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CAS No. : | 626-20-0 | MDL No. : | MFCD03427262 |
Formula : | C9H10O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PECUPOXPPBBFLU-UHFFFAOYSA-N |
M.W : | 134.18 | Pubchem ID : | 584146 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
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 |
---|---|---|
92% | Stage #1: methyl-triphenylphosphonium iodide With potassium carbonate In 1,4-dioxane at 20℃; for 1h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In 1,4-dioxane at 110℃; for 16h; Inert atmosphere; | 1 Synthesis of 3-Methoxyvinylbenzene Dissolve methyltriphenylphosphonium iodide (39.19g, 96.95mmol, 1.2eq) in 1,4-dioxane (500ml), add potassium carbonate (16.75g, 121.19mmol, 1.5eq) under nitrogen protection , Stir at room temperature for 1 hour.3-Methoxybenzaldehyde (11g, 80.79mmol, 1.0eq) was added to the reaction system.Stir at 110°C for 16 hours under nitrogen protection.The solvent was removed under reduced pressure, ethyl acetate (200ml) was added, washed with water (80ml×3), the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was purified by column chromatography (n-hexane) to obtain a yellow oily liquid (10g) , The yield is 92%). |
70.1% | Stage #1: methyl-triphenylphosphonium iodide With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; | 5.1.1. General procedure for the synthesis of styrenes General procedure: To a solution methyltriphenylphosphonium iodide (37 mmol) in dry THF (60 ml), tBuOK (40 mmol) was added in several portions, and stirring under argon was continued for 1 h. The aldehyde (14 mmol) was added, and stirring was continued for another 24 h. The reaction mixture was diluted with dichloromethane (150 ml), washed with water and brine (2 × 10 ml each), dried (Na2SO4), and the solvents were evaporated under diminished pressure. The crude product was purified by chromatography (silica gel, hexane/ethyl acetate mixtures). |
60% | Stage #1: methyl-triphenylphosphonium iodide With potassium <i>tert</i>-butylate In tetrahydrofuran at -80 - -70℃; for 1h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at -80 - 20℃; Inert atmosphere; |
43% | With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; | |
With n-butyllithium In diethyl ether; hexane for 12h; Ambient temperature; | ||
With potassium carbonate In 1,4-dioxane; water Heating; | ||
With potassium <i>tert</i>-butylate In tetrahydrofuran | ||
Stage #1: methyl-triphenylphosphonium iodide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 2h; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 20℃; for 4h; | ||
Stage #1: methyl-triphenylphosphonium iodide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 2h; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With AD-mix-α In water; <i>tert</i>-butyl alcohol at 0℃; for 9h; | |
With AD-mix-α; water; <i>tert</i>-butyl alcohol Yield given; | ||
2.9 g | With AD-mix-α In water; <i>tert</i>-butyl alcohol at 25℃; for 16h; |
96 %Chromat. | With alpha-D-glucopyranose; Escherichia coli (SSP1) In Hexadecane at 30℃; for 8h; Green chemistry; Enzymatic reaction; enantioselective reaction; | |
With AD-mix α In water; <i>tert</i>-butyl alcohol at 0℃; | Generalprocedure for dihydroxylation of styrenes: General procedure: A round-bottomed flask, equipped with amagnetic stirrer, was chargedwith 5 mL of tert-butyl alcohol, 5 mL of water, and 1.4 g ofAD-mix-α or AD-mix-β. Stirring at rt produced two clear phases; the loweraqueous phase appears bright yellow. The mixture was cooled to 0 °C whereuponsome of the dissolved salts precipitated.One mmol of olefin was addedat once, and the heterogeneous slurry was stirred vigorously at 0 °C for 6-24 h(progress was monitored by TLC). While the mixture was stirred at 0 °C, anhydroussodium sulfite (1.5 g) was addedand the mixture was allowed to warm to rt and further stirred for 30-60 min. EtOAc (10 mL) was added to the reactionmixture and after separation of the layers, the aqueous phase was furtherextracted with EtOAc (3x5 mL). The combined organic extracts were dried over anhydrousNa2SO4 and concentrated to afford the diol and theligand. This crude reaction mixture waspurified by silica gel column chromatography (100-200 mesh) elutingwith EtOAc/petroleum ether (1:1) to afford the pure1,2-diol in 80-98% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate In tetrahydrofuran Inert atmosphere; Reflux; | |
90% | Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -5 - 0℃; for 0.5h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 0 - 25℃; for 3h; | |
81% | With potassium carbonate In tetrahydrofuran at 75℃; for 10h; Inert atmosphere; |
75% | With potassium carbonate In 1,4-dioxane for 16h; Reflux; | |
73% | Stage #1: Methyltriphenylphosphonium bromide With sodium amide In diethyl ether at 20℃; for 10h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In diethyl ether at -10 - 20℃; Inert atmosphere; | |
67% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1.16667h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; | Synthesis of styrenes 2e and 2k-2l General procedure: Following the literature procedure to the solution of methyltriphenylphosphonium bromide (19.1-20.8 g, 53.4-58.1 mmol) in THF (50 ml) t-BuOK (6.5-7.1 g, 57.7-62.9 mmol) was added portionwise while vigorous stirring in Ar atmosphere for 10 minutes. The mixture was stirred for 1 hour at room temperature. Then the corresponding carbonyl compound (4-iso-propylbenzaldehyde, 3-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3.0 g, 20.2-22.0 mmol) was added dropwise. The mixture was stirred for 24 hours at room temperature. After that it was diluted with CH2Cl2 (180 ml), washed with water (3 × 15 mL), dried over Na2SO4, concentrated under reduced pressure and dried at 10-20 torr. Desired styrenes were isolated by chromatography on SiO2 with elution using PE-EA in a linear gradient of the latter from 0 to 10 vol%. |
66% | Stage #1: Methyltriphenylphosphonium bromide With potassium hydride; paraffin In tetrahydrofuran Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 0℃; | |
50.7% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 0 - 25℃; for 16h; Inert atmosphere; | 13.2; 14.2 Step 2: 1-Methoxy-3-vinylbenzene To a mixture of methyltriphenylphosphonium bromide (25.19 g, 70.51 mmol) in THF (100 ml_) was added f-BuOK (8.57 g, 76.39 mmol) in several portions at 0 °C under N2. The mixture was stirred at 0 °C for 1 hr under N2. Then 3-methoxybenzaldehyde (8 g, 58.76 mmol, 7.14 ml_) was added dropwise at 0 °C under N2. The mixture was stirred at 25 °C for 16 hr. The mixture was diluted with PE (100 ml_) and filtered. The mother liquor was concentrated under reduced pressure and the residue was purified by silica gel chromatography (PE - PE / EA = 100 / 1) to afford the title compound (4 g, 29.81 mmol, 50.7% yield) as a yellow oil. 1H NMR (400 MHz, CDCI3) d = 7.27 - 7.22 (m, 1 H), 7.02 (d, J = 7.6 Hz, 1 H), 6.98 - 6.94 (m, 1 H), 6.84 - 6.81 (m, 1 H), 6.73 - 6.66 (m, 1 H), 5.78-5.73 (m, 1 H), 5.26 (d, J = 10.8 Hz, 1 H), 3.83 (s, 3H) ppm. |
47% | With potassium carbonate In tetrahydrofuran for 16h; Inert atmosphere; Schlenk technique; Reflux; | |
44% | Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran; hexane at 0 - 20℃; Inert atmosphere; | |
With n-butyllithium Yield given. Multistep reaction; | ||
With potassium <i>tert</i>-butylate In tetrahydrofuran Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With sodium hydride In tetrahydrofuran at 0℃; for 0.25h; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 20℃; | 1.1 General procedure for the synthesis of b-azidostyrenes(9A-D) General procedure: To a cooledsolution (0 C) of methyltriphenylphosphonium bromide(1.2 equiv mol) in dry THF, NaH 60% (6 equiv mol) was slowlyadded. After 15 min. O-Pivaloyl-vanilline (6A) (1 equiv mol) wasadded and the reaction is stirred at room temperature overnight.The reaction is quenched with H2SO4 2 N and extracted withEtOAc. The organic layers were dried over Na2SO4, filtered andevaporated. The residue was purified by GCC on silica gel(PE/EtOAc 95:5 as eluant) to afford 7A as pure compound (83%). | |
With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 16h; | ||
Stage #1: Methyltriphenylphosphonium bromide In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Alkaline conditions; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 0℃; for 12h; Inert atmosphere; | General procedure for thesynthesis of substituted styrenes: General procedure: To a stirred suspension ofmethyltriphenylphosphonium bromide in THF, base (inorganic base like NaH, NaNH2or organic base like n-BuLi) wasadded under argon at 0 °C and stirred for 30 min. After the mixture was cooledagain to 0 °C, aromatic aldehyde in THF was added drop wise and stirred for 12h. The mixture was concentrated in vacuo andresidue was dissolved in water and the aqueous layer was extracted with DCM(3x35 mL). The combined organic extracts were dried over anhydrous Na2SO4,concentrated and purified by silica gel (100-200 mesh) column chromatography inpetroleum ether: ethyl acetate (95:5) to afford pure styrene (85-99% yield). | |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 0 - 20℃; for 10h; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide In tetrahydrofuran at 0℃; for 0.5h; Alkaline conditions; Inert atmosphere; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran for 12h; Inert atmosphere; | ||
With sodium hydride In tetrahydrofuran at 0 - 20℃; Inert atmosphere; | 2.7. General procedure for the synthesis of styrene (10) General procedure: To a stirred suspension of benzaldehyde (3 mmol) and methyltriphenylphosphonium bromide (1.29 g, 3.6 mmol) in THF (12 mL) was added sodium hydride (0.33 g, 13.8 mmol) under argon purge at 0 °C. After the mixture was stirred overnight at room temperature, the organic layer was washed three times with brine, dried over Na2SO4, filtered, and concentrated. The reside was purified by silica gel column chromatography (pure petroleum ether) to afford corresponding styrene 10 in a good yield. | |
With potassium carbonate In tetrahydrofuran for 12h; Reflux; Inert atmosphere; | ||
With potassium carbonate In 1,4-dioxane for 24h; Schlenk technique; Inert atmosphere; Reflux; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 1h; Stage #2: 3-methoxy-benzaldehyde In tetrahydrofuran at 20℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: N,N,2-trimethylpropionamide With trifluoromethylsulfonic anhydride In dichloromethane at -15℃; for 0.166667h; Stage #2: 3-methoxystyrene With 2,3,5-trimethyl-pyridine for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With trifluorormethanesulfonic acid; 1,5-bis-(diphenylphosphino)pentane In 1,4-dioxane at 110℃; for 48h; | |
91% | With trifluorormethanesulfonic acid In 1,4-dioxane at 110℃; for 48h; | 2.11 The scope of the reactions catalyzed by Ru (cod) (2-methylallyl) 2, DPPPent and TfOH cocatalyst is summarized in Table 2. Reactions of vinylarenes with a series of cyclic and acyclic secondary amines formed p-phenethylamines with >99% regioselectivity. In most cases the reaction yields were limited by conversion, not formation of side products. Polymerization of styrene competed with hydroamination, but no enamine from oxidative amination was formed. Various cyclic amines reacted with styrene in good to excellent yields (entries 1-5). High yields for reaction of 4-piperidone ethylene ketal and Boc-piperazine underscore that the strength of the triflic acid is leveled by the presence of the alkylamine and that late-metal catalysts tolerate Lewis basic carbonyl groups and acid-labile functionality. In contrast to hydroamination or oxidative amination with rhodium catalysts, benzylic amines such as 1,2, 3,4-tetrahydroisoquinoline reacted in good yield (entry 6) but with only 65% conversion. Table 2. Ruthenium-catalyzed hydroamination of vinylarenes with alkylamines.a 5mol% Ru (cod) (2-methylallyl) 2 HNRR'+ R"> 7mol% DPPPent/10mol% CF3SO3H NRR' R" dioxane, 100 °C, 24 h entry product yield b entry product yields Me < NJ 96% gc, d, e m NPh 50% (// ho 2 No 91% 9 Me NJ 81% / ^N. Ph Me O 3 c N 64% 10 N--j 72% Me N. COz Bu O 4 N 90% 11 e. 1. g MeO N _J 91% zu po 5 Na 82% 12 1. 9. h F3C N,) 71% r, :) o I o 6 c 65% 13 h N 51% FOC Me Me 0 7c, d, e v MHexyl 63% 14dii, NJ 40% / "Amine/Vinylarene/Ru/DPPPent/TfOH = 1: 2: 0.05 : 0.07 : 0.10 (1 mmol of amine) in 0.50 mL dioxane. b Isolated yield. c 4 mmol of vinylarene was used. d 80 °C.e 48 h. f 0. 25 mL of dioxane. g 110 °C.'iPr-DPPF was used as ligand.'1. 5 mmol of vinylarene was used.'72 h. The acyclic, secondary aliphatic and benzylic amines n-hexyl methylamine (entry 7) and N-benzyl methylamine (entry 8) added across styrene. In contrast to the palladium- catalyzed Markovnikov hydroamination, 14 the exchange of benzyl groups between amines20 was not observed. Thus, the lower yield of addition of these less reactive amines reflects 67% and 53% conversions. More hindered acyclic, aliphatic amines, such as dibutylamine, generated only trace product at 100 °C. The hydroamination of vinylarenes with morpholine in the presence of Ru (cod) (2- methylallyl) 2 and DPPPent encompassed electron-poor to electron-neutral styrenes (entries 9- 11). Further, the first transition metal-catalyzed hydroamination of a-methyl styrene was observed (entry 14). Conversions were modest, but a single addition product was observed. The combination of Ru (cod) (2-methylallyl) 2 and di-iso-propylphosphinoferrocene (DiPPF) was more active for hydroaminations of vinylarenes containing electron- withdrawing groups. For example, the reaction of vinylarenes containing 3-and 4-CF3 in the presence of 5% Ru (cod) (2-methylallyl) 2 and 7% DiPPF gave the addition products in good to moderate yields (entries 12-13), while these reactions in the presence of the catalyst with DPPPent occurred in less than 20% yield.; The general procedure was followed with 3-methoxystyrene (278 1, 2.00 mmol), morpholine (86.5 mg, 0.99 mmol) and 0.25 mL of 1, 4-dioxane. The reaction mixture was stirred at 110 °C for 48 h. After the heating, the reaction mixture was purified by flash column chromatography (20% EtOAc in hexane) to give 200 mg (91%) of the hydroamination products NMR (500 MHz, CDC13, TMS) 8 2.47-2. 56 (m, 4H), 2.57-2. 63 (m, 2H), 2.76-2. 81 (m, 2H), 3.74 (t, J= 4.5 Hz, 4H), 3.80 (s, 3H), 6.73-6. 78 (m, 1H), 6.76 (s, 1H), 6.80 (d, J= 7.6 Hz, 1H), 7.17-7. 23 (m, 1H) ; 13C IHI NMR (125 MHz, CDC13) 8 33.6, 53.9, 55.4, 60.9, 67.2, 111.5, 114.8, 121.3, 129.6, 142.0, 159.9 ; Anal. Calcd for C13H19NO2 : C, 70.56 ; H, 8.65 ; N, 6.33. Found: C, 70.46 ; H, 8.94 ; N, 6. 28. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 3-methoxystyrene With N-Bromosuccinimide; water; acetic acid In 1,4-dioxane at 0 - 20℃; Stage #2: With sodium hydroxide In 1,4-dioxane; water at 20℃; | 5.1 Example 5: Preparation of 5-{4-[2-(3-methoxyphenyl) -2-oxoethoxy]benzyl}-l,3 - thiazoIidine-2,4-dione.; Step 1: 2-(3-methoxyphenyl)oxirane; [00158] To a solution of 3-vinylanisole (5.0 g, 37.0 mmol) and acetic acid (2.1 mL, 37.0 mmol) in dioxane (33 ml) and H2O (78 ml) at O0C was added N-bromosuccinimide (7.30 g, 41.0 mmol) in three portions. The reaction was allowed to warm to R.T. and then 2M NaOH (50 ml) was added. The reaction was left to stir at RT overnight. The reaction mixture was then partitioned between water and EtOAc, and the aqueous phase was extracted with EtOAc. The combined organic phases washed with brine, dried (Na2SO4), filtered and evaporated in vacuo to give 5.60 g (100%) of the title compound as a slightly tinted oil. |
100% | Stage #1: 3-methoxystyrene With N-Bromosuccinimide; water; acetic acid In 1,4-dioxane at 0 - 20℃; Stage #2: With sodium hydroxide In 1,4-dioxane; water at 20℃; | 5.1 To a solution of 3-vinylanisole (5.0 g, 37.0 mmol) and acetic acid (2.1 mL, 37.0 mmol) in dioxane (33 mL) and H2O (78 mL) at 0 °C was added N-bromosuccinimide (7.30 g, 41.0 mmol) in three portions. The reaction was allowed to warm to R.T. and then 2M NaOH (50 mL) was added. The reaction was left to stir at RT overnight. The reaction mixture was then partitioned between water and EtOAc, and the aqueous phase was extracted with EtOAc. The combined organic phases washed with brine, dried (Na2SO4), filtered and evaporated in vacuo to give 5.60 g (100%) of the title compound as a slightly tinted oil |
100% | Stage #1: 3-methoxystyrene With N-Bromosuccinimide; acetic acid In 1,4-dioxane; water at 0 - 20℃; Stage #2: With sodium hydroxide In 1,4-dioxane; water at 20℃; | 5.1 Step 1: 2-(3-methoxyphenyl)oxirane. To a solution of 3-vinylanisole (5.0 g, 37.0 mmol) and acetic acid (2.1 mL, 37.0 mmol) in dioxane (33 mL) and H20 (78 mL) at 0 °C was added N-bromosuccinimide (7.30 g, 41.0 mmol) in three portions. The reaction was allowed to warm to RT and then 2M NaOH (50 mL) was added. The reaction was left to stir at RT overnight. The reaction mixture was then partitioned between water and EtOAc, and the aqueous phase was extracted with EtOAc. The combined organic phases washed with brine, dried (Na2S04), filtered and evaporated in vacuo to give 5.60 g (100%) of the title compound as a slightly tinted oil. |
100% | With N-Bromosuccinimide; acetic acid In 1,4-dioxane; water at 0 - 20℃; | 5.1 Step 1: 2-(3-methoxyphenyl)oxirane To a solution of 3-vinylanisole (5.0 g, 37.0 mmol) and acetic acid (2.1 mL, 37.0 mmol) in dioxane (33 mL) and H2O (78 mL) at 0° C. was added N-bromosuccinimide (7.30 g, 41.0 mmol) in three portions. The reaction was allowed to warm to RT and then 2M NaOH (50 mL) was added. The reaction was left to stir at RT overnight. The reaction mixture was then partitioned between water and EtOAc, and the aqueous phase was extracted with EtOAc. The combined organic phases washed with brine, dried (Na2SO4), filtered and evaporated in vacuo to give 5.60 g (100%) of the title compound as a slightly tinted oil. |
84% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 24h; | |
With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane; water at 20℃; for 2.5h; | ||
With 3-chloro-benzenecarboperoxoic acid | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With palladium diacetate; oxygen In phenyl cyanide at 60℃; for 24h; | |
64% | With oxygen; palladium diacetate; copper chloride (II) In phenyl cyanide at 60℃; for 14h; | 7.1 1) Preparation of 2-(1-(3-methoxyphenyl)vinyl)isoindoline-1,3-dione (compound Ig) In a 100 mL round-bottom flask, add phthalimide (3.17 g, 21.6 mmol, 1 equiv), palladium acetate (0.243 g, 1.08 mmol, 5 mol %), CuCl2(0.438 g, 3.24 mmol, 15 mol %) , benzonitrile (15 mL), stirred and warmed to 60 °C.Then 3-methoxystyrene (14.5 g, 108 mmol, 5 equiv) was slowly added dropwise, and the reaction was carried out under O2at 60° C. for 14 h.Cool to room temperature for column chromatography, the specific conditions are: packing the column with petroleum ether, and the eluent is petroleum ether:ethyl acetate=50:1, 20:1 to obtain a yellow solid (3.87g, 64% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With 5-chloro-2-hydroxybenzoic acid; boric acid; Tri(p-tolyl)phosphine for 24h; Heating; | |
With 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate; 1,2-bis[di(t-butyl)phosphinomethyl]benzene; bis(dibenzylideneacetone)-palladium(0) In dichloromethane at 20℃; for 14h; Overall yield = 76 %; Overall yield = 148 mg; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C67H51IrN2O2 In tetrahydrofuran at -78℃; for 24.1667h; optical yield given as %ee; enantioselective reaction; | |
88 % Spectr. | In tetrahydrofuran at -78 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With N-Methyldicyclohexylamine In 1,4-dioxane at 150℃; for 1h; Microwave irradiation; | 258 Example 258; 2- Amino-6- { 3 - [(E)-2-(3 -methoxy-phenyl)-vinyl] -benzyl} -3 -methyl-3H-pyrimidin-4-one (Scheme 9, F); A thick-walled glass vial was charged with a stir bar, 2-amino-6-(3-bromo-benzyl)-3-methyl-3H-pyrimidin-4-one (Scheme 9, C) (130 mg, 0.44 mmol), 3-vinylanisole (89 mg, 0.66 mmol), tris(dibenzylideneacetone)dipalladium (0) (8 mg, 0.009 mmol), tetrafluoroborate (10 mg, 0.035 mmol), iV.N-dicyclohexyhnethylamine (104 mg, 0.53 mmol) and anhydrous 1,4-dioxane (2 mL). The reaction vial was sealed and subject to microwave radiation for 1 h at 150 0C. The resultant slurry was filtered, washed with methanol (3 x 3 mL) then concentrated in vacuo. The resultant residue was subject to reverse phase purification (13-50% acetonitrile over 35 min). Appropriate fractions were concentrated via centrifugal evaporation to afford the white trifiuoroacetic acid salt of the title compound (148 mg, 73%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;palladium diacetate; In N,N-dimethyl acetamide; water; ethyl acetate; | Referential Example 40 To 5 mL of N,N-dimethylacetamide solution containing 0.50 g of <strong>[890315-72-7]tert-butyl 4-bromo-2-nitrobenzoate</strong>, 0.37 mL of 3-vinylanisole, 0.47 mL of triethylamine and 0.11 g of palladium acetate were added at room temperature and stirred under nitrogen atmosphere at 110C for 4 hours. Ethyl acetate and water were added after the reaction mixture was cooled to room temperature. The organic layer was separated and dried over anhydrous magnesium sulfate after washed with 10% citric acid aqueous solution and a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure. The obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia Chemical Ltd., eluent; hexane: ethyl acetate = 10:1] to obtain 0.20 g of tert-butyl 4-((E)-2-(3-methoxyphenyl)vinyl)-2-nitrobenzoate a pale yellow solid. 1H-NMR (DMSO-d6) delta: 1.51 (9H, s), 3.81 (3H, s), 6.90-6.94 (1H, m), 7.20-7.27 (2H, m), 7.34 (1H, t, J = 7.9 Hz), 7.43 (1H, d, J = 16.6 Hz), 7.55 (1H, d, J = 16.6 Hz), 7.84 (1H, d, J = 8.0 Hz), 7.97 (1H, d, J = 7.8 Hz), 8.21 (1H, s). | |
With triethylamine;palladium diacetate; In ISOPROPYLAMIDE; at 20 - 110℃; for 4.0h; | To N,N-dimethylacetamide 5mL solution of <strong>[890315-72-7]tert-butyl 4-bromo-2-nitrobenzoate</strong> 0.50g were added 3-vinylanisole 0.37mL, triethylamine 0.47mL and palladium acetate 0.11g at room temperature, and it was stirred under nitrogen atmosphere at 110C for 4 hours. After the reaction mixture was cooled to room temperature, ethyl acetate and water were added to it. The organic layer was separated and collected, dried over anhydrous magnesium sulfate after sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [Fuji SILYSIA Chemical Ltd., PSQ100B(spherical type), eluent; hexane:ethyl acetate=10:1] to give tert-butyl 4-((E)-2-(3-methoxyphenyl)vinyl)-2-nitrobenzoate 0.20g of pale yellow solid. 1H-NMR(DMSO-d6) delta value: 1.51(9H,s),3.81(3H,s),6.90-6.94(1H,m),7.20-7.27(2H,m),7.34(1H,t,J=7.9Hz),7.43(1H,d,J=16.6Hz),7.55( 1H,d,J=16.6Hz),7.84(1H,d,J=8.0Hz),7.97(1H,d,J=7.8Hz),8. 21(1H,s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With bis(acetylacetonate)nickel(II); diethylzinc; caesium carbonate In tetrahydrofuran at 23℃; for 12h; Inert atmosphere; | |
92% | Stage #1: 3-methoxystyrene With bis(cyclopentadienyl)titanium dichloride; isopropylmagnesium chloride; lithium bromide In diethyl ether at 30℃; for 24h; Schlenk technique; Inert atmosphere; Stage #2: carbon dioxide In tetrahydrofuran at 20℃; for 0.5h; Schlenk technique; Inert atmosphere; regioselective reaction; | |
91% | Stage #1: 3-methoxystyrene With N-(2,6-diisopropylphenyl)-N-((1E)-1-(6-[(1E)-N-(2,6-diisopropylphenyl)ethanimidoyl]pyridin-2-yl)ethylidene)amine; ethylmagnesium bromide; iron(II) chloride In tetrahydrofuran; diethyl ether at 20℃; for 2h; Inert atmosphere; Stage #2: carbon dioxide In tetrahydrofuran; diethyl ether for 0.5h; Inert atmosphere; regioselective reaction; |
66% | Stage #1: 3-methoxystyrene; carbon dioxide With neocuproine; diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; potassium carbonate In N,N-dimethyl-formamide at 20℃; for 24h; Molecular sieve; Irradiation; Stage #2: With hydrogenchloride; water regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With ammonia borane; copper(II) choride dihydrate In tetrahydrofuran; water at 80℃; diastereoselective reaction; | |
With bis-triphenylphosphine-palladium(II) chloride; tri-n-butyl-tin hydride In tetrahydrofuran at 20℃; Inert atmosphere; | ||
Stage #1: 1-ethynyl-3-methoxybenzene With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II); diisobutylaluminium hydride In tetrahydrofuran at 0 - 22℃; Inert atmosphere; Stage #2: With water; rochelle salt In tetrahydrofuran at 0℃; for 0.5h; |
90 %Chromat. | With hydrogen In ethanol at 20℃; for 3h; Schlenk technique; Sealed tube; chemoselective reaction; | |
With Dimethylphenylsilane; water In dimethyl sulfoxide at 70℃; for 0.333333h; Inert atmosphere; stereoselective reaction; | ||
96.1 %Chromat. | With hydrogen In methanol; dimethyl sulfoxide at 25℃; for 2h; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 3-methoxystyrene; tert.-butyl lithium In diethyl ether; pentane at -78℃; Cooling with acetone-dry ice; Stage #2: carbon dioxide In diethyl ether; pentane at -78 - 20℃; for 0.583333h; Stage #3: With ammonium chloride In diethyl ether; water; pentane | 15.1 Step 12-(3-methoxyphenyl)-4,4-dimethylpentanoic acidTo a solution of 1-methoxy-3-vinylbenzene (1.34 g, 10.0 mmol, 1.0 eq.) in dry Et2O (20 mL) cooled to -78 0C in a dry-ice/acetone bath, a solution of t-BuLi (768 mg, 12.0 mmol, 1.2 eq.) in pentane (7.0 mL) was added dropwise. The resulting solution turned orange, and was stirred at -78 0C for 30 mins. Dry CO2 (gas) was bubbled into the solution for 5 min at this temperature, the orange solution turned colorless quickly, and the reaction was warmed to r.t. for another 30 min. The resulting mixture was quenched with sat. aq. NH4CI (20 mL), extracted with EtOAc (50 mL x 3), washed with brine, dried over Na2SO4, and concentrated in vacuo to give the crude product, which was purified by column chromatography to obtain 2-(3-methoxyphenyl)-4,4-dimethylpentanoic acid (2.20 g, 90%), as a yellow oil. LCMS m/z 237.0 [M+H] +; 1H NMR (400 MHz, CDCl3) δ: 7.27- 7.21 (m, IH), 6.94 (d, J= 8.0 Hz, IH), 6.90 (bs, IH), 6.80 (dd, J= 8.0, 2.4 Hz, IH), 3.81 (s, 3H), 3.64 (dd, J= 8.8, 4.0 Hz, IH), 2.26 (dd, J= 14.0, 8.8 Hz, IH), 1.63 (dd, J= 14.0, 4.0 Hz, IH), 0.92 (bs, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium periodate; sodium azide; acetic acid In dimethyl sulfoxide at 75℃; for 2h; | General experimental procedure for 1,2-diazidation of alkenes and α,α-diazidation of arylketones: General procedure: To a suspension of NaN3 (15 mmol) and NaIO4 (5 mmol) in 20 ml of DMSO-glacial AcOH (4:1) was added alkenes (5 mmol) or arylketone (5 mmol), as the case may be, and the reaction mixture was stirred at 75 °C for 2 h. It was monitored by TLC and then poured into water (100 ml) and extracted with EtOAc (3 × 50 ml). The combined organic layers were washed with saturated solution of aqueous NaHCO3 (50 ml) followed by aqueous Na2S2O3 (5%, 50 ml), dried over anhyd Na2SO4. Concentration of the organic layer gave crude diazides, which were purified by silica gel-packed column chromatography using hexane/ethyl acetate (19:1) as eluent to obtain pure 1,2-diazides 2a-o or α,α-diazidoketones 4a-e, respectively. |
66% | With sodium azide; manganese(II) bromide tetrahydrate; tert-butylammonium hexafluorophosphate(V); acetic acid In acetonitrile at 22℃; Electrochemical reaction; Inert atmosphere; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 68% 2: 230 mg | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane at 43℃; for 22h; Inert atmosphere; | General procedure for the CM reaction of 4: General procedure: (E)-4,4,5,5-Tetramethyl-2-(4-styrylphenyl)-1,3,2-dioxaborolane 7a. Boronate 4a (113 mg, 0.49 mmol), styrene 5a (281 µL, 0.91 gmL-1, 2.45 mmol), Grubbs’ catalyst 6b (12 mg, 0.015 mmol), and CH2Cl2 (5 mL) were mixed in a round-bottomed flask and stirred under reflux (~ 45 °C) and nitrogen atmosphere for 6 hours. The mixture was cooled to rt, the volatiles were removed under reduced pressure and the crude product purified by flash chromatography on silica gel, hexane/CH2Cl2 6:4, to give 97 mg of the pure expected product as a white solid in 65% yield, (E)-isomer only. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With C37H40OTi In tetrahydrofuran at 100℃; for 8h; Inert atmosphere; Glovebox; Sealed tube; Schlenk technique; | |
85% | With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 20℃; for 4h; Inert atmosphere; | General procedure: [Ir(COD)Cl]2 (142 mg, 0.212 mmol) and 1,4-diphenylphosphinobutane (180 mg, 0.423 mmol) were dissolved in THF (20 mL) under nitrogen atmosphere, and into the yellow solution was added 1-methyl-2-vinylbenzene (27a) (1.00 g, 8.46 mmol). The mixture was stirred for 4 h at r.t., and evaporated. The residue was purified by silica gel chromatography (Hexane : EtOAc : = 10 : 1) to obtain 28a (2.05 g, 8.33 mmol, 98 %) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With C13H17ClN3O2Pd(1-); toluene-4-sulfonic acid In toluene at 100℃; for 18h; chemoselective reaction; | General conditions General procedure: to a mixture of 3 (0.25 mmol), 1 (10 mol %), and p-TsOH (5.00 × 10-2 mmol) in a 2 dram vial were added toluene (3 mL) and 2 (0.75 mmol). After stirring for 18 h at 100 °C, the reaction mixture was diluted with CH2Cl2 (3 mL), neutralized with Et3N (5.00 × 10-2 mmol), and filtered through Celite. The resulting solution was concentrated in vacuo then purified using flash column chromatography with silica gel (4:1 hexanes/EtOAc). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.3% | With N-Bromosuccinimide In dichloromethane at 0 - 20℃; for 20h; | 20 Preparation 20 N-[2-[2-Bromo-l-(3-methoxyphenyl)ethoxy]ethyl]-4-nitro-benzenesulfonamide Add ethylene oxide (11 mL, 220 mmol) all at once to DCM cooled to 0 °C; then add l-methoxy-3-vinylbenzene (7.09 g, 52.82 mmol) via a syringe. Stir the mixture while maintaining it 0 °C. Add N-bromosuccinimide (9.4 g, 52.82 mmol) and 4- nitrobenzenesulfonamide (8.9 g, 44.02 mmol). Wrap flask in foil and stir the reaction mixture for 20 h while maintaining it at ambient temperature. Concentrate under reduced pressure; filter; and concentrate the filtrate under reduced pressure to provide a residue. Purify the residue via flash column chromatography eluting with a 5-40% gradient of EtOAc in hexanes. Combine the product fractions, and remove the solvents under reduced pressure to provide the title compound as a dark yellow oil (14.22 g, 70.3%). MS (m/z): 459(M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With rhodium(II) pivalate In fluorobenzene at 50℃; for 4h; Inert atmosphere; | General Procedure for the Synthesis of Spirobarbiturates 3-15 and Spirothiobarbiturates 16-20. General procedure: To a solution of diazo compound 1 or 2 (1.0 mmol) and styrenes (2 mmol) in fluorobenzene (2 mL) was added rhodium pivalate (0.02mmol) at room temperature. The reaction mixture was stirredat 50 oC for 3-6 h. The solvent was evaporated underreduced pressure to give the residue. The residue was purified by flash column chromatography on silica gel to give the products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With rhodium(II) pivalate In fluorobenzene at 50℃; for 4h; Inert atmosphere; | General Procedure for the Synthesis of Spirobarbiturates 3-15 and Spirothiobarbiturates 16-20. General procedure: To a solution of diazo compound 1 or 2 (1.0 mmol) and styrenes (2 mmol) in fluorobenzene (2 mL) was added rhodium pivalate (0.02mmol) at room temperature. The reaction mixture was stirredat 50 oC for 3-6 h. The solvent was evaporated underreduced pressure to give the residue. The residue was purified by flash column chromatography on silica gel to give the products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With bis(1,5-cyclooctadiene)nickel (0); dicyclohexyl-tert-butylphosphine; triethylamine In 1,4-dioxane at 75℃; for 24h; Inert atmosphere; Glovebox; | 4.4 General procedure: Reactions of alkenes with trimethylsilyl trifluoromethanesulfonate: in a glovebox (N2 atmosphere), dicyclohexyl-tert-butylphosphine (15mol%) and Ni(COD)2 (10mol%) were added to a two dram vial equipped with a stirbar. Solid alkenes were also added at this time. Dioxane and triethylamine (5equiv) were then added sequentially, followed by liquid alkene (1equiv) if applicable. The vial was sealed with a Teflon-lined septum cap and removed from the glovebox. The reaction mixture was stirred at room temperature until homogeneous. Trimethylsilyl trifluoromethanesulfonate (3equiv) was then added via syringe at room temperature with stirring. The vessel was then heated in an oil bath at 75°C with stirring for 24h. The reaction was removed from the oil bath and cooled to room temperature. The reaction vessel was then opened to air, and brine and diethyl ether or hexanes were added. The brine layer was removed, and the organic layer was washed twice with brine. The combined aqueous layers were back-extracted twice with diethyl ether or hexanes. The combined organic layers were dried over MgSO4 and concentrated in vacuo. The product was purified using flash silica chromatography, eluting with the indicated solvent noted in parenthesis. 4.4.4 (E)-(3-Methoxystyryl)trimethylsilane (4) Following general procedure A: 3-vinyl-anisole (139 μL, 1 mmol), tBuPCy2 (38 mg, 0.15 mmol), Ni(COD)2 (27.5 mg, 0.1 mmol), Et3N (700 μL, 5 mmol), and Me3SiOTf (540 μL, 3 mmol) were reacted in dioxane (2 mL) at 75 °C for 24 h. The product was purified by flash chromatography on silica gel (5% Et2O:hexanes) and concentrated in vacuo to yield 159 mg of 4 (77%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.27 (t, J=7.8 Hz, 1H), 7.06 (d, J=7.7 Hz, 1H), 7.01 (t, J=2.0 Hz, 1H), 6.87 (d, J=19.2 Hz, 1H), 6.83 (dd, J=2.7, 0.8 Hz, 1H), 6.50 (d, J=19.1 Hz, 1H), 3.86 (s, 3H), 0.18 (s, 9H); 13C NMR (101 MHz, CDCl3) δ 159.9, 143.5, 139.9, 130.0, 129.6, 119.2, 114.0, 111.3, 55.5, -1.1; FTIR (cm-1) 2954, 1263, 865, 838. HRMS (EI) m/z, calcd for [C12H18OSi]: 206.1127; found: 206.1148. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: acetic acid; N-Bromosuccinimide / water; 1,4-dioxane / 0 - 20 °C 1.2: 20 °C 2.1: sodium hydroxide / toluene; water / 78 °C 3.1: piperidine / ethanol / Reflux 4.1: cobalt(II) chloride hexahydrate; sodium tetrahydroborate; acetic acid; [2,2]bipyridinyl / water; tetrahydrofuran 5.1: dimethyl sulfoxide; triethylamine; phosphorus pentoxide / dichloromethane / 2 h / 0 - 20 °C | ||
Multi-step reaction with 5 steps 1: acetic acid; N-Bromosuccinimide / water; 1,4-dioxane / 0 - 20 °C 2: sodium hydroxide / toluene / 78 °C 3: piperidine / ethanol / Reflux 4: sodium tetrahydroborate; acetic acid; [2,2]bipyridinyl; cobalt(II) chloride / tetrahydrofuran; water 5: dimethyl sulfoxide; phosphorus pentoxide; triethylamine / dichloromethane / 2 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With diamminedichloropalladium(II); potassium carbonate In N,N-dimethyl-formamide at 175℃; for 0.5h; Sealed tube; Microwave irradiation; diastereoselective reaction; | Heck coupling - Conditions D General procedure: The appropriate bromo aniline (1 mmol) was placed in a 10-mL glass tube together with thecorresponding styrene (1 mmol), Pd(NH3)2Cl2 (1.1 mg, 0.005 mmol), K2CO3 (0.276 g, 2 mmol) andDMF (1.5 mL). The vessel was sealed with a septum, shaken, and placed into the microwave cavity.Microwave irradiation was initiated with a potency of 25 W, the temperature being then increasedfrom room temperature to 175 C. Once this value was reached, the reaction mixture was held atthis temperature for 30 min. After allowing the mixture to cool down to room temperature, thereaction vessel was opened and the reaction mixture was filtered through a Celite pad with EtOAc.The filtrate was poured into a separating funnel, and washed with water (2 x 10 mL) and then withbrine (2 x 10 mL). After desiccation of the organic layer over anhydrous Na2SO4, the volatiles wereremoved under reduced pressure. This afforded an oily material which was subjected to columnchromatography on silica gel (hexane-EtOAc mixtures) to yield the desired stilbene derivative.Conditions D: Pd(NH3)2Cl2, K2CO3, DMF, 175 C (MW 25 W), 30 min. Yields: 13b, 72%; 14b,69%; 15b, 59%; 16b, 71%; 17b, 73%; 18b, 71%; 19b, 74%; 20b, 45%; 21b, 55% |
49% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine at 125℃; | |
With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine at 125℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With eosin Y; oxygen In dimethyl sulfoxide at 20℃; for 9h; Irradiation; Green chemistry; | General procedure for the aerobic C-C double bond cleavage and formation of aldehyde 2: General procedure: a solution of olefin 1 (1mmol) and eosin Y (1mol%) in DMSO (3mL) was irradiated with visible light (green light emitting diodes (LEDs), λmax=535nm, 2.5W) with stirring at rt for 9-12h (Table 2). After completion of the reaction (monitored by TLC), water (5mL) was added and the mixture was extracted with ethyl acetate (3×5mL). The combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography using a mixture of hexane/ethyl acetate (49:1) as eluent to afford an analytically pure sample of product 2. Characterization data of representative compounds. |
82% | With tetrahydrofuran; oxygen In water at 20℃; for 18h; Irradiation; Green chemistry; | |
78% | With iron(III) trifluoromethanesulfonate; 2-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)-6-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)pyridine; oxygen In 1,2-dichloro-ethane at 70℃; for 6h; Green chemistry; chemoselective reaction; |
96 %Chromat. | With oxygen; potassium carbonate In methanol at 130℃; for 12h; Sealed tube; Autoclave; | 9 Example 9 Add Co-N-C (5mol% relative to the substrate), 3-methoxystyrene (1mmol), K2CO3 (20mol%), and 4mL methanol into a 25mL polytetrafluoroethylene-lined autoclave, Seal the reactor, fill it with oxygen pressure to 0.4MPa, put the reactor in an oil bath at 130°C, stir and react for 12h at 400 rpm, After the reaction, the reactor was cooled to room temperature, the reactor was opened, and the internal standard biphenyl (60mg) was added. The qualitative products were detected by gas chromatography-mass spectrometry, and the yields of the substrate 3-methoxystyrene and the product 3-methoxybenzaldehyde by gas chromatography internal standard method are shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.2% | Stage #1: 3-methoxystyrene; 1-phenyl-propan-1-one With Cumene hydroperoxide; 1-ethyl-3-methylimidazolium hexafluorophosphate In water; acetonitrile at 45℃; for 0.833333h; Molecular sieve; Stage #2: In water; acetonitrile at 75℃; for 11h; | 2 Example 2 Under an air atmosphere,To the reaction kettle was added 100 mmol of the compound of the above formula (I)210 mmol of the compound of formula (II)150 mmol of the additive (108 mmolHydrogen peroxide cumene and 42 mmol1-ethyl ethyl ether-3-methylimidazole hexafluorophosphate,Wherein the hydrogen peroxide cumene is in the form of an aqueous solution having a mass percentage concentration of 85%),Additive 4A molecular sieve (the compound of formula (I) has a mass ratio of 1: 0.15) and an appropriate amount of solvent(A mixture of acetonitrile and polyethylene glycol 400 in a volume ratio of 4: 1)The mixture was stirred at 45 ° C for 50 minutes,Then 25.2 mmol of catalyst was added(A mixture of 21 mmol tetramethylammonium iodide and 4.2 mmol zirconium tetrachloride)The temperature was raised to 75 ° C and the reaction was stirred for 11 hours.After completion of the reaction, the mixture was extracted with ethyl acetate,The organic phases were combined and washed with saturated aqueous sodium thiosulfate solution,Dried over anhydrous sodium sulfate, filtered,Vacuum concentration,The residue was purified by silica gel column,I.e., the compound of formula (III) wherein MeO is methoxy,The yield was 96.2%. |
45% | With tert.-butylhydroperoxide; tetra-(n-butyl)ammonium iodide In benzonitrile at 80℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With sodium persulfate In acetonitrile at 50℃; Inert atmosphere; Green chemistry; | 2-Aryl-5-methoxy-2,3-dihydrobenzofurans 3; General Procedure General procedure: To a 10-mL round-bottomed flask equipped with magnetic stir bar was charged with TMS-protected phenol 1 (0.15 mmol), alkene 2 (0.6 mmol), Na2S2O8 (0.45 mmol), and dried MeCN (1.5 mL); the flask put under vacuum and purged with N2 (3 ×). The mixture was heated at 50 °C until consumption of starting material ceased (monitored by TLC). The mixture was filtered, and the filtrate was concentrated in vacuo. The residue was purified by flash column chromatography to give the final product. |
42% | With sodium persulfate In acetonitrile at 50℃; for 72h; Inert atmosphere; | 14 Example 14 To a 10 mL round bottom flask was added 40 mg of 4-methoxyphenoxytrimethylsilane, 145 mgSodium sulfate and 108mg of m-methoxystyrene, seal the flask replacement of nitrogen 3 times, with the needle to the reactionThe flask was charged with 2 ml of acetonitrile and reacted at 50 ° C for 72 h. After completion of the reaction, the reaction solution was filtered and concentratedAfter drying, the mixed solution of petroleum ether and ethyl acetate with volume ratio of 20: 1 was used as eluent,And purified by silica gel column chromatography to obtain 2- (3-methoxyphenyl) -5-methoxy-2,3-dihydrobenzofuranFuran, its structural formula:The resulting 2- (3-methoxyphenyl) -5-methoxy-2,3-dihydrobenzofuran was obtained as a colorless liquid in a yieldWas 42% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With diamminedichloropalladium(II); potassium carbonate In N,N-dimethyl-formamide at 175℃; for 0.5h; Sealed tube; Microwave irradiation; diastereoselective reaction; | Heck coupling - Conditions D General procedure: The appropriate bromo aniline (1 mmol) was placed in a 10-mL glass tube together with thecorresponding styrene (1 mmol), Pd(NH3)2Cl2 (1.1 mg, 0.005 mmol), K2CO3 (0.276 g, 2 mmol) andDMF (1.5 mL). The vessel was sealed with a septum, shaken, and placed into the microwave cavity.Microwave irradiation was initiated with a potency of 25 W, the temperature being then increasedfrom room temperature to 175 C. Once this value was reached, the reaction mixture was held atthis temperature for 30 min. After allowing the mixture to cool down to room temperature, thereaction vessel was opened and the reaction mixture was filtered through a Celite pad with EtOAc.The filtrate was poured into a separating funnel, and washed with water (2 x 10 mL) and then withbrine (2 x 10 mL). After desiccation of the organic layer over anhydrous Na2SO4, the volatiles wereremoved under reduced pressure. This afforded an oily material which was subjected to columnchromatography on silica gel (hexane-EtOAc mixtures) to yield the desired stilbene derivative.Conditions D: Pd(NH3)2Cl2, K2CO3, DMF, 175 C (MW 25 W), 30 min. Yields: 13b, 72%; 14b,69%; 15b, 59%; 16b, 71%; 17b, 73%; 18b, 71%; 19b, 74%; 20b, 45%; 21b, 55% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-methoxystyrene With sodium azide; Iodine monochloride In dichloromethane; acetonitrile at -20℃; Inert atmosphere; Schlenk technique; Stage #2: With potassium <i>tert</i>-butylate In diethyl ether at 0℃; for 1h; Inert atmosphere; Schlenk technique; | ||
Stage #1: 3-methoxystyrene With sodium azide; Iodine monochloride In acetonitrile at 0 - 20℃; for 12h; Stage #2: With potassium <i>tert</i>-butylate In diethyl ether at 0℃; for 12h; | ||
Multi-step reaction with 2 steps 1: bromine / dichloromethane / 1 h / 0 °C 2: sodium azide / N,N-dimethyl-formamide / 20 °C |
Multi-step reaction with 2 steps 1: sodium azide; Iodine monochloride / dichloromethane; acetonitrile / 1 h / -20 °C / Inert atmosphere 2: potassium <i>tert</i>-butylate / diethyl ether / 1.5 h / 0 °C / Inert atmosphere | ||
Stage #1: 3-methoxystyrene With sodium azide; Iodine monochloride In dichloromethane; acetonitrile at -15 - 20℃; for 12h; Stage #2: With potassium <i>tert</i>-butylate In diethyl ether at 0℃; for 12h; | Synthesis of vinyl azides 1a-l (General procedure) General procedure: To a stirred suspension of sodium azide (3.3 mmol, 215 mg) in dry MeCN (6 mL) at -15 °C the solution iodine monochloride (3.3 mmol, 563 mg) in DCM (2 mL) was added over 20 min and then stirred for additional 20 min. Then a solution of corresponding styrene (3 mmol in 2 mL of MeCN) was added dropwise and the reaction mixture was allowed to warm to room temperature and stirred for 12 h. The reaction mixture was poured into water (20 mL) and extracted with Et2O (3 × 20 mL). The combined extracts were washed with 5% aqueous Na2S2O3 solution (20 mL) followed by water (20 mL), then dried with MgSO4 and concentrated in vacuo to give a mixture of the diazide and the desired vinyl azide. This mixture was redissolved in Et2O (10 mL) at 0 °C and treated with t-BuOK (3.3 mmol, 370 mg), then stirred for 12 h, after which time TLC analysis indicated complete conversion to the vinyl azide. The mixture was washed with water (10 mL), brine (10 mL), dried with Na2SO4 and concentrated in vacuo (15-20 mmHg, bath temperature ca. 30-35 °C). The crude residue was purified by column chromatography on silica gel using hexanes as eluent to give pure vinyl azide as colorless oil. | |
Multi-step reaction with 2 steps 1: bromine / dichloromethane / 2 h / 20 °C / Cooling with ice 2: sodium azide / N,N-dimethyl-formamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With copper diacetate In 1,2-dichloro-ethane at 80℃; for 0.25h; regioselective reaction; | Established standard procedure for olefin oxyamination reaction General procedure: To a 1 Dram vial with Teflon-coated micro stir bar was added carboxylic acid 1 (1.2 mmol, 3 equiv), O-benzoylhydroxylamine 3 (0.4 mmol, 1 equiv), and copper(II) acetate (0.08 mmol, 0.2 equiv), followed by addition of anhydrous 1,2-dichloroethane (2.0 mL) and olefin 2 (1.2 mmol, 3 equiv). The resulting solution was stirred at 80 °C for 15 min until the consumption of O-benzoylhydroxylamine 3 (monitored by TLC). The resulting reaction mixture was cooled to room temperature and filtered through a plug of activated, neutral Al2O3 (Brockman grade I, 58-60Å). The filtrate was concentrated under reduced pressure, providing the crude reaction mixture. The crude reaction mixture was purified by silica column chromatography unless otherwise noted. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: 3-methoxystyrene; 2-chloro-1,3,2-benzodioxaborole With N-Methyldicyclohexylamine; (bis(3,5-di-tertbutylphenyl)(tert-butyl)phosphine)<SUB>2</SUB>PdCl<SUB>2</SUB>; lithium iodide at 70℃; for 24h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol at 20℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: palladium diacetate; triethanolamine / 1 h / 100 °C / Inert atmosphere 2: boron tribromide / dichloromethane / 1 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With (R)-((4,4?-bi-1,3-benzodioxole)-5,5?-diyl)bis(bis(3,5-di-t-butyl-4-methoxyphenyl))phosphine; palladium diacetate; In hexane; at 50℃; for 48h;Inert atmosphere; Sealed tube; | (R) -DTBM-SEGPHOS represents a chiral ligand, and HCOOPh stands for <strong>[1864-94-4]phenyl formate</strong>.Under the argon atmosphere, palladium acetate (0.025 mmol, 0.0056 g), chiral ligand (R) -DTBM-SEGPHOS (0.05 mmol, 0.059 g), 0.5 mL of n-hexane, 3-i 3-methoxystyrene having the formula 3-i(0.5 mmol, 0.0671 g) and <strong>[1864-94-4]phenyl formate</strong> (1.5 mmol, 0.1832 g). Tighten the cap seal to adjust the heating plate temperature to 50 After cooling for 48 hours, the mixture was cooled to room temperature and separated by column chromatography (petroleum ether: 100% by volume of ethyl acetate)0.1205 g of a colorless liquid (R) -2- (3-methoxyphenyl) propionate (see structure 4-i described in the above reaction scheme) 94%, branched and linear ratio> 20: 1, enantiomeric excess 95 HPLC conditions: chiral OJ-H column, n-hexane: isopropanol volume ratio of 90:10, flow rate: 1.0 mL / min, absorption Wavelength: 224nm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With copper(l) cyanide; manganese(III) triacetate dihydrate In N,N-dimethyl-formamide at 20℃; for 3h; Schlenk technique; Inert atmosphere; regioselective reaction; | |
78% | With manganese(II) acetate; copper(l) chloride In methanol at 20℃; Inert atmosphere; | 9.1; 9.2; 9.3 Example 9: Synthesis of 2- (3-methoxyphenyl) -3-diphenoxyphosphinylpropanenitrile The reaction procedure is as follows: 3-methoxystyrene and diphenylphosphine oxide as raw materials,A solution of 3-methoxystyrene (0.054 g, 0.4 mmol), diphenylphosphine oxide (0.243 g, 1.2 mmol), trimethylcyanosilane (0.079 g, 0.8 mmol), CuCl (0.12 g) (0.12 mmol), manganese acetate (0.107 g, 0.4 mmol) and methanol (3 mL) under argon at room temperature;TLC tracks the reaction until it ends completely;The crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1: 1) to give the desired product (yield 78%). |
With tetrabutylammonium tetrafluoroborate; copper(II) bis(trifluoromethanesulfonate) In 2,2,2-trifluoroethanol; N,N-dimethyl-formamide at 0℃; Inert atmosphere; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: oxygen; styrene monooxygenase / Enzymatic reaction 2: styrene oxide isomerase / Enzymatic reaction | ||
64 mg | With dichloro bis(acetonitrile) palladium(II); p-benzoquinone In water; <i>tert</i>-butyl alcohol for 1h; | Synthesis of compounds 8b, 8f, 8j. General procedure: PdCl2(MeCN)2 (0.13 equiv), p-benzoquinone (0.6equiv) were suspended in heated tert-butanol (5 mL) at 85°C. Subsequently water (0.5 equiv)and the respective styrene (0.50 equiv) were added and then the mixture was stirred at 85°C for 1 h. Afterwards the mixture was cooled on ice until solid to stop the reaction. In the next step the mixture was heated again to 30°C and subsequently the 2-(3-oxoisoindolin-4-yl)hydrazin-1-ium chloride 11a suspension (raw product obtained as described above, H2SO4 (98%, 0.88mL), water (1.46 mL) and ethanol (4.39 mL)) was added. The mixture was stirred at 50°C for2.5 h. After completion of the reaction, water (20 mL) was added and then the suspension wasextracted with ethyl acetate (5 x 15 mL). The combined organic phases were dried over Na2SO4and the solvent was evaporated under vacuum mounting the mixture on silica gel (1.5 g). Purificationwas done by column chromatography (toluene/ethyl acetate/acetic acid(5/5/0.5) andrecrystallization from ethanol. recrystallization from ethanol.3-(2-Chlorophenyl)-6,7-dihydropyrrolo[3,4-g]indol-8(1H)-one (8b). From PdCl2(MeCN)2 (7mg, 25 μmol), p-benzoquinone (125 mg, 1.18 mmol), 2-chlorostyrene (127 μL, 1.00 mmol)and 2-(3-oxoisoindolin-4-yl)hydrazin-1-ium chloride (11a, 670 mg, raw product obtained asdescribed above). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In benzene at 20℃; for 12h; Inert atmosphere; Glovebox; Irradiation; Sealed tube; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With ammonium carbonate; tetra-(n-butyl)ammonium iodide In water at 20℃; for 3h; Electrochemical reaction; stereoselective reaction; | |
70% | With potassium iodide In tetrahydrofuran; water at 30℃; Electrochemical reaction; | 4.2 General procedure 2. Synthesis of vinyl sulfones 3aa-3fa, 3ab-3ap (Table2) General procedure: An undivided cell was equipped with a carbon plate anode (5 cm2) and a Fe plate cathode (5cm2) and connected to a DC regulated power supply. The solution of sulfonyl hydrazide 1a-1f (300mg, 1.01-1.61mmol), alkene 2a-2p (1.93-3.22mmol, molar ratio 1.2 or 2mol 2/mol 1) and supporting electrolyte KI (2.02-3.22mmol, molar ratio 2mol/mol 1) in 30mL of THF-H2O (1:1) was electrolyzed using constant current conditions (60 or 270mA/cm2) at 30°C, under magnetic stirring. During electrosynthesis the reaction mixture is cooled externally. Then electrodes were washed with EtOH (2×30mL). The solvent from combined organic phases was removed under reduced pressure. The residue was diluted with EtOAc (50mL) and washed with saturated aqueous solution of Na2S2O3 (8mL), brine (2×8mL) and water (2×8mL), dried over Na2SO4, concentrated under reduced pressure and dried at 10-20 torr. The desired products 3aa-3fa, 3ab-3ap were isolated by chromatography on SiO2 with elution using PE-EA in a linear gradient of the latter from 10 to 50vol%. The yield when the reaction was performed with current density 270mA/cm2 is reported in the parentheses. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.9% | at 80 - 120℃; for 5h; Inert atmosphere; | 1.1 Preparation of o-benzyloxy-3’-methoxystilbene (1) Check the high-pressure reactor cooling system, the vacuum system is normal, high-pressure reactor intact;(2) connected to the autoclave nitrogen 0.3Mpa pressure test 1 hour, 1 hour pressure drop less than 0.05Mpa;(3) in the reactor was added:(4) reactor oil bath temperature was raised 120 ° C, ethylene was introduced into the nitrogen, at room temperature with nitrogen three times, each pressure0.3mpa force to maintain ethylene pressure 0.3Mpa reaction;(5) After the start of the reaction, the pressure of ethylene is observed at any time, ethylene gas is replenished in time as the pressure of ethylene decreases,Maintain the pressure at 0.3Mpa, until the pressure is no longer declining, the detection of raw materials disappeared up to GC testing, the residual brominated anisole ≤ 1% for the completion of the logo, 3 hours after the start of the reaction in the control test, between the bromoanisole reaction almost done;(6) After the reaction was completed, the reactor was evacuated ethylene gas, and replaced three times with nitrogen, then pressure relief to atmospheric pressure, addingO-Benzyloxy bromobenzene 177g (0.45mol, 1eq), temperature 120 , re-timing, the reaction was continued for 5 hours, the reaction was maintained at a nitrogen atmosphere, the pressure is atmospheric pressure;(7) Marked by time, cooled to below 80 ° C after 5 hours, filtered through a Buchner funnel, filtered to remove about 2/3 DMF under reduced pressure, and added with 95% of industrial ethanol 60g, stirred and crystallized to obtain a solid weighing 153g. HPLC purity 92.2%;(8) the solid obtained in (7) with 5 times ethanol, or 95% of industrial ethanol 750g, heated to 50-70 hot melt, and thenAfter being allowed to stand for 1 hour at room temperature, the mixture was filtered through a Buchner funnel and filtered to obtain 125 g of a solid.(9) HPLC purity 99.2%; mp 84.9 ° C ~ 88.6 ° C; yield: 84.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | 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 |
56% | 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With [2,2]bipyridinyl; manganese(II) acetate; copper(l) chloride In acetone at 50℃; | 6 Example 6 Synthesis of Diphenyl(2-(3-methoxyphenyl)-2-thiocyanoethyl)phosphine Oxygen With 3-methoxystyrene and diphenylphosphine oxide as raw materials, the reaction steps are as follows:To the reaction flask was added 3-methoxystyrene (0.054 g, 0.4 mmol), phenoxyphosphor (0.081 g, 0.4 mmol), trimethylsilylisothiocyanate (0.157 g, 1.2 mmol), CuCl (0.04 g, 0.04 mmol), bipyridyl (0.006 g, 0.04 mmol), manganese acetate (0.107 g, 0.4 mmol) and acetone (5 mL), reaction at 50 °C; TLC tracking reaction until complete;The crude product obtained after the reaction was separated by column chromatography (ethyl acetate:dichloromethane = 1:10) to obtain the targetProduct (yield 88%). |
78% | With [2,2]bipyridinyl; manganese(III) triacetate dihydrate; copper(ll) bromide at 10℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tert.-butylnitrite; silver carbonate In water at 50℃; | 5 Example 5: Synthesis of 2-(3-methoxyphenyl)-2-hydroxyiminoethyldiphenylphosphine oxide With 3-methoxystyrene and diphenylphosphine oxide as raw materials, the reaction steps are as follows:3-methoxystyrene (0.054 g, 0.4 mmol) was added to the reaction flask.Phosphorus phenoxide (0.081 g, 0.4 mmol),Tert-butyl nitrite (0.082 g, 0.8 mmol),Silver Carbonate (0.02g, 0.08 mmol),Water (2·5 mL), 50°C reaction;(2) TLC tracks the reaction until complete;(3) The crude product obtained after completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to give the target product (yield 81%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With [2,2]bipyridinyl; copper(II) bis(trifluoromethanesulfonate); potassium carbonate In acetonitrile at 120℃; for 16h; Schlenk technique; Inert atmosphere; | Copper-Catalyzed Synthesis of γ-Amino Esters 4; General Procedure General procedure: To a Schlenk tube were added alkene 1 (0.2 mmol), α-bromoalkyl ester 2 (0.4 mmol), amine 3 (0.4 mmol), Cu(OTf)2 (10 mol%), 2,2′-bipyridine (L1; 20 mol%), K2CO3 (2 equiv), and MeCN (2 mL). Then the tube was charged with argon, and the contents were stirred at 120 °C for 16 h until complete consumption of the starting materials as monitored by TLC and/or GC-MS analysis. After completion of the reaction, the contents were concentrated under vacuum, and the resulting residue was purified by silica gel column chromatography (hexane/EtOAc) to afford the desired γ-amino ester 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With indium(III) triflate; water; C26H37NOP2Ru In 1,4-dioxane at 150℃; for 36h; Inert atmosphere; Sealed tube; Green chemistry; | |
33% | With manganese(II) bromide; water; lithium perchlorate; copper dichloride In acetonitrile at 60℃; for 8h; Sealed tube; Inert atmosphere; Electrochemical reaction; regioselective reaction; | |
100 %Chromat. | With 1,1,1,3,5,5,5-heptamethyltrisiloxan In ethanol at 60℃; for 12h; |
Multi-step reaction with 2 steps 1: lithium aluminium tetrahydride; iron(III) chloride; hydrogen / tetrahydrofuran / 24 h / 23 °C 2: NADPH; 9-(2-mesityl)-10-methylacridinium perchlorate; oxygen; ketoreductase-P1-B12 / acetonitrile; water / 24 h / 23 °C / Irradiation; Enzymatic reaction |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With eosin In acetonitrile at 20℃; Irradiation; Green chemistry; | General procedure for visible light mediated alkylation of amine substrates via direct HAT General procedure: A flame-dried 10 mL flask was charged with amine 1 (1.0 mmol), substituted styrene 2 (1.0 mmol) and MeCN (3 mL). Eosin Y (2.0 mol%) was added to the mixture. The mixture was allowed to stir opening in air, and be irradiated with a high power blue LEDs [18 W, λ = 469 nm] for 8-12 hrs. at room temperature, until all of the starting material disappeared. The solvent was removed on a rotary evaporator under reduced pressure and the residue was subjected to column chromatography isolation on silica gel by elution with hexane to hexane / ethyl acetate (10:1) to afford the corresponding product 3(a-n) in high yield (65-97%) in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With trimethylsilylazide; benziodoxole; water In dichloromethane at 20℃; for 17h; Inert atmosphere; Schlenk technique; | 31 Example 31 Under an argon atmosphere, 3-methoxystyrene (0.5 mmol) was added to the Schlenk reaction tube, Diisopropyl azodicarboxylate (0.6 mmol),TMSN3 (0.7 mmol), Benzodoxole (0.05 mmol), Water (0.25 mmol), dry dichloromethane (1 mL), Stir at room temperature for 17 h (TLC monitoring). After the reaction was completed, the reaction was completed by adding saturated sodium hydrogencarbonate (2 mL).Extracted with ethyl acetate (5 mL × 3), dried over anhydrous sodium sulfate.The solvent was removed under reduced pressure to give a crude product.a mixed solvent of petroleum ether: ethyl acetate = 20:1 as a developing solvent,The product 31 was isolated by silica gel column chromatography from 200-300 mesh.The yield was 94%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 48.5h; | 1.1 Step 1 Synthesis of 1-benzyl-3-(3-methoxyphenyl)pyrrolidine 3-methoxy-1-vinylbenzene (10 g, 74.5 mmol, 10.34 mL, 1 eq) was dissolved in dichloromethane (250 mL) and trifluoroacetic acid (0.85 g, 7.45 mmol, 552 uL, 0.1 eq). N-(Methoxymethyl)-N-(trimethylsilylmethyl)benzylamine (35.4 g, 149 mmol, 2 eq) was added dropwise at 0 ° C, and was added dropwise over 30 min.The reaction was stirred at room temperature for 48 hours, and the reaction mixture was diluted with dichloromethane (250 mL)The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated.The residue was purified by silica gel chromatography (eluent: petroleum ether: ethyl acetate = 10:1 to 1:1)A pale yellow solid (13 g, yield 65%) was obtained. |
65% | With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 48.5h; | 2 Synthesis of 1-benzyl-3-(3-methoxyphenyl)pyrrolidine Dissolve 3-methoxyvinylbenzene (10g, 74.5mmol, 1eq) in dichloromethane (250mL),Add trifluoroacetic acid (0.85g, 7.45mmol, 0.1eq), add dropwise N-(methoxymethyl)-N-(trimethylsilylmethyl)benzylamine (35.4g, 149mmol, 2eq) at 0 ), the drip is finished within 30 minutes.The reaction was raised to room temperature and stirred for 48 hours,The reaction solution was diluted with dichloromethane (250 mL) and washed with water (300 mL) three times. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was chromatographed on silica gel (eluent: petroleum ether: ethyl acetate = 10:11:1) was purified to obtain a pale yellow solid (13g, yield 65%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With zirconocene dichloride; lithium methanolate In toluene at 100℃; for 8h; Inert atmosphere; | 40 Example 40 A method for preparing geminal diboron compounds by selective 1,1-diboration of olefins: Add Cp2ZrCl2 (0.01 mmol, 2.9 mg) to the reaction tube in sequence,MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), 3-methoxystyrene 1 m (0.2 mmol, 27 μL),The reaction was stirred at 100 °C for 8 h under a nitrogen (1 atm) atmosphere. GC-MS detection reaction is completed.Add 3 mL of methanol at room temperature, then spin-dry the solvent under reduced pressure, and purify the product by silica gel column chromatography, using petroleum ether: ethyl acetate (10 mL: 1 mL) as the eluent,1,1-[bis(pinacol borate)]-3-methoxybenzeneethane was obtained as a colorless oil3m (52 mg, 67%). |
67% | With zirconocene dichloride; lithium methanolate In toluene at 100℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With N-Bromosuccinimide; triethylamine tris(hydrogen fluoride) In dichloromethane at 20℃; | 4.2.1.1 1-(2-Bromo-1-fluoroethyl)-3-methoxybenzene (2) Similarly to the general procedure 40, 3-methoxystyrene (1) (2.45g, 18.24mmol) was reacted with triethylamine-trishydrofluoride (Et3N·3HF, 10.0mL, 55.63mmol, 3 equiv) and N-bromosuccinimide (NBS, 3.9g, 21.9mmol, 1.2 equiv). After neutralization with ammonia and extraction with pentane, 2 was isolated and purified by column chromatography (silica gel, pentane) to give a colorless liquid. Yield: 1.58g (37%). 1H NMR (300MHz, CDCl3): δ 3.62 (m, 2H, 1-CBrH2), 3.82 (s, 3H, O-CH3), 5.60 (ddd, 3JH,H=4.2, 3JH,H=7.7, 2JH,F=46.9Hz, 1H, 2-CFH), 6.90 (dq, 4JH,H=0.7, 4JH,H=1.6Hz, 2H, CHar), 6.93 (m, 1H, CHar), 7.32 (dt, 4JH,H=1.1, 3JH,H=7.6Hz, 1H, CHar). 13C NMR (75MHz, CDCl3): δ 34.3 (d, 2JC,F=28.1Hz, C-Br), 55.3 (s, OCH3), 92.7 (d, 1JC,F=178.7Hz, C-F), 111.2 (d, 3JC,F=7.3Hz, Car), 114.7 (d, 3JC,F=1.6Hz, Car), 117.9 (d, 3JC,F=6.6Hz, Car), 129.8 (s, Car), 138.6 (d, 2JC,F=20.3Hz, Car), 159.8 (s, C-OMe).19F NMR (282MHz, CDCl3): δ -175.20 (ddd, 3JH,F=15.9, 3JH,F=25.9, 1JH,F=46.9Hz, 1F, CHF). MS (GC/EI): m/z (%) 232/234 (45/44) [M+], 212/214 (38/37) [M+ - HF], 153 (8) [M+ - Br], 139 (100) [M+-CH2Br], 133 (20) [212-Br], 109 (25), 77 (32) [C6H5+], 89 (4), 63 (48), 57 (10), 51 (20) [C4H3+]. |
With N-Bromosuccinimide; triethylamine tris(hydrogen fluoride) In dichloromethane at 0 - 20℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With 2,3,6,7-tetramethoxy-9(10H)-anthracenone; caesium carbonate In dimethyl sulfoxide at 25℃; for 18h; Irradiation; Sealed tube; regioselective reaction; | General Procedure for the Carboxylation of Hetero(arenes) and Styrenes- GP2a General procedure: To a dry flat-bottomed crimp vial (5 mL) equipped with stirring bar, was added the arene (if solid)(0.1 mmol) and 2,3,6,7-tetramethoxyanthracen-9(10H)-one (6.3 mg, 0.02 mmol, 20 mol %). Cs2CO3 (98 mg,3 equiv.) was quickly added and the vial was sealed with a Supelco aluminium crimp seal with septum(PTFE/butyl). The vial was then evacuated and refilled with CO2 (5×) via syringe needle. The reactionmixture was dissolved in DMSO (1 mL, dry and degassed by bubbling with N2) and the arene (0.1 mmol) (ifliquid) was added via syringe. The vial was sealed with two layers of Parafilm and then had gaseous CO2added via a Luer Lock Monoject (20 ccm) syringe, into the head space. The vial was then irradiated fromthe bottom side with blue LED light and a constant reaction temperature (25°C) was maintained byemploying a water-cooling circuit connected to a thermostat. After 18 hrs of reaction time the pressure wasreleased. For product isolation, the reaction mixtures of 4 reactions run in parallel were combined andtransferred with water and Et2O into a separating funnel. The ether layer was extracted with water (3×) andthe combined aqueous layers were acidified with aq. HCl (2M) to adjust to an acidic pH. The aqueous layerwas extracted with EtOAc (3×) and the combined EtOAc layers were dried over Na2SO4, filtered andconcentrated in vacuo. The crude material was purified by silica flash column chromatography usingmixtures of hexanes and ethyl acetate with 0.5% HOAc (v/v) as eluents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tert.-butylhydroperoxide; copper diacetate In acetonitrile at 80℃; for 15h; | General procedure for the synthesis of 2-acetylphenyl 4-methoxybenzoate General procedure: To an oven-dried pressure tube charged with 2-acetylphenol 1a(68.0 mg, 0.5 mmol), Cu(OAc)2 (18.0 mg, 20 mol %, 0.1 mmol) andTBHP (0.50 mL, 2.50 mmol, 5.5 M in decane) in MeCN (1.0 mL) was added 4-methoxystyrene 2a (134 mg, 1.0 mmol). The resultant reaction mixture was allowed to stir in pressure tube at 80 C for 15 h. After completion of reaction as monitored by TLC, the reaction mixture was cooled at room temperature and evaporated onto silica gel. Purication of product by silica gel column chromatography (n-hexane/EtOAc, 15:1) furnished the 2-acetylphenyl 4-methoxybenzoate 3aa (109 mg) in 81% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tert.-butylhydroperoxide; copper diacetate In acetonitrile at 80℃; for 15h; | General procedure for the synthesis of 2-acetylphenyl 4-methoxybenzoate General procedure: To an oven-dried pressure tube charged with 2-acetylphenol 1a(68.0 mg, 0.5 mmol), Cu(OAc)2 (18.0 mg, 20 mol %, 0.1 mmol) andTBHP (0.50 mL, 2.50 mmol, 5.5 M in decane) in MeCN (1.0 mL) was added 4-methoxystyrene 2a (134 mg, 1.0 mmol). The resultant reaction mixture was allowed to stir in pressure tube at 80 C for 15 h. After completion of reaction as monitored by TLC, the reaction mixture was cooled at room temperature and evaporated onto silica gel. Purication of product by silica gel column chromatography (n-hexane/EtOAc, 15:1) furnished the 2-acetylphenyl 4-methoxybenzoate 3aa (109 mg) in 81% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tert.-butylhydroperoxide; copper diacetate In acetonitrile at 80℃; for 15h; | General procedure for the synthesis of 2-acetylphenyl 4-methoxybenzoate General procedure: To an oven-dried pressure tube charged with 2-acetylphenol 1a(68.0 mg, 0.5 mmol), Cu(OAc)2 (18.0 mg, 20 mol %, 0.1 mmol) andTBHP (0.50 mL, 2.50 mmol, 5.5 M in decane) in MeCN (1.0 mL) was added 4-methoxystyrene 2a (134 mg, 1.0 mmol). The resultant reaction mixture was allowed to stir in pressure tube at 80 C for 15 h. After completion of reaction as monitored by TLC, the reaction mixture was cooled at room temperature and evaporated onto silica gel. Purication of product by silica gel column chromatography (n-hexane/EtOAc, 15:1) furnished the 2-acetylphenyl 4-methoxybenzoate 3aa (109 mg) in 81% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tert.-butylhydroperoxide; copper diacetate In acetonitrile at 80℃; for 15h; | General procedure for the synthesis of 2-acetylphenyl 4-methoxybenzoate General procedure: To an oven-dried pressure tube charged with 2-acetylphenol 1a(68.0 mg, 0.5 mmol), Cu(OAc)2 (18.0 mg, 20 mol %, 0.1 mmol) andTBHP (0.50 mL, 2.50 mmol, 5.5 M in decane) in MeCN (1.0 mL) was added 4-methoxystyrene 2a (134 mg, 1.0 mmol). The resultant reaction mixture was allowed to stir in pressure tube at 80 C for 15 h. After completion of reaction as monitored by TLC, the reaction mixture was cooled at room temperature and evaporated onto silica gel. Purication of product by silica gel column chromatography (n-hexane/EtOAc, 15:1) furnished the 2-acetylphenyl 4-methoxybenzoate 3aa (109 mg) in 81% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With Co(3,5-di<SUP>t</SUP>Bu-QingPhyrin); potassium carbonate In chlorobenzene at 20℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; enantioselective reaction; | V. General Procedure for Enantioselective Aziridination of Styrenes General procedure: To an over-dried Schlenk tube, [Co(Por)] (2 mol %) and K2CO3 (0.5 mmol) were added.The Schlenk tube was then evacuated and backfilled with nitrogen for 3 times. TheTeflon screw cap was replaced with a rubber septum and TrocN3 (0.1 mmol), styrene(0.3 mmol) and PhCl (1 mL) were added. The Schlenk tube was then purged withnitrogen for 2 minutes and the rubber septum was replaced with a Teflon screw cap.The mixture was then stirred at room temperature for 24 h. After the reaction finished,the resulting mixture was concentrated in vacuo and the residue was purified by flashsilica gel chromatography to afford the desired products. The silica gel was pre-treatedwith 1% Et3N/hexanes. In most cases, the product was visualized on TLC using UVlamp and/or the cerium ammonium molybdate (CAM) stain. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C29H43Br2N2NiO3P; sodium t-butanolate In toluene at 110℃; for 48h; Inert atmosphere; | 4 Example 4 The divalent nickel (II) complex is used as a catalyst to catalyze the hydroheteroarylation reaction of m-methylstyrene and benzofuran Under argon protection, add catalyst (35.9 mg, 0.05 mmol, 10 mol%), sodium tert-butoxide (48 mg, 0.5 mmol), and benzofuran (55 μl, 0.5 mmol) into the reaction flask in sequence , M-Methoxystyrene (98 μl, 0.75 mmol),Toluene (1.5 ml) was used as the solvent, and the reaction was carried out at 110 oC for 48 hours. The reaction was terminated with water.The reaction product was extracted with ethyl acetate, separated and purified by column chromatography(Using petroleum ether as the developing agent), the yield is 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With [2,2]bipyridinyl; copper(II) bis(trifluoromethanesulfonate); Sodium hydrogenocarbonate In acetonitrile at 100℃; for 24h; Schlenk technique; Inert atmosphere; | Method A General procedure: Sulfonyl chloride 4 (0.4 mmol, 2.0 equiv.), Cu(OTf)2 (10 mol%) and NaHCO3 (0.6 mmol, 3.0 equiv.) were weighed into a Schlenk tube. The reaction vessel was capped and subjected to three vacuum-purge/nitrogen-flush cycles. Then vinylarene 3 (0.2 mmol, 1.0 equiv.) in MeCN (1.5 mL) was added through the side-arm by syringe. The reaction was stirred under nitrogen at 100 °C for 24 h. After reaction, the mixture was cooled to room temperature. Volatile solvent and reagents were removed by rotary evaporation and the residue was purified by silica gel flash chromatography using petroleum ether/EtOAc (50:1 to 15:1) to afford the desired product 5 or 6. |
95% | With 2.9-dimethyl-1,10-phenanthroline; triethylamine; copper(II) bromide In 1,2-dichloro-ethane at 130℃; for 0.0166667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With C37H40OZr In toluene at 100℃; for 12h; Inert atmosphere; Glovebox; Sealed tube; Schlenk technique; |
Tags: 626-20-0 synthesis path| 626-20-0 SDS| 626-20-0 COA| 626-20-0 purity| 626-20-0 application| 626-20-0 NMR| 626-20-0 COA| 626-20-0 structure
[ 22255-22-7 ]
(E)-1,3-Dimethoxy-5-(4-methoxystyryl)benzene
Similarity: 0.90
[ 22255-22-7 ]
(E)-1,3-Dimethoxy-5-(4-methoxystyryl)benzene
Similarity: 0.90
[ 22255-22-7 ]
(E)-1,3-Dimethoxy-5-(4-methoxystyryl)benzene
Similarity: 0.90
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Code | Phrase |
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P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
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P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
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P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
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Code | Phrase |
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P304 | IF INHALED: |
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P306 | IF ON CLOTHING: |
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P322 | |
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P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
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P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
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P378 | |
P380 | Evacuate area. |
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P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
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P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
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P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
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P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
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P370 + P378 | In case of fire: |
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P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
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P405 | Store locked up. |
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P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
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P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
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Disposal | |
Code | Phrase |
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Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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