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CAS No. : | 2687-12-9 | MDL No. : | MFCD00000986 |
Formula : | C9H9Cl | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 152.62 | Pubchem ID : | - |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.11 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 46.14 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
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) : | -4.94 cm/s |
Log Po/w (iLOGP) : | 2.3 |
Log Po/w (XLOGP3) : | 3.23 |
Log Po/w (WLOGP) : | 2.83 |
Log Po/w (MLOGP) : | 3.47 |
Log Po/w (SILICOS-IT) : | 3.29 |
Consensus Log Po/w : | 3.02 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.13 |
Solubility : | 0.112 mg/ml ; 0.000736 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.9 |
Solubility : | 0.191 mg/ml ; 0.00125 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.49 |
Solubility : | 0.0493 mg/ml ; 0.000323 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.87 |
Signal Word: | Danger | Class: | 8,6.1 |
Precautionary Statements: | P260-P280-P284-P305+P351+P338-P310 | UN#: | 2922 |
Hazard Statements: | H302-H314-H330-H334 | Packing Group: | Ⅱ |
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 |
---|---|---|
90 %Chromat. | With iron(III) chloride; tetraphenylsilane In <i>tert</i>-butyl alcohol at 80℃; for 24 h; | In a 25 mL reaction flask, ferric chloride (0.05 mmol), ene 1ag (0.5 mmol), tetraphenyl disilane (2.0 mmol) and tert-butanol (2.0 mL) were added successively to the 25 mL reaction flask.After mixing at room temperature, the reaction mixture was reacted at 80 ° C for 24 h.The reaction was completed, aqueous ammonia (0.5 mL) was added and stirred for 1 h.Then, 5 mL of water was added and extracted with ether (5 mL x 3). The organic phases were combined and the solvent was evaporated under reduced pressure. Column chromatography gave 90percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; p-toluenesulfonyl chloride; In dichloromethane; for 4h;Inert atmosphere; Reflux; | General procedure: Triethylamine (Et3N, 250mg, 2.5mmol) was added to a solution of commercially available cinnamyl alcohols (2.0mmol) in CH2Cl2 (15mL) at rt. p-Toluenesulfonyl chloride (TsCl, 420mg, 2.2mmol) was slowly added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 4h. The reaction mixture was cooled to rt. Substituted sulfinic sodium salt (3.0mmol) was added to a solution of the resulting cinnamyl chlorides at rt. A co-solvent of water (5mL) and 1,4-dioxane (10mL) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 6h. The reaction mixture was cooled to rt. The solvent was concentrated under reduced pressure. The residue was diluted with water (10mL) and the mixture was extracted with EtOAc (3×30mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc=6/1?2/1) afforded skeleton 3. Skeleton 3 is known and the analytical data are consistent with those in the literature.10 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | In n-heptane; water at 100℃; for 5h; Yields of byproduct given; | |
In n-heptane; water at 100℃; for 3h; variation of catalyst, organic phase, reaction time; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With sodium formate In water; toluene at 100℃; for 3h; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With n-butyllithium; In tetrahydrofuran; hexane; at 0 - 20℃; for 2.5h; | To a suspension of Part A compound (1.00 g, 4.21 mmol) in THF (25 mL) at 0C was added n-butyllithium in hexanes (3.53 mL, 8.84 mmol) dropwise at such at rate to maintain the internal temperature near 0C. The resulting bright yellow solution was stirred at 0C for 0.5 h and treated with <strong>[2687-12-9]cinnamyl chloride</strong> (0.79 g, 4.63 mmol). The mixture was slowly warmed to room temperature and stirred for 2 h when it was diluted with water (40 mL) and ethyl acetate (40 mL). The layers were separated, the organic fraction dried (Na2SO4) and concentrated. The remainder was triturated with hexanes and the resulting solid recrystalized from hot methanol to give 1.20 g (79%) of title compound as white needles. mp 144C. TLC Silica gel (3:7 ethyl acetate/hexane) Rf=0.6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With n-butyllithium; In tetrahydrofuran; hexane; at 0 - 20℃; for 1.5h; | To a suspension of 500 mg (1.99 mmol) of Example 11 Part A compound in 10 mL of THF, at 0C under argon, was added dropwise 2.5 mL (3.98 mmol) of n-BuLi (1.6 M in hexanes). The resulting orange solution was stirred at 0C for 0.5 h at which time 305 muL (2.19 mmol) of <strong>[2687-12-9]cinnamyl chloride</strong> was added. The reaction was warmed to RT and allowed to stir for 1 h at which time it was diluted with 1:1 ethyl acetate/water (30 mL). The organics were dried (NaSO4) and evaporated to dryness. Purification by crystallization from hot methanol provided 350 mg (48%) of title compound as a white solid. mp 95-97C. TLC Silica gel (1:1 hexanes/ethyl acetate) Rf = 0.59. MS (CI-NH3, + ions) m/e 368 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 60℃; for 2h; | To a solution of 4-hydroxy-2,3,6-trimethylphenyl acetate (10.0 g, 51.5 mmol) in N,N-dimethylformamide (100 mL) was added 1-chloro-3-phenyl-2-propene (7.86 g, 51.5 mmol) and potassium carbonate (7.10 g, 51.5 mmol) and the mixture was stirred under an argon atmosphere at 60 C. for 2 hours. This reaction mixture was poured into water and extracted twice with ethyl acetate. The combined extract was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was crystallized from methanol to obtain the title compound (13.0 g, yield 81%). m.p.: 104-107 C. 1H-NMR (CDCl3) delta: 2.06 (3H, s), 2.13 (3H, S), 2.18 (3H, s), 2.34 (3H, s), 4.66 (2H, dd, J=5.6, 1.2 Hz), 6.43 (1H, dt, J=16.2, 5.6 Hz), 5.63 (1H, s), 6.74 (1H, d, J=16.2 Hz), 7.24-7.46 (5H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Distilled H20 in a three-necked roundbottom flask is purged with nitrogen for 30 minutes. PdCI2 and KCI are subsequently added to the flask and the solution is stirred at room temperature for 1 h. Then, optionally substituted (R4)n-allyl chloride is added and the resulting reaction mixture is stirred at room temperature overnight (18-20 hrs). The reaction is extracted with chloroform, and the aqueous layer washed with chloroform three times. The organic layers are combined, dried over MgS04, filtered and concentrated in vacuo. The crude product is recrystallised from chloroform and methyl fe/ -butyl ether, and the resulting solid is isolated by filtration and dried in vacuo | ||
With potassium chloride; In water; for 24h;Inert atmosphere; Sealed tube; | A)In a two-necked flask equipped with a magnetic stirrer,250 mL of distilled water was added and argon was bubbled in for 30 minutes;B)Continue to maintain through the argon gas flow,PdCI2 (10 mmol, 1.77 g, 1 equiv) and KCl (2.84 g,4equiv),And then sealed with a rubber stopper to the mouth of the flask,The mixture in the flask was stirred for 1 hour;C)The excess of <strong>[2687-12-9]cinnamyl chloride</strong> (Ph-allyl) Cl (4.58 g, 3 equiv) was injected into the reaction flask through a rubber stopper,The resulting system continued to react for 24 hours;D)The reaction mixture was extracted three times with chloroform,The organic phases were combined,Dried over anhydrous MgSO4, filtered, the solvent removed under reduced pressure,To obtain the corresponding dimer;E)N- [2-bis (1-adamantyl) phosphophenyl] morpholine (2.2 mmol, 1.02 g) and 15 mL of dry tetrahydrofuran (THF) were charged in a single jar equipped with a magnetic stirrer,1 mmol of the above-mentioned palladium dimer was added to dissolve the ligand,Close the lid,The mixture was stirred at room temperature for 3 hours;F)The solvent was then removed under reduced pressure,A solid was obtained.The solid was pulverized in pentane,Filtered and recrystallized from 10 mL of dichloromethane (DCM) / pentane (1: 1 weight ratio)dry,Pulverization can be obtained palladium complex catalyst 2.37g. | |
General procedure: Distilled H2O in a three-necked roundbottom flask ispurged with nitrogen for 30 minutes. PdCl2 and KCl aresubsequently added to the flask and the solution is stirred atroom temperature for 1 h. Then, optionally substituted(R4)-allyl chloride is added and the resulting reactionmixture is stirred at room temperature overnight (18-20 irs).The reaction is extracted with chloroform, and the aqueouslayer washed with chloroform three times. The organiclayers are combined, dried over MgSO4, filtered and concentrated in vacuo. The crude product is recrystallised fromchloroform and methyl tert-butyl ether, and the resultingsolid is isolated by filtration and dried in vacuo; PdCl2 (590 mg, 3.33 mmol); KCl (473 mg, 6.67 mmol); <strong>[2687-12-9]cinnamyl chloride</strong> (1.39 mL, 9.99 mmol); H2O (83 mL). Thedimer is obtained as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3-Ethyl-3-oxetane methanol (27.03 g, 0.2326 mole), toluene (100 ml), tetrabutyl ammonium hydrogen sulfate (17.38 g, 0.0512 mole) and 50percent sodium hydroxide solution (300 ml) were combined in a 1L 4-neck round bottom flask equipped with a condenser, mechanical mixer and oil bath. The mixture was stirred vigorously and the oil bath was heated to 90 C. at which temperature the solids were totally dissolved. Cinnamyl chloride (35.50 g, 0.2326 mole) was added over approximately 35 minutes. The reaction was heated at 90 C. with mixing for an additional 1.25 hour and then allowed to cool to room temperature. The organic phase was isolated in a separatory funnel and washed four times with 20percent sodium chloride solution (200 ml each). As a result, the washes changed from cloudy yellow to hazy colorless and the pH of the washes dropped from 12 to 6. The last of four more washes (200 ml) using distilled water was an emulsion, which separated over night. After the emulsion separated, a clear orange organic fraction was collected and mixed for one hour with silica gel (60 g). Solids were then filtered out, and the reaction solution was stripped of toluene in vocuo resulting in a clear orange liquid with a viscosity of <100 cPs at 25 C., and a volatility of 93percent at 200 C. as measured by thermogravimetric analysis (TGA). H1 NMR: 7.15-7.51 (m, 5H), 6.12-6.25 (d, 1H), 6.30-6.42 (m, 1H), 4.51-4.71 (d, 2H), 4.41-4.51 (d, 2H), 4.15-4.25 (d, 2H), 3.65 (s, 2H), 1.85-1.90 (m, 2H), 1.85-1.95 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With phosphorus tribromide; In diethyl ether; at 0 - 20℃; for 1.5h; | A solution of phosphorous tribromide (3.2 mmol) in anhydrous diethyl ether (20 mL) was dropped into a solution of 3-chloro-1-phenylpropan-1-ol (2.9 mmol) in diethyl ether (30 mL) under stirring at 0-5C in 30 min. The reaction mixture was further stirred for 1h at room temperature. Aqueous sodium acetate (5%, 20 mL) was slowly added into the reaction mixture. The organic layer was separated and again washed with 5% sodium acetate (20 mL x 2) then with brine (10 mL x 3), water (5 mL) and dried over sodium sulfate. Sodium sulfate was filtered off and washed with diethyl ether (5 mL x 3) and filtrate was concentrated under reduced pressure to afford an oil which was dissolved in dry DMF (3 mL) and the clear solution was added into a pre-cooled (0-5C) mixture of sodium hydride (11.7 mmol) and 4-(trifluromethyl)phenol (3.5 mmol) in dry DMF (5 mL) under stirring over a period of 10 min. The mixture was slowly heated to 110-115C in 1h with stirring in an oil bath. The reaction mixture was further stirred at 110-115C for 8h. The mixture was cooled to room temperature, carefully poured over ice (5 g) and extracted with ethyl acetate (15 mL x 3). The organic layer was washed with brine (5 mL x 3) and then with water (5 mL). Organic layer was dried over sodium sulfate, washed with ethyl acetate (5 mL x 3) and concentrated to furnish crude compound which was further purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium carbonate; potassium iodide; In methanol; toluene; for 20h;Reflux; | A mixture of <strong>[2687-12-9]cinnamyl chloride</strong> (905 ml, 6.5 mol), diisopropylamine (1.37 1, 9.75 mol), potassium carbonate (0.90 kg, 6.5 mol), potassium iodide (54 g, 0.325 mol), toluene (2.1 l) and methanol (0.50 1) is stirred at reflux temperature for 20 hours. The mixture is cooled to 25 C and water (5.2 1) is added. Phases are separated and the organic phase is extracted with brine. Organic phase is concentrated under reduced pressure (50 C) and then water (10.4 1) and toluene (2.6 l) are added and the pH is adjusted to 2 by addition of concentrated hydrochloric acid (-500 ml). The resulting mixture is stirred for 15 minutes and the phases are separated. The aqueous phase is re-extracted twice with toluene (2 x 2.6 l). Then the pH of the aqueous phase is adjusted to 12 by addition of 8 M aqueous sodium hydroxide solution (750 ml). To the resulting white suspension is added heptane (5.2 l) and the mixture is stirred for 15 minutes. Phases are separated and aqueous phase is re-extracted twice with heptane (2 x 2.6 l). Combined organic phases are dried over Na2SO4 and concentrated to give 1.32 kg (93 % yield) of DIPCA. |
40% | With sodium iodide; In ethanol; at 20 - 85℃; | EXAMPLE 1 Obtaining 2-(3-N,N-diisopropylamine-1-phenylpropyl)-4-carboxyphenol (IV'a) Diisopropylamine (2.77 1, 19.65 mol) and sodium iodide (16.95 g, 0.13 mol) were loaded onto a solution of <strong>[2687-12-9]cinnamyl chloride</strong> (1 kg, 6.55 mol) in ethanol (3 1/kg) at 20/25C. The mixture was heated at internal 80-85C, the reaction conditions being maintained for 3-4 hours until the end of such reaction. The mixture was cooled at 40-45C and distilled to an internal volume of 1.3 1. The mixture was then cooled at 20-25C, water (4 1) and toluene (3 1) was added and the pH was adjusted to 1.0-1.5. The phases were decanted and dichloromethane (4 1) was loaded onto the aqueous phase, adjusting the pH again to 11.5-12.0. The phases were decanted and the organic phase was washed with water (4 1). Once the phases were decanted, the organic phase was distilled at atmospheric pressure to an internal volume of 1.3 1 in order to then load heptane (0.5 1). Again, it was distilled to 1.3 1 and heptane (2 1) was loaded. The suspension which was obtained was filtered by a prelayer, which was washed with heptane (0.5 1). The filtered organic phase was distilled at atmospheric pressure to an internal volume of 1.3 1. The amine content of the reaction mixture was determined by the potentiometric titration thereof. Acetic acid (1.2 l/kg of amine), 4-hydroxybenzoic acid (0.63 kg/kg of amine, 1 equivalent), and, then, sulfuric acid (1.1 l/kg of amine, 4.5 equivalents) were loaded onto the mixture. It was heated at internal 80-85C, the reaction conditions being maintained for 5-6 hours until the end of the reaction. The reaction mixture was cooled to 35-40C and water (10 l/kg of amine) and ethyl acetate (10 l/kg of amine) were loaded. The phases were decanted and the organic phase was washed out with water (5 l/kg). The aqueous phases were pooled; toluene (5 l/kg of amine) was loaded, the phases were decanted and n-butanol (10 l/kg of amine) was loaded onto the aqueous phase, the pH was adjusted to 7 and it was decanted. The organic phase was distilled to an internal amine volume of 1.5-2.0 l/kg and then heptane (8 l/kg of amine) was loaded. The product which crystallized was cooled at 5-10C, filtered and washed with heptane (5 l/kg of amine). The product was then dried in an oven with air circulation for 10-12 hours, obtaining a product with an overall molar yield of 40% and with a purity greater than 90%. NMR (1H) DMSO: H8: doublet 0.8-0.9 ppm 12H, H5: multiplet 2.0-2.1 ppm 2H, H6: multiplet 2.3 ppm 2H, H7: multiplet 2.8-3.0 ppm 2H, H4: triplet 4.3 ppm 1H, H1: doublet 6.8 ppm 1H, H11: multiplet 7.1 ppm 1H, H10-9: multiplet 7.1-7.3 ppm 4H, H2: doublet 7.5 ppm 1H, H3: singlet 7.8 ppm 1H. NMR(13C) DMSO: 20.52; 20.57; 30.74; 36.11; 39.72; 48.04; 114.35; 125.56; 126.43; 128.59; 128.68; 129.02; 129.47; 129.77, 145.34; 157.76; 169.90. |
With sodium iodide; In ethanol; at 20 - 85℃; | EXAMPLE 1Obtaining 2- (3-N,N-diisopropylamine-l-phenylpropyl) -A- carboxyphenol (IVa)(IVa) Diisopropylamine (2.77 1, 19.65 mol) and sodium iodide(16.95 g, 0.13 mol) were loaded onto a solution of <strong>[2687-12-9]cinnamyl chloride</strong> (1 kg, 6.55 mol) in ethanol (3 I/kg) at 20/250C. The mixture was heated at internal 80-850C, the reaction conditions being maintained for 3-4 hours until the end of such reaction.The mixture was cooled at 40-450C and distilled to an internal volume of 1.3 1. The mixture was then cooled at 20- 25C, water (4 1) and toluene (3 1) was added and the pH was adjusted to 1.0-1.5. The phases were decanted and dichloromethane (4 1) was loaded onto the aqueous phase, adjusting the pH again to 11.5-12.0. The phases were decanted and the organic phase was washed with water (4 1) . Once the phases were decanted, the organic phase was distilled at atmospheric pressure to an internal volume of 1.3 1 in order to then load heptane (0.5 1) . Again, it was distilled to 1.3 1 and heptane (2 1) was loaded.The suspension which was obtained was filtered by a prelayer, which was washed with heptane (0.5 1) . The filtered organic phase was distilled at atmospheric pressure to an internal volume of 1.3 1.The amine content of the reaction mixture was determined by the potentiometric titration thereof. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: To a solution of [Ru(Cp*)Cl2]2 (1) (6.2 mg, 1.5 mol%) and K2CO3 (226 mg, 1.63 mmol) in dry acetonitrile (0.5 mL) in a schlenk tube was added <strong>[2687-12-9]cinnamyl chloride</strong> (92 mul, 0.65 mmol). The resulting mixture was stirred at room temperature under a nitrogen atmosphere for 20 min followed by a slow addition of the corresponding phenols (0.98 mmol) (Table 2) in dry acetonitrile (1 mL) over 15 minutes. The reaction mixture was stirred for another 16 h at room temperature and then filtered through a celite plug and washed with dichloromethane (10 mL). The filtrate was evaporated under reduced pressure and purified by silica gel column chromatography to afford the branched product. Characterization data and copies of NMR spectra were provided below |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | General procedure: 4-[(4-Methylphenyl)sulfonyl]amino}benzoic acid (10 mmol, 2.91 g), DMF (10 mL) and n-hexane washed sodium hydride (30 mmol, 0.72 g) were stirred at room temperature for 40 min followed by the addition of alkylating reagent (alkyl iodide/bromide or acid chloride, 10 mmol). The whole reaction mixture was stirred till the completion of the reaction (Table 1 for reaction details) and poured into crushed ice in a beaker. The pH of the mixture was adjusted to 4.0 with 1 N HCl. White precipitates were produced, filtered and washed twice with distilled water. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | General procedure: In a solution of compound 1 (250 mg, 0.96 mmol) in 3 ml anhydrous DMF, Cs2CO3 (407.28 mg, 1.25 mmol) was added. The mixture was stirred at room temperature for 1 h under anhydrous condition. Then methyl iodide (0.09 ml, 1.44 mmol) was added to the reaction mixture slowly and stirred at r.t. for 17 h. After completion of the reaction as indicated by TLC, saturated NaCl solution was added. The reaction mixture was extracted with ethyl acetate (3 × 25 ml). The combined organic layer was washed with water (2 × 50 ml), followed by brine solution (1 × 50 ml). The organic layer was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude mass was subjected to column chromatography using 100-200 mesh silica gel when the desired product was obtained by eluting the column with 30% EtOAc/60-80 C Petrolium ether as solvent system. (94% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | General procedure: In a solution of compound 1 (250 mg, 0.96 mmol) in 3 ml anhydrous DMF, Cs2CO3 (407.28 mg, 1.25 mmol) was added. The mixture was stirred at room temperature for 1 h under anhydrous condition. Then methyl iodide (0.09 ml, 1.44 mmol) was added to the reaction mixture slowly and stirred at r.t. for 17 h. After completion of the reaction as indicated by TLC, saturated NaCl solution was added. The reaction mixture was extracted with ethyl acetate (3 × 25 ml). The combined organic layer was washed with water (2 × 50 ml), followed by brine solution (1 × 50 ml). The organic layer was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude mass was subjected to column chromatography using 100-200 mesh silica gel when the desired product was obtained by eluting the column with 30% EtOAc/60-80 C Petrolium ether as solvent system. (94% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | General procedure: In a solution of compound 1 (250 mg, 0.96 mmol) in 3 ml anhydrous DMF, Cs2CO3 (407.28 mg, 1.25 mmol) was added. The mixture was stirred at room temperature for 1 h under anhydrous condition. Then methyl iodide (0.09 ml, 1.44 mmol) was added to the reaction mixture slowly and stirred at r.t. for 17 h. After completion of the reaction as indicated by TLC, saturated NaCl solution was added. The reaction mixture was extracted with ethyl acetate (3 × 25 ml). The combined organic layer was washed with water (2 × 50 ml), followed by brine solution (1 × 50 ml). The organic layer was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude mass was subjected to column chromatography using 100-200 mesh silica gel when the desired product was obtained by eluting the column with 30% EtOAc/60-80 C Petrolium ether as solvent system. (94% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile; at 0 - 20℃; for 2h;Inert atmosphere; | General procedure: To a mixture of halide (3.3 mmol, 1.1 equiv) and a solution of ROP(O)H2 (0.5 M in solvent, 6 mL, 3 mmol, 1 equiv) in a dry flask under N2, was added DBU (0.5 mL, 3.3 mmol, 1.1 equiv) at 0C. The stirred mixture was allowed to warm to rt over 2 h. The organic layer was washed with hexane (2x) and concentrated under reduced pressure. The residue obtained was purified by column chromatography over silica gel (hexane to EtOAc) to give the expected H-phosphinate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
181 mg | Stage #1: (2-(2,5-dimethylthiophen-3-yl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane); cinnamyl chloride With bis(dibenzylideneacetone)-palladium(0) In methanol at 20℃; for 0.166667h; Inert atmosphere; Glovebox; Stage #2: With potassium fluoride In methanol at 20℃; for 24h; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With caesium carbonate; silver(I) iodide; In N,N-dimethyl-formamide; at 60℃; under 11251.1 Torr; for 24h;Autoclave; | Representative experimental procedure for carboxylative coupling reaction Taking the carboxylative coupling of 4-methylphenylacetylene, <strong>[2687-12-9]cinnamyl chloride</strong> (2a), and CO2 as example: A 70 mL oven dried autoclave containing a stir bar was charged with AgI (0.5 mg, 0.002 mmol) and Cs2CO3 (978 mg, 3.0 mmol). 4-Methylphenylacetylene (232 mg, 2.0 mmol), <strong>[2687-12-9]cinnamyl chloride</strong> (458 mg, 3.0 mmol), and 20 mL dry DMF were added with syringe, respectively, after purging the autoclave with CO2 three times. The sealed autoclave was pressurized to appropriate pressure with CO2. The reaction mixture was stirred at 60 C for 24 h, then the autoclave was cooled to room temperature and the remaining CO2 was vented slowly. The reaction mixture was diluted with water (30 mL) and extracted with ethyl acetate (3*30 mL). The combined organic layers were washed with water and brine, dried over Na2SO4, and filtered. The solvent was removed under vacuum. The product (E)-cinnamyl 4-methylphenylpropiolate (3b) (502 mg, 1.82 mmol, 91% yield) was isolated by column chromatography on silica gel (ethyl acetate/petroleum ether: 1:25). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane; water; for 6h;Inert atmosphere; Reflux; | General procedure: Triethylamine (Et3N, 250mg, 2.5mmol) was added to a solution of commercially available cinnamyl alcohols (2.0mmol) in CH2Cl2 (15mL) at rt. p-Toluenesulfonyl chloride (TsCl, 420mg, 2.2mmol) was slowly added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 4h. The reaction mixture was cooled to rt. Substituted sulfinic sodium salt (3.0mmol) was added to a solution of the resulting cinnamyl chlorides at rt. A co-solvent of water (5mL) and 1,4-dioxane (10mL) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 6h. The reaction mixture was cooled to rt. The solvent was concentrated under reduced pressure. The residue was diluted with water (10mL) and the mixture was extracted with EtOAc (3×30mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc=6/1?2/1) afforded skeleton 3. Skeleton 3 is known and the analytical data are consistent with those in the literature.10 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of Fluoxetine hydrogen chloride 498 mg (1.45 mmol), sodium hydride 0.14 g (5.8 mmol) and N,N-dimethyl formamide (10 ml) was stirred at room temperature for 30 min, followed by the addition of cinnamyl chloride 407 mul (2.9 mmol). Stirring was continued for a period of 3 h and the contents were then poured over crushed ice. The precipitated product was isolated, washed and crystallized from methanol, giving off white Block-like crystals, suitable for X-ray analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | General procedure: To a solution of the 3a-d (2 mmol) in dry DMF (10 mL) wasadded sodium hydride (60% dispersion in mineral oil, 96 mg,2.4 mmol) at 0 C. After stirring for 15 min, the alkyl halide(2.4 mmol) was added at 0 C. The resulting mixture was stirredat 75 C for 12 h. Thereafter, the solvent was evaporated off in vacuo. The residue was purified by flash column chromatographyusing dichloromethane/petroleum ether as eluent to give targetcompounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With iodine; magnesium; In tetrahydrofuran; at 20 - 50℃;Inert atmosphere; Sonication; | A flame dried 100 mL round-bottomed flask under Ar was charged with chlorotrioctylstannane (2.0 g mL, 4.05 mmol), <strong>[2687-12-9]cinnamyl chloride</strong> (0.8 g, 5.3 mmol),magnesium powder (0.14 g, 5.7 mmol), a crystal of iodine and dry THF (50 mL). The resulting mixture was sonicated at 50 C for 6 h and was then stirred overnight at room temperature. Water (50 mL) was added and the mixture was transferred to a separating funnel. The water layer was separated and the remaining organic layer was diluted with heptane (100 mL), washed with acetonitrile (2 x 50 mL), water (50 mL) and finally againwith acetonitrile (3 x 50 mL). Drying on MgSO4, filtration and concentration in vacuo afforded a crude product, which was purified by column chromatography on silica gel using petroleum ether as the eluent, providing trioctyl(3-phenylallyl)stannane (1.42 g, 2.5 mmol, 62 %) as a faint yellow oil. ?H-NMR (CDC13, 400 MHz) & 7.40-7.26 (m, 2H), 7.25-7.20 (m, 2H), 7.12-7.06 (m, 1H),6.39 (dt, 1H, I = 15.5, 8.8 Hz), 6.17 (dt, 1H, I = 15.5, 1.0 Hz), 2.04-1.84 (m, 2H), 1.68-1.40 (m, 6H), 1.36-1.16 (m, 30H), 0.98-0.82 (m, 15 H); ?3C-NMR (100 MHz, CDC13):138.9, 131.3, 128.5, 125.8, 125.3, 125.1, 34.5, 32.0, 29.4, 29.3, 27.0, 22.8, 16.3, 14.2, 10.0;?9Sn-NMR (149.2 MHz, CDC13) & -12.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: To a solution of [Ru(Cp*)Cl2]2 (1) (6.2 mg, 1.5 mol%) and K2CO3 (226 mg, 1.63 mmol) in dry acetonitrile (0.5 mL) in a schlenk tube was added <strong>[2687-12-9]cinnamyl chloride</strong> (92 mul, 0.65 mmol). The resulting mixture was stirred at room temperature under a nitrogen atmosphere for 20 min followed by a slow addition of the corresponding phenols (0.98 mmol) (Table 2) in dry acetonitrile (1 mL) over 15 minutes. The reaction mixture was stirred for another 16 h at room temperature and then filtered through a celite plug and washed with dichloromethane (10 mL). The filtrate was evaporated under reduced pressure and purified by silica gel column chromatography to afford the branched product. Characterization data and copies of NMR spectra were provided below |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | Stage #1: 2-methyl-3-phenylpropanoic acid With lithium diisopropyl amide In tetrahydrofuran; hexane at 0 - 20℃; Inert atmosphere; Stage #2: cinnamyl chloride In tetrahydrofuran; hexane at 20℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | at 180℃; for 8h; | Through a reaction represented by Reaction Formula (2-1) below, a compound represented by Formula (13-1) was generated. [0122] More specifically, 15.2 g (100 mmol) of a compound represented by Formula (12-1) and 25 g (150.6024 mmol) of triethyl phosphite were put into a 200-ml flask, and the content of the flask was mixed at 180 C. for 8 hours to obtain a mixture. [0123] Next, the thus obtained mixture was cooled to room temperature and the excess triethyl phosphite was distilled off under reduced pressure to obtain the compound (white liquid) represented by Formula (13-1) in an amount of 24.1 g (yield: 90%). |
90% | at 180℃; for 8h; | In the reaction (R10), the compound (A1-1) was reacted with triethyl phosphite to obtain a compound (B1-1). Specifically, 15.2 g (0.10 mol) of the compound (A1-1) and 25.0 g (0.15 mol) of triethyl phosphite were added to a flask having a capacity of 200 mL. The content of the flask was stirred at 180 C. for 8 hours and then cooled to room temperature. Subsequently, unreacted triethyl phosphite contained in the content of the flask was distilled off under reduced pressure. Thereby, a compound (B1-1) which is a white liquid was obtained. The yield of the compound (B1-1) was 22.9 g, and the yield of the compound (B1-1) from the compound (A1-1) was 90%. |
87% | at 180℃; for 8h; | Specifically, a 200 mL flask containing 15.3 g (0.1mol) of compound lb and 25 g (0.15 mol) of triethyl phos-phite was stirred for 8 hours at 180 C.Next, afier cooling the flask to room temperature, excess triethyl phosphite was evaporated under reduced pressure to yield 22 g (percentage yield: approximately 87%) ofthe compound 3b (white liquid). |
at 180℃; for 8h; | In the reaction (r-1 '), a benzene derivative (3A') (15.2 g, 0.1 mol) and triethyl phosphite represented by the chemical formula (B) (25 g, 0.15 mol ), And the mixture was stirred at 180 C. for 8 hours and then cooled to room temperature. Thereafter, unreacted or remaining triethyl phosphite was distilled off under reduced pressure to obtain a phosphonate derivative (3C ') as a white liquid. The yield from the benzene derivative (3A ') of the phosphonate derivative (3C') was 23.5 g (yield: 92 mol%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | General procedure: In a solution of compound 1 (321 mg, 1.0 mmol) in anhydrous DMF (3 mL), Cs2CO3 (358 mg, 1.1 mmol) was added and the mixture was stirred at r.t. for 1 h. Then, benzyl bromide (0.13 mL, 1.1 mmol) was added slowly to the reaction mixture and the reaction mixture was stirred at r.t. After completion of the reaction (1 h) as indicated by TLC, a brine solution was added. The reaction mixture was extracted with ethyl acetate (3 * 25 mL). The combined organic layer was washed with water (2 * 50 mL), then with the brine solution (1 * 50 mL). The organic layer was dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude mass was subjected to column chromatography using 100-200 mesh silica gel when the desired product was obtained by eluting the column with 20% EtOAc/60-80 C Petroleum ether as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | General procedure: A representative procedure of skeleton 4 is as follows: K2CO3 (400 mg, 2.9 mmol) was added to a solution of 3 (1.0 mmol) in acetone (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Cinnamyl chloride (1.05 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt, concentrated, and extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=6:1 to 1:1) afforded 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 20℃; for 3h; | To a solution of 2.94 g (0.02 mol) of isatin in 20 mL of DMF with stirring at 10C was slowly added 0.84 g (0.02 mol) of sodium hydride (60% suspension in mineral oil). After 30 min, 2.92 mL (0.02 mol) of <strong>[2687-12-9]cinnamyl chloride</strong> was added to the resulting purple solution followed by stirring at room temperature for 3 h. The reaction mixture was poured into 100 g of crushed ice. Next, the resulting precipitate was filtered off, washed with hexane, and dried in a vacuum(18 mmHg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With formic acid; sodium nitrite; In acetonitrile; at 80℃; for 8h;Schlenk technique; | General procedure: A Schlenk tube was charged with olefins 1 (0.4 mmol), NaNO2 (138 mg, 2 mmol), HCOOH (0.5 mL, 10 mmol), and CH3CN(4.5mL). The reaction mixture was stirred at 70 C under air atmosphere for 4 h. After cooling to room temperature, the solution was filtered to remove the solid by-product then was washed with ethyl acetate (3×10 mL). The solution was concentrated under vacuum and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to obtain the desired product 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium azide; sodium L-ascorbate; In water; at 70℃; for 3h; | General procedure: The aromatic/aliphatic azide (1 mmol), alkyne (1 mmol), copper complex 3 (0.05 mol%) and sodium ascorbate 5 mol% (3 mL) were measured in a 5 mL glass vessel and the reaction mixture was heated at 70 C for 2.5 h. After completion of the reaction, it was cooled to room temperature and diluted with ethyl acetate. The copper complex 3 was removed by centrifugation and the organic layer was extracted with ethyl acetate, dried over MgSO4 and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (EtOAc/hexane, 1:4) to give the corresponding triazole. |
89% | With sodium azide; In ethanol; water; at 20℃; for 0.166667h;Sonication; | General procedure: A mixture of alkyne (1 mmol), alkyl halide (1 mmol), NaN3 (1.2 mmol) and functionalized graphene oxide Cu(I) complex (0.005 g) as a catalyst were added to a mixture of water and EtOH (1:1) (6 mL) as solvent and the reaction mixture was soncated in ultrasonic apparatus with 70W power. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was filtered through celite and the isolated catalyst was washed three times with ethanol (3 10 mL). The organic layer was separated and dried by rotary evaporator until the solid product precipitated. In order to further purification, recrystallization of the product was performed at 5:1 EtOAc:MeOH to yield the pure desired products. The products were characterized by 1H NMR, 13C NMR, FT-IR and melting points and the spectral data of synthesized compounds were compared with authentic samples as followed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium fluoride; bis(acetylacetonato)palladium(II); tetrabutyl-ammonium chloride; In tetrahydrofuran; at 90℃; for 24h;Autoclave; Inert atmosphere; | In a 25 mL high pressure dad, Palladium acetylacetonate (15.2 mg, 0.05 mmol) was added, Tetrabutylammonium chloride (277.9 mg, 1.0 mmol), Potassium fluoride (58.lmg, 1.0 [eta] [eta] & lt; 1 & gt;), And a stirring magnet was charged. After nitrogen substitution three times, Add <strong>[2687-12-9]cinnamyl chloride</strong> to high pressure dad (152.6 mg, 1.0 mmol,), Tetrahydrofuran (2 mL), Boronic acid pinacol ester (168. Omg, 1.O mmol), The charging port and the charging port are then closed. Carbon dioxide high pressure cylinders are connected to one atmosphere of carbon dioxide gas. The autoclave was stirred in a 90 C oil bath for 24 hours. After completion of the reaction, Slowly release the excess carbon dioxide, The reaction solution was transferred onto a 30 cm high silica gel column, Using petroleum ether: ethyl acetate as a developing solvent of 100: 1 column, The pure product was isolated, The yield of this reaction was 95%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium fluoride; C52H80N2O39Pd; In water; at 60℃; for 0.5h; | General procedure: Aryl, benzyl or allyl halides (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (1.5mmol), C1 (5×10-6 mol%) and H2O (2.0mL) were added into a sealed tube and the mixture was stirred at 60C for a few hours. After the reaction, the aqueous phase was extracted with ethyl acetate for 3 times (3×7mL). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | Adding p-methoxybenzoic acid (0.25 mmol, 48.0 mg) in a sealed tube, PhCH2CH2CH(Bpin) 2 (0.375 mmol, 139.8 mg), the reaction tube was replaced with a nitrogen atmosphere, and then 2 mL of tetrahydrofuran was added. Will reactThe tube was placed at -30 C, and under a nitrogen atmosphere, methyl lithium (0.625 mmol, 1.6 mol / L in Et 2 O) was added and stirred for 10 min.The reaction was then placed in a pot at 100 C for 24 h. Subsequently, <strong>[2687-12-9]cinnamyl chloride</strong> was added to the reaction tube under a nitrogen atmosphere.(0.5 mmol, 83.3 mg), continued to react at 100 C for 6 h. At the end of the reaction, water and ethyl acetate were added for extraction and column chromatography.The product was isolated in a yield of 61%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In neat (no solvent); at 80℃; for 0.0833333h;Microwave irradiation; Green chemistry; | General procedure: Briefly, a mixture of alkylimidazoles such as 1-methyl-1H-imidazole (MIM), 1-hexyl-1H-imidazole(HIM), 1-octyl-1H-imidazole (OIM), and 1-decyl-1H-imidazole (DIM) (1 mmol), as well as cinnamylchloride (1 mmol) solvent-free were microwaved to 200 MW at 80 C for 5 min (optimumreaction condition). Reaction completion was marked by separation of dense IL. Products suchas 1-methyl-3-cinnamylimidazolium chloride [CMIM]Cl, 1-hexyl-3-cinnamylimidazolium chloride[CHIM]Cl, 1-octyl-3-cinnamylimidazolium chloride [COIM]Cl, and 1-decyl-3-cinnamylimidazolium chloride [CDIM]Cl were isolated by decanting toluene to remove any unreacted starting materialsand solvents. Subsequently, ILs were rinsed with diethyl ether (4 10 mL) separating afterward thislatter layer by decantation. In each case, ILs were finally dried under reduced pressure to get rid of thevolatile organic compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In neat (no solvent); at 80℃; for 0.0833333h;Microwave irradiation; Green chemistry; | General procedure: Briefly, a mixture of alkylimidazoles such as 1-methyl-1H-imidazole (MIM), <strong>[33529-01-0]1-hexyl-1H-imidazole</strong>(HIM), 1-octyl-1H-imidazole (OIM), and 1-decyl-1H-imidazole (DIM) (1 mmol), as well as cinnamylchloride (1 mmol) solvent-free were microwaved to 200 MW at 80 C for 5 min (optimumreaction condition). Reaction completion was marked by separation of dense IL. Products suchas 1-methyl-3-cinnamylimidazolium chloride [CMIM]Cl, 1-hexyl-3-cinnamylimidazolium chloride[CHIM]Cl, 1-octyl-3-cinnamylimidazolium chloride [COIM]Cl, and 1-decyl-3-cinnamylimidazolium chloride [CDIM]Cl were isolated by decanting toluene to remove any unreacted starting materialsand solvents. Subsequently, ILs were rinsed with diethyl ether (4 10 mL) separating afterward thislatter layer by decantation. In each case, ILs were finally dried under reduced pressure to get rid of thevolatile organic compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In neat (no solvent); at 80℃; for 0.0833333h;Microwave irradiation; Green chemistry; | General procedure: Briefly, a mixture of alkylimidazoles such as 1-methyl-1H-imidazole (MIM), 1-hexyl-1H-imidazole(HIM), <strong>[21252-69-7]1-octyl-1H-imidazole</strong> (OIM), and 1-decyl-1H-imidazole (DIM) (1 mmol), as well as cinnamylchloride (1 mmol) solvent-free were microwaved to 200 MW at 80 C for 5 min (optimumreaction condition). Reaction completion was marked by separation of dense IL. Products suchas 1-methyl-3-cinnamylimidazolium chloride [CMIM]Cl, 1-hexyl-3-cinnamylimidazolium chloride[CHIM]Cl, 1-octyl-3-cinnamylimidazolium chloride [COIM]Cl, and 1-decyl-3-cinnamylimidazolium chloride [CDIM]Cl were isolated by decanting toluene to remove any unreacted starting materialsand solvents. Subsequently, ILs were rinsed with diethyl ether (4 10 mL) separating afterward thislatter layer by decantation. In each case, ILs were finally dried under reduced pressure to get rid of thevolatile organic compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In neat (no solvent); at 80℃; for 0.0833333h;Microwave irradiation; Green chemistry; | General procedure: Briefly, a mixture of alkylimidazoles such as 1-methyl-1H-imidazole (MIM), 1-hexyl-1H-imidazole(HIM), 1-octyl-1H-imidazole (OIM), and <strong>[33529-02-1]1-decyl-1H-imidazole</strong> (DIM) (1 mmol), as well as cinnamylchloride (1 mmol) solvent-free were microwaved to 200 MW at 80 C for 5 min (optimumreaction condition). Reaction completion was marked by separation of dense IL. Products suchas 1-methyl-3-cinnamylimidazolium chloride [CMIM]Cl, 1-hexyl-3-cinnamylimidazolium chloride[CHIM]Cl, 1-octyl-3-cinnamylimidazolium chloride [COIM]Cl, and 1-decyl-3-cinnamylimidazolium chloride [CDIM]Cl were isolated by decanting toluene to remove any unreacted starting materialsand solvents. Subsequently, ILs were rinsed with diethyl ether (4 10 mL) separating afterward thislatter layer by decantation. In each case, ILs were finally dried under reduced pressure to get rid of thevolatile organic compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In dichloromethane; for 9h;Reflux; | 4.1.7 7-(3-Phenyl-allyl)-1,3,5-triaza-7-phosphonia-tricyclo[3.3.1.13,7]decane; chloride (7e) Yield 88% (0.271 g); pale yellow solid; mp 203-205 C; 1H NMR (500 MHz, DMSO-d6) δ [ppm]: 7.59 (d, J = 6.5 Hz, 2H), 7.59 (t, J = 6.0 Hz, 2H), 7.34 (t, J = 6.0 Hz, 1H), 6.85 (d, J = 13.0 Hz, 1H), 6.47-6.43 (m, 1H), 5.01 (d, J = 9.5 Hz, 2H), 4.95 (d, J = 9.5 Hz, 2H), 4.52 (d, J = 11.0 Hz, 1H), 4.39-4.36 (m, 3H), 3.92-3.90 (m, 2H), 3.86-3.85 (m, 2H), 3.69 (d, J = 6.5 Hz, 2H); 13C NMR (125 MHz, DMSO-d6) δ [ppm]: 141.2, 135.8, 129.3, 129.1, 127.7, 115.3, 78.8, 69.7, 63.8, 52.5, 52.3, 45.9, 45.8; HRMS (ESI, M+) calcd. for C15H21N3P 274.1473, found 274.1448. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | To a DMF (7.0 mL) solution of N-Boc-p-toluenesulfonamide (1.00 g, 3.69 mmol) was added 60% sodium hydride (0.22 g, 5.53 mmol) at 0 C. The reaction mixture was stirred for 15 min at room temperature. To the mixture at 0 C were added <strong>[2687-12-9]cinnamyl chloride</strong> (0.675 g, 4.42 mmol) and 15-crown-5-ether (0.22 g, 3.69 mmol) at 0 C. The mixture was stirred for 12 h and poured into water (50 mL). The S19 organic layer was separated and the aqueous layer was extracted with AcOEt. The combined organic layer was washed with H2O (50 mL 2) and dried over MgSO4. The solvent was removed under reduced pressure. The residue was precipitated from n-hexane and filtered off to give the titled compound (1.35 g, 95%) as white powders. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With C19H21ClNNiOP; In tetrahydrofuran; diethyl ether; at 20℃; for 24h; | General procedure: A 50 mL Schlenk tube was charged with 1b (1.0-2.5 mol%), the respective allylic electrophile(1.0 mmol), Et2O (2.5-5 mL, 0.2 M based on the electrophile), and the aryl Grignard reagent (1.5-3.0equiv.) at room temperature. The coupling reaction was carried out at room temperature for 24 h.After quenching with 1 M HCl aq. (5 mL), the aqueous layer was extracted with EtOAc (5 3 mL).The combined organic layers were washed with brine (10 mL) and dried over anhydrous MgSO4.After filtration and removal of all volatiles from the filtrate, the residue was purified by columnchromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hemin; water; sodium nitrite at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate; benzyl ((11bS)-2,6-bis(3,5-di(tert-butyl)-4-methoxyphenyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphosphepin-4-yl)-L-prolinate; N-ethyl-N,N-diisopropylamine; carbonic acid dimethyl ester at 40℃; Sealed tube; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | 1,4-difluoro-2-nitrobenzene (75.0 g), ethyl acetate (375 mL),Add 5% palladium on carbon (4.0 g) to the reaction vessel,In a hydrogen atmosphere,The mixture was stirred at 25-60C for 4 hours.The solid is filtered off,Water (375 mL) in the filtrate,Add sodium bicarbonate (59.4g),Cinnamyl chloride (86.0 g) was slowly flowed in at a temperature not exceeding 0C.After the inflow ends,Stir for 1 hour. Liquid separation was performed, and the organic layer was washed twice with water (375 mL). The organic layer was concentrated under reduced pressure, and toluene (375 mL) was added to the residue for recrystallization to obtain the title compound (100.0 g) as a white solid (81% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium carbonate; In N,N-dimethyl-formamide; at 70 - 80℃;Inert atmosphere; | General procedure: To a well-stirred solution of 6a-e (1 mmol) in 4 mL of dry DMF was added the suitable organic halides (5.0-6.0 mmol) followed by K2CO3 (5.0-8.0 mmol) and the reaction mixture was heated at 70-80 C with stirring until the reaction was completed. The progress of the reaction was checked by TLC, which showed the appearance of new spots with higher Rf value than the starting compound. After the completion of the reaction, water was added to it and extracted with dichloromethane, washed successively with water and brine and then dried over anhydrous Na2SO4. The residue after solvent evaporation in vacuo, was purified by silica gel column chromatography (10% EtOAc : hexane). cis-3-pentyl-1,4-diphenyl-3-phenylsulfonyl-beta-lactam 7d |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With 1,1,2,2-tetramethyl-1,2-ethanediamino-N,N'-bis(3,5-di-tert-butylsalicylidene)-cobalt(II); phenylsilane; tetrabutylammonium tetrafluoroborate; C19H28N2O6; copper(II) bis(trifluoromethanesulfonate); acetic acid; In N,N-dimethyl-formamide; at 0℃;Electrolysis; Inert atmosphere; Sealed tube; | General procedure: In a 2 dram vial, ligand 4 (7.6 mg, 0.02 mmol,10 mol%) and Cu(OTf)2 (3.6 mg, 0.01 mmol, 5 mol%) were dissolved in DMF (1.0 ml) under a N2 atmosphere, and the mixture was stirred for 2 h before use (Solution A). An oven-dried, 10 ml two-neck glass tube was equipped with a magnetic stir bar, a rubber septum, a threaded Teflon cap fitted with electrical feedthroughs, a carbon felt anode (1 × 0.5 × 0.6 cm3; connected to the electrical feedthrough via a graphite rod that was 9 cm in length and 2 mm in diameter) and a platinum plate cathode (1.0 × 0.5 cm2). To this reaction vessel, TBABF4 (132 mg)was added. The cell was sealed and flushed with nitrogen gas for 5 min, followed by the sequential addition via syringe of the olefin substrate (0.2 mmol, 1.0 equiv., dissolved in 1 ml DMF) and HOAc (60 mul, 1 mmol, 5 equiv.), Co(salen) 3 (0.6 mg,0.001 mmol, 0.5 mol%, dissolved in 1 ml DMF) and Solution A. A nitrogen-filled balloon was adapted through the septum to sustain a nitrogen atmosphere. The reaction vessel was then cooled to 0 C. PhSiH3 (24 mg, 0.22 mmol, 1.1 equiv.) and TMSCN (50 mul, 0.4 mmol, 2 equiv.) were dissolved in DMF (1.0 ml), and the resulting solution was added to the glass tube via syringe. Electrolysis was initiated at a cell potential of 2.3 V at 0 C. Upon full consumption of the olefin starting material as determined by thin-layer chromatography analysis, the electrical input was removed. The mixture was diluted with ethyl acetate (60 ml) and then washed with water (40 ml) and brine, dried over anhydrous Na2SO4 andconcentrated under reduced pressure. The residue was subjected to flash columnchromatography on silica gel (eluted with hexanes and ethyl acetate) to yield the desired product. See Extended Data Fig. 1a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0) In 1,4-dioxane; water at 60℃; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: imidazolidone With sodium hydride In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: cinnamyl chloride In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; | 4.2.1. Preparation of compounds PL-1~PL-6 and compounds 1-5 General procedure: The starting material, 5, 6-dihydro-1H-pyridin-2-one, 2-piperidone, propyleneurea, 2-imidazolidone and 2-piperazinone(1 equiv.) was added to tetrahydrofuran or dichloromethane undernitrogen, and added NaH (3 equiv.) to the reaction mixture at0 C for 15 min. Then, () - cinnamyl chloride (1 equiv.) was addedto the mixture with stirring at 20 C for 30 min. The reaction wasquenched with saturated NaHCO3 solution, and then extractedtwice with ethyl acetate. The combined extracts were then washedsuccessively with H2O, brine, and dried over anhydrous Na2SO4.After concentration under reduced pressure, the residue wasquickly purified by using a flash silica gel column (PE/EtOAc). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(trichloromethyl) carbonate In 1,2-dichloro-ethane at 0 - 40℃; for 2h; | 22 Example 16. Synthesis of 2-chloro-5-methylpyridine (R=methyl, R1=H, chlorinating agent is bis(trichloromethyl carbonate) General procedure: Add 135g crude amide (content 90%, 0.87mol), 1,2-dichloroethane 100mL, DMF 74.1g (99.0%, 1.0mol, 1.15eq) into the 1L reaction flask, stir well, and use a low temperature reaction bath Cool down to about 0°C, then use a constant pressure dropping funnel to slowly drop a solution of 191.2g (99.0%, 0.64mol, 0.73eq) bis(trichloromethyl)carbonateand 400mL 1,2-dichloroethane, during the dropping process, the internal temperature should not exceed 20°C. After dripping, slowly heat up to about 40°C and keep it for 2h.Then, vacuum distillation removes most of the solvent. When the temperature in the kettle reaches about 100°C (at this time, the solvent 1,2-dichloroethane has been distilled off), switch the receiving bottle,Collect 2-chloro-5-methylpyridine (CMP) and base hydrochloride, steam to an internal temperature of about 165°C, and end when there is almost no fraction. The collected CMP and its CMP hydrochloride (5-substituted 2-chloropyridine such as CMP are weak organic bases). In the hydrochloride formed, pyridine and hydrogen chloride are not closely combined. Taking CMP hydrochloride as an example, when heated to the boiling point of CMP, it dissociates into CMP and hydrogen chloride.After being cooled, they are combined together to form hydrochloride, which behaves like this under normal pressure or reduced pressure) The mixture is neutralized with a 10wt% aqueous sodium hydroxide solution to pH=9-10, and then separated into layers.The aqueous phase was extracted with 200 mL*3 of 1,2-dichloroethane, the organic layers were combined, dried over anhydrous sodium sulfate, and then distilled under reduced pressure with a water pump.Collect 104.1 g of the distillate at 118-120°C (98.5% by weight), a colorless and transparent liquid, with a yield of 92.0%. |
Tags: 2687-12-9 synthesis path| 2687-12-9 SDS| 2687-12-9 COA| 2687-12-9 purity| 2687-12-9 application| 2687-12-9 NMR| 2687-12-9 COA| 2687-12-9 structure
[ 21087-29-6 ]
(E)-(3-Chloroprop-1-en-1-yl)benzene
Similarity: 1.00
[ 21087-29-6 ]
(E)-(3-Chloroprop-1-en-1-yl)benzene
Similarity: 1.00
[ 21087-29-6 ]
(E)-(3-Chloroprop-1-en-1-yl)benzene
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[ 13565-07-6 ]
(E)-3-(p-Tolyl)acryloyl chloride
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