chloro-2,4-dihydroxybenzoic acid methyl ester (10.2 g, 10.0 g at 100% w/w, 0.0493 mol, 1.0 mol eq) iniV-methyl pyrrolidone (40 ml, 4.0 rel vol), was added s potassium carbonate (17.40 g, 17.05 g at 100% w/w, 0.1233 mol, 2.5 mol eq) with stirring. 2-Bromo-2-methyl-propionic acid tert-bntyl ester (67.42 g, 66.07 g at 100% w/w, 0.2961 mol, 6.0 mol eq) was added in one portion together followed by tetrabutylammonium bromide (3.25 g, 3.18 g at 100 % w/w, 0.0098 moles, 0.2 mol eq). The temperature of the reaction mass was raised to 60-650C and maintained at this temperature for 16 h. On o completion, the reaction mixture was cooled 30-35 0C. The insoluble potassium salts were removed by filtration through Celite and the solids were washed with iV-methyl pyrrolidone (20 ml, 2.0 rel vol). The pH of the combined filtrates was adjusted to around 4 using dilute HCl solution then water (100 ml, 10.0 rel vol) added. The solution was extracted with dichloromethane (100 ml, 10 rel vol), the organic layer was washed with 5 water (150 ml, 15.0 rel vol) then evaporated to dryness at 35 0C under vacuum. The excess of 2-bromo-2-methyl-propionic acid tert-butyl ester and 2-methylacrylic acid tert-butyl ester by product were removed by applying a high vacuum (20-25 mbar) at 60 - 65 0C for <n="89"/>approximately one h. 4-(l-fert-Butoxycarbonyl-l-methylethoxy)-5-chloro-2- hydroxybenzoic acid methyl ester was obtained as an oil, weight 16.0 g (72.2% yield). 1H NMR (300 MHz, CDCl3): delta 10.73 (s, IH), 7.82 (s, IH), 6.36 (s, IH), 3.92 (s, 3H), 1.66 (s, 6H), 1.44 (S5 9H). | |
72.2% | Step 1. 4-(l-tert-butoxycarbonyl-l-methylethoxy)-5-chloro-2-hydroxybenzoic acid methyl ester; To a solution of 5-chloro-2,4-dihydroxybenzoic acid methyl ester (10.2 g, 10.0 g at 100% w/w, 0.0493 mol, 1.0 mol eq) in TV-methyl pyrrolidone (40 ml, 4.0 rel vol), was added <n="14"/>potassium carbonate (17.40 g, 17.05 g at 100% w/w, 0.1233 mol, 2.5 mol eq) with stirring. 2-Bromo-2-methyl-propionic acid tert-butyl ester (67.42 g, 66.07 g at 100% w/w, 0.2961 mol, 6.0 mol eq) was added in one portion together followed by tetrabutylammonium bromide (3.25 g, 3.18 g at 100 % w/w, 0.0098 moles, 0.2 mol eq). The temperature of the reaction mass was raised to 60-650C and maintained at this temperature for 16 h. On completion, the reaction mixture was cooled 30-35 0C. The insoluble potassium salts were removed by filtration through Celite and the solids were washed with TV-methyl pyrrolidone (20 ml, 2.0 rel vol). The pH of the combined filtrates was adjusted to around 4 using dilute HCl solution then water (100 ml, 10.0 rel vol) added. The solution was extracted with dichloromethane (100 ml, 10 rel vol), the organic layer was washed with water (150 ml, 15.0 rel vol) then evaporated to dryness at 35 0C under vacuum. The excess of 2-bromo-2-methyl-propionic acid tert-butyl ester and 2-methylacrylic acid tert-butyl ester by product were removed by applying a high vacuum (20-25 mbar) at 60 - 65 0C for approximately one h. 4-(l-tert-Butoxycarbonyl-l-methylethoxy)-5-chloro-2- hydroxybenzoic acid methyl ester was obtained as an oil, weight 16.0 g (72.2% yield). 1R NMR (300 MHz, CDCl3): delta 10.73 (s, IH), 7.82 (s, IH), 6.36 (s, IH), 3.92 (s, 3H), 1.66 (s, 6H), 1.44 (s, 9H). | |
72.2% | With tetrabutylammomium bromide; potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 60 - 65℃; for 16h; | Step 1. 4-(l-tert-butoxycarbonyl-l-methylethoxy)-5-chloro-2-hydroxybenzoic acid methyl ester. To a solution of 5-chloro-2,4-dihydroxybenzoic acid methyl ester (10.2 g, 10.0 g at 100% w/w, 0.0493 mol, 1.0 mol eq) in TV-methyl pyrrolidone (40 ml, 4.0 rel vol), was added potassium carbonate (17.40 g, 17.05 g at 100% w/w, 0.1233 mol, 2.5 mol eq) with stirring. 2-Bromo-2-methyl-propionic acid tert-butyl ester (67.42 g, 66.07 g at 100% w/w, 0.2961 mol, 6.0 mol eq) was added in one portion together followed by tetrabutylammonium bromide (3.25 g, 3.18 g at 100 % w/w, 0.0098 moles, 0.2 mol eq). The temperature of the reaction mass was raised to 60-650C and maintained at this temperature for 16 h. On completion, the reaction mixture was cooled 30-35 0C. The insoluble potassium salts were removed by filtration through Celite and the solids were washed with TV-methyl pyrrolidone (20 ml, 2.0 rel vol). The pH of the combined filtrates was adjusted to around 4 using dilute HCl solution then water (100 ml, 10.0 rel vol) added. The solution was extracted with dichloromethane (100 ml, 10 rel vol), the organic layer was washed with water (150 ml, 15.0 rel vol) then evaporated to dryness at 35 0C under vacuum. The excess of 2-bromo-2-methyl-propionic acid tert-butyl ester and 2-methylacrylic acid tert-butyl ester by product were removed by applying a high vacuum (20-25 mbar) at 60 - 65 0C for approximately one h. 4-(l-ter£-Butoxycarbonyl-l-methylethoxy)-5-chloro-2- hydroxybenzoic acid methyl ester was obtained as an oil, weight 16.0 g (72.2% yield). 1H NMR (300 MHz, CDCl3): delta 10.73 (s, IH), 7.82 (s, IH), 6.36 (s, IH), 3.92 (s, 3H), 1.66 (s, 6H), 1.44 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper(I) bromide In toluene at 85℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With methanol; water; caesium carbonate In toluene at 20℃; for 12h; | |
With dmap In water at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With carbon dioxide In benzene at 35°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With carbon dioxide In benzene under irradiation with visible light at 30°C for 3 h;; observed by NMR spectroscopy;; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With azobis(2-cyanobutane) In ethanol at 78℃; for 6h; | 8 Example 8; Preparation of Polymer 8 (Solution Polymerization in Ethanol); The following feeds were prepared at 20° C. with stirring: Feed 1: 123 g t-BA 55 g t-BMA 41 g HEMA 15 g MAA 5 g AA 200 g Ethanol Feed 2: 7 g Wako V 59 50 g Ethanol At 20° C., a mixture of 300 g of ethanol, 15% of the total amount of feed 1, and 15% of the total amount of feed 2 were prepared. The mixture was heated to 78° C. under atmospheric pressure. After 78° C. had been reached, feed 1 and feed 2 were started at the same time. Feed 1 was metered in over the course of 3 h, and feed 2 was metered in over the course of 4 h with a constant feed stream. The reaction mixture was maintained at 78° C. throughout the entire feed. When feed 2 was complete, the reaction mixture was kept at 78° C. for a further 2 h, then cooled to room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2,2'-azobis(isobutyronitrile) In butanone at 80℃; for 6h; | 3 Example 3; Production of copolymer 2 represented by the following structural formula and containing -SC3H6C(CF3)2OH group as the end group; In a container retained at the nitrogen atmosphere, 150 g of MEK, 28.9 g of γ-butyrolactone-2-yl methacrylate (hereinafter abbreviated as GBLM), 24.2 g of tert-butyl methacrylate (hereinafter abbreviated as TBMA) and 1.65 g of the compound (1-c) obtained in the example 1 as a chain transfer agent were placed and dissolved to prepare a monomer feed solution. Also, in another container retained at the nitrogen atmosphere, 20 g of MEK and 1.5 g of AIBN as a polymerization initiator were placed and dissolved to prepare an initiator feed solution. In a polymerization chamber retained at the nitrogen atmosphere, 65 g of MEK was placed and warmed to 80° C. with stirring, and subsequently, the monomer feed solution and the initiator feed solution were fed into the polymerization chamber retained at 80° C. over 4 hours to polymerize. Feed ratios of the basic ingredient monomers and the chain transfer agent were shown in Table 1. After the completion of feeding, the reaction was matured for two hours with retaining at 80° C. After the polymerization, the polymer solution was cooled to the room temperature and added into methanol dropwise to precipitate. The precipitate was filtrated and washed with methanol. Then the resultant wet cake was dried in a vacuum dryer to yield white polymer powder (copolymer 2). When the content of the terminal structure derived from the thiol compound in the obtained polymer was calculated by 13C-NMR measurement, it was 1.5 mol % based on the total number of monomer units contained in the polymer. Characteristics of the copolymer 2 and the peel strength and the peel mode of the coating film obtained as is the case with the example 1 were shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2,2'-azobis(isobutyronitrile) In tetrahydrofuran at 60℃; for 6h; | Preparation of macro-monomer B; In 100 mL of THF were dissolved 50 g of tert-butylmethacrylate, 0.29 g of 2-mercaptoethanol, and 0.55 g of N,N-azobisisobutylonitrile; the resulting reaction solution was stirred and refluxed at 60°C for 6 hours with nitrogen gas bubbling; and then, the reaction solution was re-precipitated in a mixed solvent of water/methanol = 1/1 to obtain 35 g of a reaction product. The reaction product, that is, a tert-butylmethacrylate polymer, was analyzed by size elimination chromatography (SEC) to obtain the molecular weights of Mw/Mn = 18,000/9,600. The number corresponding to k in the foregoing formula (6) was about 70. In 400 mL DMF, 20 g of the resulting tert-butylmethacrylate polymer were dissolved; 0.43 g of NaH (oil dispersion) and 3.20 g of tetrabutylphosphonium bromide were added, and the resulting reaction solution was stirred at room temperature for 3 hours, 3.0 g of 4-vinylbenzylchloride were further added, and the reaction solution was stirred at room temperature for 24 hours; and then, the reaction solution was re-precipitated in a mixed solvent of water/methanol = 1/1 to obtain 18 g of a reaction product. Then, 18 g of the resulting reaction product were dissolved in 200 mL of ethanol; 20 mL of concentrated hydrochloric acid and 0.8 g of hydroquinone were added to the ethanol solution, which was then refluxed at 70°C for 6 hours so as to hydrolyze the reaction product into polymethacrylic acid. After the ethanol was distilled off, the remaining solvent was replaced by ion-exchanged water. The reaction product was further dialyzed with ion-exchanged water until the reaction product showed pH-neutral. And then, the reaction product was freeze-dried to obtain an end-functionalized methacrylic acid polymer with vinylbenzyl. The resulting end-functionalized methacrylic acid polymer with vinylbenzyl was analyzed by 1H-NMR. A peak assigned to the vinylbenzyl proton was identified. Thus prepared methacrylic acid polymer was named as macro-monomer B. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-methylpropenal With tert-butylhypochlorite In tetrachloromethane at 20 - 50℃; for 5.5 - 6.5h; Stage #2: <i>tert</i>-butyl alcohol With triethylamine In tetrachloromethane at 0 - 20℃; for 19.5h; | 13 The procedure of Example 12 was repeated except a mixture of 5.287 g of t-butanol and 2.021 g of triethylamine was used instead of n-butanol. The process conditions and yield are shown in Table 2.; TABLE 2 Diol/ Reaction Time Yield Example Methacrylate Alcohol Conditions (hr.) (%) 12 n-butyl n- same as 18.5 56.3 methacrylate butanol Example 11 13 t-butyl t- added TEA 19.5 57.4 methacrylate butanol 14 allyl allyl same as 15.5 88.1 methacrylate alcohol Example 11 15 2-ethylhexyl 2-ethyl same as 1.5 69.8 methacrylate hexanol Example 11 16 cyclohexyl cyclohex same as 2 47.4 methacrylate anol Example 11 17 phenyl phenol same as 2 50.4 methacrylate Example 11 18 glycidyl glycidol same as 2.5 41.1 methacrylate Example 11 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With 2,2'-azobis(isobutyronitrile) In tetrahydrofuran at 70℃; | 2 APPLICATION EXAMPLE 2 Tetrahydrofuran (20 mL), tert-butyl methacrylate (2.13 g), 2-methyl-2-adamantyl methacrylate (4.69 g) and 4-ethoxy-9-oxo-8-oxa-bicyclo[4.3.0]non-3-yl methacrylate (4.02 g) are mixed in a reactor. Next, an initiator 2,2'-azo-bis-isobutyronitrile (AIBN) (1.1 g) is added to perform an overnight reaction at 70° C., subsequently tetrahydrofuran (20 mL) is added therein. Next, the solution is transferred into a container containing hexane (1L) to generate white precipitate. The precipitate is then dried by filtration to obtain white powders (6.83 g), i.e., the formula (IV-1) polymer. The yield is 63%. Weight-average molecular weight of the polymer measured with GPC is 19,200, and glass transition temperature (Tg) is 121° C. |
Yield | Reaction Conditions | Operation in experiment |
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78% | With 2,2'-azobis(isobutyronitrile) In tetrahydrofuran at 65℃; | 1 APPLICATION EXAMPLE 1 Tetrahydrofuran (20 mL), tert-butyl methacrylate (2.13 g), 2-methyl-2-adamantyl methacrylate (4.69 g) and 9-methoxy-5-oxo-4-oxa-tricyclo[5.2.1.02,6]dec-8-yl methacrylate (3.99 g) are mixed in a reactor, and then an initiator 2,2'-azo-bis-isobutyronitrile (AIBN) (1.1 g) is added therein to perform the reaction at 65° C. After the reaction is completed, the solution to which tetrahydrofuran (20 mL) is added is transferred into a container containing hexane (1L) to generate white precipitate. The precipitate is then dried by filtration to obtain white powders (8.43 g), i.e., the formula (III-1) polymer. The yield is 78%. Weight-average molecular weight of the polymer measured with GPC is 14,100, and the glass transition temperature (Tg) is 169° C. |
Yield | Reaction Conditions | Operation in experiment |
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With 1-[(2-bromo-2-methylpropionyl)oxy]-2-propene In benzene at 60℃; for 1.5h; | 1 Example 1; Synthesis of α-allyl,ω-bromine terminated poly(t-BMA) macromonomer via ATRP CuBr (44.1 mg, 0.3 mmol) was added under argon to a dry round- bottom flask (rbf) equipped with a stirrer bar. The flask was sealed with a rubber septum, degassed and back-filled with argon three times and left under argon. Deoxygenated benzene (2.5 ml) and HMTETA (83. [6 JUL,] 0.3 mmol) were added via argon-purged syringes and stirred until the copper (I) bromide-HMTETA complex was formed, as indicated by a change from a cloudy white suspension to a clear, colorless solution and then to a slightly greenish suspension. Then t-BMA (5 ml, 30 mmol) and dodecane (0.2 ml, GC standard) were added under argon and the reaction vessel was placed in an oil bath maintained at [60 C.] After the addition of ABIB (97. [8] L, 0.6 mmol), an initial sample was taken at time t = [0] and the reaction was stirred until stirring stopped after about 90 minutes due to the formation of a very viscous dark green suspension. GC analysis showed 65% of monomer conversion. The reaction mixture was characterized by GPC : [MN = 6198, MW/MN =] 1. 16 ; [BY'H] NMR [(CDC13),] which gave the following 8 values: t-butyl-CH3 protons: [1.] 4-1. 5 ppm, methacrylate a-H3 protons: 1. [0-1.] 2 ppm, [BACKBONE-CH2-PROTONS] : [1.] 8-1. 85 ppm; allyl end group protons: CH2= : 5. [2-5.] 4ppm, [=CH- :] 5. [9-6.] 0 [PPM,-CH2- :] 4. [5-4.] 7 ppm); and by [MALDI-TOF] : a-allyl, co-bromine terminated poly (t-BMA) macromonomer-major series: mlz [=] [n x 142 (t- BMA) + 79/81 (Br) + 127 (initiator fragment)] and minor series: [M/Z = [N] x (142-57) + [79/81] + 127] that is believed to correspond to the loss of t-butyl group [(MW] [= 57)] during preparation of the sample by treating with acid. The reaction mixture was subjected to the next step in the reaction sequence, described below, without first isolating the [A-ALLYL. O-BROMINE] terminated poly (t-BMA) macromonomer from the reaction mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.5% | Stage #1: triethylsilane With 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene at 20℃; for 0.5h; Neat (no solvent); Stage #2: tert-Butyl methacrylate at 3.5 - 6℃; for 5.5h; Neat (no solvent); Cooling with ice water; | 4 Example 4; Synthesis of 1-tert-butoxy-2-methyl-1-triethylsiloxypropene through reaction of tert-butyl methacrylate with triethylsilane A 100-mL four-necked flask equipped with a Dimroth reflux condenser, stirrer, thermometer and dropping funnel was purged with nitrogen. The flask was charged with 258 mg of I-1330, 7.7 mg (0.015 mmol) of tris(pentafluorophenyl)-borane and 11.6 g (0.10 mol) of triethylsilane, which were stirred at room temperature for 0.5 hour. The flask was cooled in an ice water bath to an internal temperature of 3.5°C. From the dropping funnel, 13.5 g (0.095 mol) of tert-butyl methacrylate was added dropwise over 2.5 hours. During the period, the internal temperature rose to 6°C at maximum. After the completion of dropwise addition, the reaction mixture was stirred at 3-3.5°C for 3 hours whereupon triethylsilane disappeared as confirmed by GC analysis. The reaction mixture contained a small amount of white solids. The reaction mixture was distilled in vacuo, whereby 24.8 g of a colorless clear fraction having a boiling point of 73-75°C/0.3 kPa was collected. From the results of NMR and MS analysis, the liquid was identified to be the title compound, 1-tert-butoxy-2-methyl-1-triethylsiloxypropene. The yield based on triethylsilane was 81.5%.1H-NMR (CDCl3, 300 MHz): δ (ppm) 1.55 (3H, d, J=0.4 Hz), 1.54 (3H, d, J=0.4 Hz), 1.27 (9H, s), 0.98 (9H, dt, J=0.6 Hz, 7.8 Hz), 0.69 (6H, dq, J=1.1 Hz, 7.9 Hz) 13C-NMR (CDCl3, 75.6 MHz): δ (ppm) 146.7, 95.6, 78.9, 29.1, 18.2, 17.5, 6.7, 5.2 29Si-NMR (CDCl3, 59.7 MHz): δ (ppm) 20.1 MS (EI): m/z 258 (M+), 229, 202, 173, 157, 133, 115, 103, 87, 75, 70, 57, 41 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 1,1-Diphenylpropyllithium In tetrahydrofuran at -78℃; for 15h; | 2.B The color of the initiator remained dark purple until the addition of monomer. t-Butyl methacrylate (0.44 g, 3.1 mmol) (tBMA) monomer was first introduced slowly over a 1-2 minute period and the initiator color immediately changed to pale yellow. 15 minutes after the addition of tBMA, benzyl 2-ethylacrylate (BzEA) (8 g, 42.1 mmol) were added all at once and reaction was allowed to proceed to completion for 15 hours. The polymerization mixture was stopped by adding 2 mL of methanol, stirred for 20 minutes and then poured into 300 mL of methanol. The polymer was separated by filtration and redissolved in 20 mL of THF and precipitated into 300 mL of methanol. Drying in a vacuum oven at 30° C. for 24 hours yielded poly(t-butyl methacrylate)-block-poly(benzyl 2-ethyl acrylate) (8.2 g, 98%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate In ISOPROPYLAMIDE; toluene | Synthesis of (E)-3-[6-methoxy-5-(4-methyl-1H-imidazol-1-yl)pyridin-2-yl]-2-methylacrylic acid Synthesis of (E)-3-[6-methoxy-5-(4-methyl-1H-imidazol-1-yl)pyridin-2-yl]-2-methylacrylic acid A mixture of 6-chloro-2-methoxy-3-(4-methyl-1H-imidazol-1-yl)pyridine (400 mg), an allylpalladium chloride dimer (32.8 mg), tri-o-tolylphosphine (54.4 mg), sodium acetate (441 mg), dimethylacetamide (0.640 mL), tert-butyl methacrylate (0.724 mL) and toluene (2 mL) was stirred in a nitrogen atmosphere at 120°C for 3.5 hours. The reaction solution was left to cool to room temperature. Then, a silica gel was added and the reaction solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent: heptane-ethyl acetate system) to obtain 313 mg of tert-butyl (E)-3-[6-methoxy-5-(4-methyl-1H-imidazol-1-yl)pyridin-2-yl]-2-methylacrylate. The ester was diluted with trifluoroacetic acid (2.48 mL) and methylene chloride (2.48 mL), and the reaction solution was stirred at room temperature for 3.5 hours. The reaction solution was concentrated under reduced pressure to obtain 260 mg of the title compound. The property value of the compound is as follows. ESI-MS; m/z 274 [M++H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With oxygen; copper diacetate; palladium dichloride In 1,4-dioxane; dimethyl sulfoxide at 115℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: diethyl N-(diphenylmethylene) aminomethyl phosphonate With (R)-13-[2-(3,4-dimethoxyphenyl)ethyl]-8,9,12,13,14,15,17,18-octahydro-11H-dinaphtho[1,2-p:1,2-n][1,4,10,13,7]tetraoxazacycloheptadecine In toluene at -78℃; for 0.166667h; Inert atmosphere; Stage #2: tert-Butyl methacrylate In toluene at -78℃; Inert atmosphere; enantioselective reaction; | 4.3. Typical procedure for the synthesis of 5 General procedure: A stirred mixture of 3 (0.5 g, 1.5 mmol), catalyst 1 (0.15 mmol) and NaOtBu (0.192 g, 2 mmol) in abs. toluene (7 mL) was cooled to 78 °C under an argon atmosphere. After 10 min., a toluene solution (3 mL) of the acrylic acid derivative 4 (1.8 mmol) was added. After stirring for the given time at 78 °C, the reaction was quenched with saturated aqueous NH4Cl and extracted with toluene. The combined organic extracts were dried over MgSO4, and the toluene was evaporated under reduced pressure. Product 5 was isolated by column chromatography on silica using EtOAc-hexane = 7:3 (for 5a, b, c, e, f) and CH2Cl2-MeOH = 9:1 (for 5d) as eluent. Catalyst 1 was also recovered during column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With N-Methyldicyclohexylamine;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In 1,4-dioxane; at 120℃;Inert atmosphere; | Example 223Atert-Butyl(2E)-3-(3-amino-4-cyanophenyl)-2-methylacrylate; Under argon, a mixture of 2.0 g (10.15 mmol) of <strong>[304858-65-9]2-amino-4-bromobenzonitrile</strong>, 2.165 g (2.5 ml, 15.23 mmol) of tert-butyl 2-methylacrylate, 93 mg (0.10 mmol) of tris(dibenzylideneacetone)-dipalladium, 41 mg (0.20 mmol) of tri-tert-butylphosphine and 2.4 ml (11.17 mmol) of N,N-di-cyclohexylmethylamine in 20 ml of dioxane was heated to 120 C. and stirred at this temperature overnight. The reaction was checked (TLC, mobile phase cyclohexane/ethyl acetate 9:1), and another 10 mg of tris(dibenzylideneacetone)dipalladium, 10 mg of tri-tert-butylphosphine and 500 mul of tert-butyl 2-methylacrylate were then added and the mixture was stirred at 120 C. for a further 4 h. The reaction mixture was then filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethylacetate 9:1?4:1). This gave 1.375 g of the title compound (52% of theory).LC-MS (Method 4): Rt=1.33 min; m/z=259 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In N,N-dimethyl-formamide at 150℃; for 2h; Inert atmosphere; | 135A Example 135Atert-butyl(2E)-3-(3-amino-4-chloro-2-methylphenyl)-2-methylacrylate and tert-butyl 2-(3-amino-4-chloro-2-methylbenzyl)acrylate; 1.50 g (6.80 mmol) of 3-bromo-6-chloro-2-methylaniline, 2.90 g (20.4 mmol) of tert-butyl methacrylate and 4.74 ml (34.0 mmol) of triethylamine were dissolved in 10.0 ml of DMF. Three times, the reaction solution was evacuated and in each case vented again with argon. After addition of 152.7 mg (0.68 mmol) of palladium(H) acetate and 414.1 mg (1.36 mmol) of tri-2-tolylphosphine, the mixture was once more evacuated twice and in each case vented with argon. The reaction mixture was then stirred at 150° C. for 2 h. After cooling, the mixture was filtered through celite and the residue was washed with DMF. The filtrate was concentrated under reduced pressure and the residue was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 100:1). This gave 1.59 g of a mixture of the two title compounds (ratio about 2:1, 83% of theory).LC-MS (Method 4): Rt=1.45 min; m/z=226 (M-C4H8)+and Rt=1.49 min; m/z=282 (M+H)+.1H-NMR (400 MHz, DMSO-d6): tert-butyl(2E)-3-(3-amino-4-chloro-2-methylphenyl)-2-methyl-acrylate: δ [ppm]=1.49 (s, 9H), 1.75 (d, 3H), 2.02 (s, 3H), 5.12 (s, 2H), 6.44 (d, 1H), 7.11 (d, 1H), 7.51 (s, 1H).1H-NMR (400 MHz, DMSO-d6): tert-butyl 2-(3-amino-4-chloro-2-methylbenzyl)acrylate: δ [ppm]=1.42 (s, 9H), 1.98 (s, 3H), 3.45 (s, 2H), 4.97 (s, 2H), 5.15 (d, 1H), 6.01 (d, 1H), 6.38 (d, 1H), 7.02 (d, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 54% 2: 38% | With silver(I) acetate; palladium diacetate In dimethyl sulfoxide; N,N-dimethyl-formamide at 115℃; for 48h; | Typicalprocedureforpalladium(II)-catalyzedoxidativeHeckcouplingofthiazole-4-carboxylate: General procedure: A reaction tube was charged with methyl 4-phenylthiazole-4-carboxylate (1a, 0.5 mmol), olefin 2 (0.75 mmol, 1.5 equiv), Pd(OAc)2 (11 mg, 0.05 mmol, 10 mol%), AgOAc (167 mg, 1 mmol, 2.0 equiv), DMF (1.5 ml) and DMSO (0.15 ml). The mixture was vigorously stirred at 115 °C (oil temperature). After stirring for 48 h, the mixture was cooled to room temperature, diluted with ethyl acetate and filtered. The filtrate was washed with saturated NaHCO3, water and brine, dried over Na2SO4, and concentrated in vacuo to give dark residue, which was purified by flash chromatography on silica gel to afford the cross coupling product 3a (155 mg, 90%) as off-white solid |
Yield | Reaction Conditions | Operation in experiment |
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With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 140℃; for 16h; | 5 3- {2-[4-(4-Chloro-benzyloxy)-phenyl]-6,7-dihydro-4H-furo[3,2-c]pyridine- 5-yl}-2-methyl-propionic acid t-butyl ester (9b, Ra=4Cl, Rb=H). To a solution of compound 13a (0.25g, 0.74mmol) in DMF (5ml) in a 25ml pyrex bottle were added 1,8- diazabicyclo[5.4.0]undec-7-ene (0.33ml, 2.21mmol) and t- butylmethacrylate (0.24ml, 1.47mmol). The mixture was heated at 140°C for 16hrs. The solution was cooled and 5% NaHCC>3 was added (10ml) and extracted with diethyl ether/EtOAc, 1/1, v/v. The organic layer was washed with water (4x20ml), dried on MgSC>4, concentrated in vacuo and the residue was purified by silica gel column chromatography (diethyl ether/petroleum ether, 9/1 to 4/1, v/v, Rf 0.65) to give pure 9b (Ra=4Cl, Rb=H, O. lg, 28%) as a colorless oil. LC-MS (Method A): Rt 1.88, [M+H] 482. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 125℃; for 100h; | 5 3-[2-(4-Benzyloxy-phenyl)-4,5,6,7-tetrahydro-oxazolo[4,5-c]pyridine]-2- methyl-propionic acid t-butyl ester (28b).To a solution of compound 27(Ra=Rb=H, 13.45g, 43.9mmol) in DMF (270ml) was added 1,8- diazabicyclo[5.4.0]undec-7-ene (3eg) and t-butylmethacrylate (28.54ml,175.6mmol, 4eq). The mixture was heated at 125°C for lOOhrs. The solution was cooled and 5% NaHCOe was added (15ml/mmol) and extracted with diethyl ether/EtOAc, 1/1, v/v. The organic layer was washed with water (4x), dried on MgSCU, concentrated in vacuo and the residue was purified by silica gel column chromatography (eluent: diethyl ether/petroleum ether, 1/2 to 3/1, v/v) to give 23b (Ra=Rb=H, 14.58g, 74%) as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 140℃; | Tert-butyl 3-{6-hydroxy-2H-spiro[l-benzofuran-3,4'-piperidine]-l'-yl}-2- methyl-propanoate. To a solution of 2H-spiro[l-benzofuran-3,4'-piperidin]-6- ol (565 mg; 2.76 mmol) in N,N-dimethylformamide (5.00 niL) was added tert- butyl methacrylate (0.9 niL; 5.52 mmol) and DBU (1.24 mL; 8.28 mmol) The resulting mixture was heated at 140°C in a sealed flask overnight. After cooling to RT the reaction mixture was partitioned between 5% aqueous NaHC03 solution and EtOAc. The layers were separated and the organic layer was dried (Na2S04), filtered, and concentrated. The residue was purified by column chromatography (S1O2, Et20: hexanes 1:1) to afford the product (0.45 g,47%). NMR (400 MHz, CDCl3-d) δ ppm 6.91 (d, J =8.0 Hz, 1H), 6.29 - 6.36 (m, 2H) 5.80 (bs, 1H), 4.34 (s, 2H), 2.88 - 2.96 (m, 1H), 2.75 - 2.84 (m, 1H), 2.51- 2.66 (m, 2 H), 2.26 - 2.35 (m, 1H), 1.96 - 2.10 (m, 2H), 1.83 - 1.93 (m, 2H), 1.65- 1.69 (m, 2H), 1.48 (s, 9H), 1.11 (d, J=8.5Hz, 3H). Rt 1.13 min (System B), [M+H]+ 348.1 |
47% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 140℃; for 16h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With bromine In tetrachloromethane at 0 - 20℃; Inert atmosphere; | 4.1.2. Synthesis of tert-butyl 2,3-dibromo-2-methylpropanoate (9) A solution of tert-butyl methacrylate (8.15 mL, 50 mmol) in CCl4 was cooled to 0 °C and added 2.65 mL of bromine (51 mmol) and stirred for 16 h at room temperature. The reaction mixture was then quenched with saturated sodium bisulfate and diluted with ether. The organic phase was extracted with ether three times and dried over Na2SO4. Combined organic layer was concentrated under reduced pressure to afford 15 g (quant. as light yellow oil) of desired compound 9.1H NMR (CDCl3) δ 4.18(dd, J = 0.49, 9.75 Hz, 1H), 3.70(d, J = 9.75 Hz, 1H), 1.98(d, J = 0.49 Hz, 3H), 1.51(s, 9H).13C NMR (CDCl3) δ 167.0, 82.8, 56.6, 38.2, 27.2, 25.9.Mass spectra (EI) 289 (M+4-CH3), 287 (M+2-CH3), 285 (M-CH3), 231 (M+4-OtBu), 229 (M+2-OtBu), 227 (M-OtBu), 203 (M+4-OtBu-CO), 201 (M+2-OtBu-CO), 119 (M-OtBu-CO).HRMS (EI) m/z Calcd for C7H11O281Br2: 288.9085. Found 288.9088 [M-CH3], m/z Calcd for C7H11O279Br81Br: 286.9105. Found 286.9102 [M-CH3], m/z Calcd for C7H11O279Br2: 284.9125. Found 284.9135 [M-CH3]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h; Inert atmosphere; | Typical experimental procedure for mono Heck cross coupling Reaction General procedure: A mixture of 4-iodotoluene (5 g, 22.93 mmol), ethyl acrylate (4.587 g, 45.87 mmol) and potassium carbonate (6.330 g, 45.87 mmol) was taken in DMF (15 ml) and then added SS-Pd (10.27 g, 2 mol% Pd). The reaction mixture was heated at 100 oC for 6 h under nitrogen atmosphere. After cooling the reaction mixture was diluted with 15ml of ethyl acetate and washed with cold water. The organic layer was finally washed with brine and dried over anhydrous Na2SO4. The crude mixture was purified by column chromatography (EtOAc:Hexane, 1:99), afforded (E)-ethyl 3-p-tolylacrylate 1 as colourless liquid (4.051g, 93% yield) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With potassium carbonate at 80℃; Micellar solution; | A typical Heck reaction was performed in a double walledglass reactor with reflux condenser at ambient pressure. 153 μL (1.34 mmol) alkene (e.g. styrene) and 158 L (1.50 mmol) arylhalide (e.g. iodobenzene) were dissolved in 46 mL organic sol-vent or aqueous microemulsion in the presence of 0.276 g(2.00 mmol) K2CO3as base and stirred at desired reactiontemperature.1.2-1.4 g of the immobilized catalyst containing15 mg (0.067 mmol) Pd(OAc)2on silica was added to the reactionmixture and the reaction was started. For the Heck reaction withhomogeneous catalyst only 15 mg (0.067 mmol) of palladium (II)acetate was added. The reaction progress was monitored by mea-suring the reactant concentrations at different reaction times byhigh performance liquid chromatography (HPLC). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium carbonate at 80℃; Micellar solution; | A typical Heck reaction was performed in a double walledglass reactor with reflux condenser at ambient pressure. 153 μL (1.34 mmol) alkene (e.g. styrene) and 158 L (1.50 mmol) arylhalide (e.g. iodobenzene) were dissolved in 46 mL organic sol-vent or aqueous microemulsion in the presence of 0.276 g(2.00 mmol) K2CO3as base and stirred at desired reactiontemperature.1.2-1.4 g of the immobilized catalyst containing15 mg (0.067 mmol) Pd(OAc)2on silica was added to the reactionmixture and the reaction was started. For the Heck reaction withhomogeneous catalyst only 15 mg (0.067 mmol) of palladium (II)acetate was added. The reaction progress was monitored by mea-suring the reactant concentrations at different reaction times byhigh performance liquid chromatography (HPLC). |
Yield | Reaction Conditions | Operation in experiment |
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With osmium(VIII) oxide; water; 4-methylmorpholine N-oxide In acetone; <i>tert</i>-butyl alcohol at 20℃; | 57.A Step A Osmium(VIII) oxide (2.0 mL, 0.327 mmol) was added to a solution of 4-methylmorpholine 4-oxide (8.44 g, 72.1 mmol), water (10 mE), acetone (7.5 mL) and tBuOH (6.7 mL). tert-Butyl methacrylate (5.71 mL, 35.2 mmol) in acetone (10 mL) was added dropwise and the reaction mixture was stirred at room temperature over the weekend. The reaction mixture was quenched with dilute aqueous NaHSO3. The phases were separated, and the organic layer was dried over sodium sulfate and concentrated to afford crude tert-butyl 2,3- dihydroxy-2-methylpropanoate (6.2 g, 35.2 mmol, 100 % yield) which was taken forward without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With iron(II) phthalocyanine In dichloromethane at 0℃; for 0.5h; Inert atmosphere; | General procedure for synthesis of 1 General procedure: To a mixture of carbazate (1.5 mmol), alkene (0.5 mmol), and [Fe(Pc)] (5 mol %), freshly distilled CH2Cl2 (2 mL) were added under nitrogen at 0 C. Then T-Hydro (4 mmol, 8 equiv) was dropped into the mixture under nitrogen at 0 C. T he mixture was stirred at 0 C for 30 min. The resulting mixture was filtered through a pad of silica with ethyl acetate as eluent. The solvent was evaporated under vacuum to give the crude product 1. NMR yield was determined by 1H NMR using dibromomethane as an internal standard. The residue was purified by flash column chromatography on silica gel (eluent: ethyl acetate/petroleum ether) to give the product 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With triethylamine In ethanol at 20℃; for 48h; | 10 20.0 g (0.056 mol) trimethylolpropan trimercaptoacetate 7 (TMPMA), 31.9 g (0.224 mol) 'butyl methacrylate 12, 250 ml. ethanol and 5.7 ml. (0.056 mol) triethyl amine were stirred at room temperature for 48h. Thereafter the solvent was evaporated and a residue was obtained. Highly pure material was obtained via silica gel chromatography [dichloromethane/ methanol (10:0.5)] and high vacuum treatment (80°C for 10 h) to remove traces of solvent (29.4 g, 67 %). NMR (400 MHZ, CDCI3) δ = 4.09 (s, 6H, CCH20), 3.24 (s, 6H, COCH2S), 2.90-2.83 (dd, 3H, SCH2C), 2.68-2.62 (dd, 2H, SCH2C), 2.56 (m, 3H, CCHC), 1 .53-1.47 (q, 2H, CH3CH2C), 1 .43 (s, 27 H, C(CH3)3), 1 .20-1 .18 (d, 9H, CHCH3), 0.93-0.88 (t, 3H, CH2CH3). nD: 1 .4838; Abbe's numbers o: 50.80 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With sodium methylate In methanol at 20℃; for 48h; | 14 2 ethyl, 2-(2thio-tbutylmethyacrylate) 1 ,3 d thio'butylmethacrylate) ETT 2 ethyl, 2-(2thio-tbutylmethyacrylate) 1 ,3 d thio'butylmethacrylate) ETT (0260) 4.50 g (0.014 mol) of triacetate 15 are dissolved at room temperature in a mixture of 25 ml methanol containing 1 10 mg of sodium methanolate and 8.3 g (0.058 mol) 'butyl methacrylate and stirred for 48 h. The mixture is evaporated, the resulting residue dissolved in (0261) dichloromethane and subsequently extracted with 1 N HCI, water and brine, filtered over sodium sulfate and evaporated. The oily residue is purified by silica gel chromatography [hexane/ ethylacetate (10:0.5)] and high vacuum treatment (80°C for 10 h) to remove traces of solvent (7.2 g, 82 %). NMR (400 MHZ, CDCI3) δ = 2.83-2.78 (dd, 3H, SCH), 2.63 (s, 6 H, SCH2), 2.59-2.52 (m, 6 H, CH2S, CCHC), 1 .45-1 .42 (m, 29H, CH3CH2C, CCH3), 0.88-0.81 (t, 3H, CH2CH3). nD: 1 .4842; Abbe's numbers υ: 50.20 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7.2 g | With triethylamine In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 72h; | 6 Di-t-butyl-,3'-(((1 ,4-dithiane-2,5-diyl)bis(methylene)) bis(sulfanediyl))bis(2- methylpropanoate) BSMD-'BuMA Dithiol 1 (5.0 g, 23.5 mmol) and t-butyl methacrylate 8 (13.4 g, 94.3 mmol) were dissolved in a mixture of 20 ml dimethylformamide and tetrahydrofuran (1 :1 (vohvol)) at room temperature. The reaction was started by the addition of 3.2 ml (23.5 mmol) triethyl amine. After three days at room temperature the mixture was evaporated in high vacuum and the residue was taken up in dichloro methane and successively extracted with 1 N hydrogen chloride, water and brine. The organic phase was then filtered over MgS04 and removed in vacuum giving a yellow oil which was purified via silica gel chromatography [heptane/ ethyl acetate (10:1 )] yielding 7.2 g of a clear liquid which consisted of two isomers. NMR (400 MHZ, CDCI3) δ = 1 .2 (d, 6H), 1.48 (s, 18H), 2.5-3.5 (m,16H). nD: 1 .5227; Abbe's numbers υ: 44.26 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.00 g | With triethylamine; lithium bromide In tetrahydrofuran at 20℃; for 2h; | (rac)-(2S,4S,5R)-4-tert-butyl 2-ethyl 5-(4-bromo-3-iodophenyl)-4-methylpyrrolidine-2,4-dicarboxylate, 32: To a suspension of 4-bromo-3-iodobenzaldehyde (1.24 g, 4.0 mmol) and glycine hydrochloride (0.838 g, 6.0 mmol) in acetonitrile (6 mL), triethylamine (0.836 g, 6.0 mmol) was added and reaction mixture was left stirring at room temperature for 4 h. The solvent of the reaction mixture was then evaporated under vacuum and the residue was dissolved in ethyl acetate (25 mL) and washed with brine solution (3 x 25 mL). The organic layer was dried over sodium sulphate and the solvent evaporated under vacuum to give the desired imine intermediate which was used in the next step without further purification. The imine intermediate was dissolved in THF (6 mL) and tert-butyl methacrylate (1.138 g, 8.0 mmol) was added followed by lithium bromide (0.694 g, 8.0 mmol) and triethylamine (1.11 g, 8.0 mmol). The reaction mixture was left stirring at room temperature for 2 h after which the solvent of the reaction mixture was then evaporated under vacuum and the residue was dissolved in ethyl acetate (25 mL) and washed with brine solution (3 x 25 mL). The organic layer was dried over sodium sulphate and the solvent evaporated under vacuum to give the desired crude product as a yellow oil which was purified using flash silica chromatography 1:9 EtOAc/hexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: butanone With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: tert-Butyl methacrylate In tetrahydrofuran at 0 - 20℃; Inert atmosphere; | |
57% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 0.833333h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate In 1,4-dioxane at 110℃; for 16h; Microwave irradiation; | A round bottom flask was charged with (E)-4-methyl-N'-((E)-3- phenylallylidene)benzenesulfonohydrazide (0.795 g, 2.64 mmol) , a stirbar, and 1,4-dioxane (40 mL, 0.125 M) before the addition of potassium carbonate (547 mg, 3.96 mmol) and tert- butyl methacrylate (1.67 g, 13.2 mmol). The reaction mixture was heated to 110 °C in a microwave for 16 hours. The reaction mixture was cooled and the volatiles were evaporated under reduced pressure. The crude material was diluted with MTBE and filtered on a pad of celite. The filtrate was evaporated under reduced pressure. The crude residue was purified by column chromatography (silica 24 g, 5% to 50% to Ethyl acetate in hexanes) to afford racemic (E)-tert-butyl l-methyl-2-styrylcyclopropanecarboxylate as a mixture of 1,2-cis and 1,2-trans isomers. LCMS (ESI+): 203 (M-tBu+H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With 3-chloro-benzenecarboperoxoic acid In cyclohexane at 0 - 90℃; | |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 30℃; for 20h; | A tert-butyl 2-methyloxirane-2-carboxylate To a 2000 mL 3 -neck round bottom flask fitted with a condenser, a solution of tert-butyl methacrylate (44 g, 309 mmol) in CH2CI2 (1000 mL) was added portion wise w-CPBA (120 g, 557 mmol). The resulting solution was stirred at 30 °C for 20 hours, resulting large amount of precipitate. The slurry was filtered, to the filtrate was added in small portions of saturated sodium thiosulfate solution (about 100 mL, added in small portions until no more heat is generated). The aqueous was separated and the organic phase was washed with saturated NaHC03 (2x400 mL) and brine (400 mL), dried over Na2S04, filtered and concentrated to obtain the title compound. 1H- MR (400 MHz, Chloroform-d) δ 3.02 (d, J= 5.95 Hz, 1 H), 2.68 (d, J= 6.17 Hz, 1 H), 1.51 (s, 3 H), 1.46 (s, 9 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hafnium metal complex In ethanol at 40℃; for 5h; Green chemistry; | 2.14 Preparation Example 14 To the 50 mL round bottom flask was added pentaerythritol 1.0 mmol and acrylate (R1 = H, R2 = methyl, R3 = H) 4.0mmol, the catalyst with the main I (ΜA = Hf, R5 , R6, R7 = ethyl, R4, R8 = H, X = OSO2C8F17, ligand solvent molecule is water, 1,4-dioxane) 0.5mol%, 10 mL of ethanol was added dropwise, the reaction was carried out at 40 °C for 5 h, 2,6-di-tert-butylphenol 4.0 mmol was added and the reaction was carried out at 200 °C for 3 h. After the reaction, the target compounds A, C and D (R1 = Η, R2 = methyl) were obtained by column chromatography. The yields were 33 %, 31% and 28% respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With copper(II) oxide In water; acetone at 95℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With iron(III) chloride; potassium <i>tert</i>-butylate In N,N-dimethyl acetamide at 25℃; for 12h; Glovebox; Schlenk technique; Irradiation; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(II) acetate hydrate; (R)-segphos In diethyl ether at 20℃; for 5h; Inert atmosphere; Overall yield = 82 %; Overall yield = 100 mg; Optical yield = 38 %ee; | 8 Example 8 Under nitrogen protection and stirring,(R)-(+)-SEGPHOS (L6, R5=Ph) (7.4 mg), Cu(OAc)2H2O (2.2 mg) were added to the dry reaction flask.Diethyl ether (1.0 mL),Polymethylhydrogensiloxane (48 μL).To the above solution was added dropwise tert-butyl methacrylate (130 μL) while stirring at room temperature.A solution of methyl 3-benzoylpropionate (77 mg) in ether (4.0 mL),Continue to react for 5h.Then saturated aqueous NH4F (2 mL) was added,And continue stirring for 30 minutes,Phase,Extract the aqueous phase with ether (3 x 10 mL)The combined organic phases are washed with saturated saline solution,Drying with anhydrous sodium sulfate,After concentration,After column chromatography, colorless liquid γ-phenyl-γ-(1-methyl-1-tert-butoxycarbonylethyl)-γ-cyclobutyrolactone (100 mg, yield 82%, ee value) was isolated. 38%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With tert.-butylnitrite; manganese(III) triacetate dihydrate In decane; acetonitrile at 20℃; for 5h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2,4,6-Triisopropylthiophenol; sodium t-butanolate In 1-methyl-pyrrolidin-2-one; <i>tert</i>-butyl alcohol at 25℃; for 24h; Schlenk technique; Sealed tube; Irradiation; | 1.S1-1.S8 S1: Transfer the dry Schlenk tube (10mL) with magnets to the glove box,Add sodium tert-butoxide (48mg, 0.5mmol, 2.5 times equivalent);S2: Take the Schlenk tube out of the glove box and connect it to the double-row tube connected to the CO2 cylinder. Under the condition that the Schlenk tube is sealed, the double-row tube is pumped with CO2 at least 3 times, and the N2 in the branch is removed to make It is filled with CO2 gas;S3: Add NMP (2mL), tert-butanol (38μL, 0.4mmol, 2 times equivalent), 2,4,6-triisopropylthiophenol (95mg, 0.4mmol, 2 times equivalent) and Reaction substrate (1) (0.2mmol);S4: Seal the Schlenk tube and place it under liquid nitrogen. After it is completely frozen,Open the Schlenk tube and keep it pumped for 5 minutes; then close the Schlenk tube,After thawing completely, put it under liquid nitrogen to degas, do this twice;S5: After thawing for the second time, open the Schlenk tube to fill it with CO2 atmosphere,To the pressure in the pipe is 1 atmosphere;S6: Place the reaction solution 1cm away from the 30W blue LED light source,Stir the reaction at room temperature (25°C) for 24h;S7: The reaction was quenched with 3 mL ethyl acetate and 1.5 mL 2N hydrochloric acid,After extraction with ethyl acetate for 6 times, the organic phase was directly concentrated and spin-dried to obtain the initial product;S8: The initial product is purified by flash column chromatography to obtain the pure desired product (2),The eluent used for purification is a mixture of petroleum ether, ethyl acetate and glacial acetic acid.The volume ratio of petroleum ether to ethyl acetate in the mixture is 10:1, and the mass fraction of glacial acetic acid is 0.4-0.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane at 40℃; Inert atmosphere; | 1.5 Step 5: Synthesis of 7,4'-diacetyl-8-(2-methyl-2-pentenoate tert-butyl ester-yl) dihydroflavonoid (compound 1a-5) Add 200mg (0.52mmol) 7,4'-diacetyl-8-allyldihydroflavone, 1g (7mmol) methacrylic tert-butyl ester, and 212mg (0.25mmol) second-generation Grubbs catalyst into the reaction flask. 30 mL of dichloromethane was reacted at 40°C under nitrogen protection and monitored by TLC. After the reaction was completed, the solvent was rotary evaporated and passed through a flash chromatography column (ethyl acetate/petroleum ether=3%-10%) to obtain 150 mg of an oily liquid with a yield of 58%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With sodium hydroxide In methanol at 20℃; Inert atmosphere; | 1.7 Step 5: Synthesis of 3’-allyl-2’-hydroxy-4,4’-dimethoxymethoxychalcone General procedure: Under the protection of nitrogen, add 1.7g (7.2mmol) 1a-c, 24mL methanol/60% sodium hydroxide aqueous solution (3:1) to the reaction flask, stir to completely dissolve the solid, then add 1.2g (7.2mmol) 1a-d, Stir at room temperature, monitored by TLC. After the reaction, spin dry methanol, add dilute hydrochloric acid to adjust the pH to 5-6, extract with ethyl acetate/water, combine the organic phases, wash with saturated sodium chloride solution, dry with anhydrous sodium sulfate, spin dry the solvent, add ethanol to precipitate The solid was filtered to obtain 1.5 g of a yellow solid with a yield of 56%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With lithium tert-butoxide In dimethyl sulfoxide at 25℃; for 12h; Schlenk technique; Irradiation; Glovebox; | 2 Experimental General procedure: To an oven-dried Schlenk tube (25 mL) containing a stirring bar was charged with 4-alkyl DHP 1 (0.2 mmol, 1.0 equiv.),alkene 2 (0.3 mmol, 1.5 equiv., if solid) and transferred toglovebox to add LiOtBu (64.0 mg, 0.8 mmol, 4.0 equiv.).The tube was then evacuated and back-filled with CO2 forthree times. Subsequently, 2 (if liquid) and dimethyl sulfoxide(DMSO) (3.0 mL) were added under CO2 atmosphere.The reaction was stirred in water bath and irradiated with a30 W blue light-emitting diode (LED) lamp (3 cm away,with a cooling fan to keep the reaction temperature at25-30 °C) for 12 h. The resulting mixture was quenched by2 mL of 2N HCl (aq.), 4 mL of H2O and diluted with 4 mL ofEtOAc and then stirred for 10 min and extracted by EtOAcfor 4 times and the combined organic phases were concentratedin vacuo. The residue was purified by silica gelflash column chromatography (CH2Cl2 as eluent) to give thepure desired alkylative carboxylation product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With pyrrolidine; Diphenylacetaldehyde; oxygen In ethanol; water at 20℃; for 16h; Inert atmosphere; Irradiation; | 46 Example 8 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-1-octanol (b) General procedure: Add diphenylacetaldehyde (45.0 mg, 0.50 mmol, 1.0 equiv.) To a 20 mL two-necked eggplant-shaped flask equipped with a stir bar, reduce the pressure with a vacuum pump, and then return to normal pressure with argon. I went there times. To this, 1,2-dichloroethane (2.5 mL), styrene (29 μL, 0.25 mmol) and pyrrolidine (44 μL, 0.53 mmol, 2.1 equiv.),1-Iodotridecafluorohexane (180 μL, 0.75 mmol, 3.3 equiv.) And water (25 μL, 5.0 equiv.) Were charged, and light irradiation was carried out with a 23 W-CFL lamp for 16 hours at room temperature with stirring. rice field.After completion of the reaction, a crude product was obtained by concentrating with an evaporator, and the yield of the target product was calculated by 19F-NMR measurement using trifluoromethylbenzene as an internal standard substance.The yield of the target product was 41%.The target product 3,3,4,4,5,5,6,6,7,7 purified and isolated by silica gel column chromatography (hexane / ethyl acetate = 10/1 to 8/1 vol / vol). , 8,8,8-Tridecafluoro-1-phenyl-1-octanol (b) had the following analytical values. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5% | With Bromotrichloromethane; rhodamine 6G; potassium hydroxide at 20℃; for 18h; Irradiation; Inert atmosphere; | General procedure: Under argon atmosphere, to a flask containing crushed KOH (140 mg, 2.5 mmol) was added a solution of 3e (204 mg, 1.0 mmol), BrCCl3 (296 L, 3.0 mmol), and rhodamine 6G (24 mg, 0.050 mmol) in degassed MeOH (10 mL) at room temperature. The stirred reaction mixture was irradiated with a white LED lamp (1000 lm) at room temperature. After being stirred for 19 h, the reaction mixture was filtered with folded filter paper which was then washed with MeOH several times. The filtrate was concentrated under reduced pressure. Purification of the residue by flash silica gel column chromatography (AcOEt/hexanes, 1:10 to 1:2) afforded product 6 (53 mg, 21%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; tetrabutylammonium nitrate; potassium carbonate In 1,2-dimethoxyethane at 20℃; for 24h; Irradiation; Sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With air In dimethyl sulfoxide at 30℃; for 12h; Sealed tube; Schlenk technique; chemoselective reaction; | β-Hydroxysulfides 3; General Procedure General procedure: A mixture of amide 1 (0.2 mmol), thiophenol derivative 2 (0.3 mmol), and DMSO (2 mL) was added to a 25 mL flame-dried Young-type tube under air atmosphere, and then the tube was sealed and the contents were stirred at 30 °C for the indicated reaction time (Schemes 2 and 3). After evaporation of the solvent under reduced pressure, the residue was purified by flash column chromatography on silica gel to give the desired product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 75% 2: 19% | With bis((-)pinanediolato)diboron; 3-pentyl isonicotinate; methoxybenzene at 100℃; for 12h; Inert atmosphere; Schlenk technique; diastereoselective reaction; |
Tags: 585-07-9 synthesis path| 585-07-9 SDS| 585-07-9 COA| 585-07-9 purity| 585-07-9 application| 585-07-9 NMR| 585-07-9 COA| 585-07-9 structure
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