Structure of 696-62-8
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Sokolnicki, Tomasz ; Stefanowska-Kątna, Kinga ; Czapik, Agnieszka ; Walkowiak, Jędrzej ; Franczyk, Adrian ;
Abstract: A novel approach towards synthesizing new metalloid-substituted olefins has been accomplished by transforming (E)-1,2-diboryl-1-silylethenes through two consecutive Suzuki–Miyaura coupling reactions. This methodology provides an effective and selective way to obtain new, structurally different products, such as (E)-1-silyl-1-boryl-2-arylethens, (1E,3E)-1-silyl-1-boryl-2-alkenylethens, and (E)-1-silyl-1-aryl1-2-aryl2ethenes, which are difficult to synthesize through hydrometallation reactions and related processes. Due to the presence of reactive motifs (silyl group, Bpin moiety, and Csp2-H bond) in the structure of the final products, these molecules might be considered powerful building blocks in modern chemistry. With the aid of demetallation and cross-coupling reactions, they might be further functionalized into several invaluable chemicals, i.e., tetrasubstituted olefins (anti-cancer drugs, fluorescence materials), compounds with high π-conjugation, and polymers.
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Keywords: (E)-1-silyl-1,2-diboryl-ethenes ; aryl iodides ; (E)-(2-iodovinyl)benzenes ; Suzuki–Miyaura cross-coupling ; substituted olefins ; building blocks
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Zhao, Spencer ; Loh, Kang Yong ; Tyson, Jonathan ; Kadur, Chandan ; Bertozzi, Carolyn ; Deisseroth, Karl , et al.
Abstract: Catalytic reactions of a broad range of abiotic molecules and macromolecules are beyond the native capabilities of mammals. Natural enzymes from prokaryotes or plant-based eukaryotes have limited substrate scopes. Therefore, broadening the range of catalytic bond-forming reactions that function in physiological conditions would enable the syntheses of a vast array of molecules directly within biological systems. This approach may provide an alternative way to modulate cellular behaviors if such molecules can be synthesized with spatiotemporal control on specific cell types in living systems; furthermore, restricting synthesis to well-defined cells or cell-types would enable a potentially transformative approach of treating cells as separable reaction vessels within living organisms. Herein, we use genetic targeting to incorporate an organic photocatalytic dye onto specific cell types to enable in-situ light-controlled and spatially defined chemical synthesis of non-natural molecules. We demonstrate, for the first time, a photo-patterned organic coupling reaction in the extracellular matrix of living cells under dilute, aqueous, aerobic physiological conditions. A 6-fold contrast in reaction yield can be achieved between two adjacent HEK293FT cells with and without light exposure. The above photocatalysis can be initiated using mild confocal laser stimulation as low as 16 μW/mm2 at multiple wavelengths. Furthermore, the cell-type specific photocatalyzed C-H functionalization coupling reactions taking place on cell surfaces are used to demonstrate anabolic construction of non-natural products. The above findings lay an important foundation for developing future abiotic cell-type specific chemical syntheses in living organisms.
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CAS No. : | 696-62-8 |
Formula : | C7H7IO |
M.W : | 234.03 |
SMILES Code : | COC1=CC=C(I)C=C1 |
MDL No. : | MFCD00001056 |
InChI Key : | SYSZENVIJHPFNL-UHFFFAOYSA-N |
Pubchem ID : | 69676 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 9 |
Num. arom. heavy atoms | 6 |
Fraction Csp3 | 0.14 |
Num. rotatable bonds | 1 |
Num. H-bond acceptors | 1.0 |
Num. H-bond donors | 0.0 |
Molar Refractivity | 45.65 |
TPSA ? Topological Polar Surface Area: Calculated from |
9.23 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
2.26 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
2.95 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
2.3 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
2.72 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
2.81 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
2.61 |
Log S (ESOL):? ESOL: Topological method implemented from |
-3.58 |
Solubility | 0.062 mg/ml ; 0.000265 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (Ali)? Ali: Topological method implemented from |
-2.81 |
Solubility | 0.366 mg/ml ; 0.00156 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-3.48 |
Solubility | 0.0771 mg/ml ; 0.00033 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-5.63 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
2.0 |
* 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 |
---|---|---|
80% | Stage #1: With 2,2,6,6-tetramethylpiperidinyl-lithium In toluene at 20℃; for 0.25 h; Glovebox Stage #2: With palladium(l) tri-tert-butylphosphine iodide dimer In toluene at 20℃; Glovebox |
General procedure: Inside the glovebox, lithium 2,2,6,6-tetramethylpiperidide (LiTMP, 70.7 mg, 0.48 mmol, 1.2 eq.) was dissolved in toluene (1.5 mL) and carbonyl compound (3, 0.48 mmol, 1.2 eq.) was added. After 15 min of stirring at ambient temperature a solution of Pd(I) iodo dimer (2, 3.5 mg, 0.004 mmol, 1 molpercent for aryl iodides; 17.4 mg, 0.02 mmol, 5 molpercent for aryl bromides) and aryl halide (4, X = I or Br, 0.4 mmol, 1.0 eq.) in toluene (0.5 mL) was added. After 4-18 h of further stirring at ambient temperature (reaction progress was monitored by GCMS), the crude was directly adsorbed onto silica (washing with diethyl ether) and purified by flash column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In N,N-dimethyl-formamide; at 140℃; for 24h; | General procedure: CuI (0.05 equiv), 1,10-phenanthroline (0.1 equiv) and K2CO3 (2 equiv) were placed in an oven-dried screw-capped test tube with Teflon-lined septum that was filled with nitrogen. About 2.5 mL of dry DMF was then added at room temperature. Now the corresponding aryl iodide (1.0 mmol) was added followed by MBI or FMBI (1.0 equiv) and the tube was placed in the preheated oil bath at 140 C and the reaction mixture was magnetically stirred for 22 h. After complete disappearance of iodobenzene (the progress of the reaction was followed by TLC), the reaction mixture was allowed to cool to room temperature. Then water was added and the reaction mixture was extracted with ethyl acetate. After removal of the solvent in vacuum, the crude residue was purified by column chromatography.5- (or 6-) (Difluoromethoxy)-2-(phenylsulfanyl)-1H-benzimidazole (1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With 18-crown-6 ether; potassium carbonate; In 1,2-dichloro-benzene; at 150℃; for 48h;Inert atmosphere; Schlenk technique; | General procedure: 1,1-Bis(4-aminophenyl)cyclohexane(0.98 g, 3.68 mmol), 4-iodotoluene (4.81 g, 22.1 mmol) and 18-crown-6 (0.39 g, 1.47 mmol) were dissolved in o-dichlorobenzene(18 ml) in a two-necked round-bottomed flaskequipped with a magnetic stirrer and a reflux condenser. Afterheating the mixture above 150 C, dry potassium carbonatepowder (3.31 g, 24.0 mmol) and copper bronze (0.94 g, 14.7 mmol) were added. After 48 h, the mixture was cooled,filtered and o-dichlorobenzene was removed by distillation.The crude products were further purified using silica-gelcolumn chromatography (dichloromethane-n-hexane 1:4 v/v),which afforded the product as a white powder [yield 1.24 g,54%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; potassium carbonate; triphenylphosphine; In benzene; at 150℃; for 24h;Sealed tube; | General procedure: In a 30-mL sealed tube, <strong>[2622-63-1]1-methyl-2-phenylbenzimidazole</strong> (1, 0.25mmol), [RuCl2(p-cymene)]2 (0.0125 mmol), Ph3P (0.075 mmol),K2CO3 (0.50 mmol), and iodoarene (0.25 mmol) were combined inanhydrous benzene (2 mL) under air. The mixture was then stirredat 150 °C for 24 h. The mixture was cooled to r.t., diluted with EtOAc, and filtered through a small pad of Celite. The filtrate was concentrated in vacuo and purified by flash chromatography (silicagel, EtOAc?hexane) to give the analytically pure 2-(biphenyl-2-yl)benzimidazoles. 2-(4?-Methoxybiphenyl-2-yl)-1-methyl-1H-benzoimidazole (2a) Pale yellow oil; yield: 76 mg (96percent); Rf = 0.26 (hexane?acetone,3:1).1H NMR (400 MHz, CDCl3): delta = 7.85 (d, J = 7.8 Hz, 1 H, HAr), 7.71(d, J = 7.6 Hz, 1 H, HAr), 7.50?7.62 (m, 2 H, HAr), 7.47 (t, J = 7.3Hz, 1 H, HAr), 7.20?7.35 (m, 2 H, HAr), 7.17 (d, J = 7.6 Hz, 1 H,HAr), 7.13 (d, J = 8.8 Hz, 2 H, HAr), 6.73 (d, J = 8.8 Hz, 2 H, HAr),3.73 (s, 3 H, OMe), 3.02 (s, 3 H, NMe).13C NMR (100 Hz, CDCl3): delta = 158.8, 154.1, 143.1, 141.2, 135.5,132.5, 132.1, 130.3, 129.7 (2 CAr), 129.6, 128.7, 127.1, 122.3,122.0, 119.7, 114.0 (2 CAr), 109.5, 55.1 (OMe), 30.2 (NMe).HRMS (FAB): m/z [M + H]+ calcd for C21H19ON2: 315.1497; found: 315.1507. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73%; 20% | With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; mesitylenecarboxylic acid; potassium carbonate; In toluene; at 150℃; for 24h;Sealed tube; | General procedure: In a 30-mL sealed tube, <strong>[2622-63-1]1-methyl-2-phenylbenzimidazole</strong> (1, 0.25mmol), [RuCl2(p-cymene)]2 (0.0125 mmol), Ph3P (0.075 mmol),K2CO3 (0.50 mmol), and iodoarene (0.25 mmol) were combined inanhydrous benzene (2 mL) under air. The mixture was then stirredat 150 °C for 24 h. The mixture was cooled to r.t., diluted with EtOAc, and filtered through a small pad of Celite. The filtrate was concentrated in vacuo and purified by flash chromatography (silicagel, EtOAc?hexane) to give the analytically pure 2-(biphenyl-2-yl)benzimidazoles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With copper(l) iodide; 1,10-Phenanthroline; sodium t-butanolate; In toluene; at 120℃; for 48h;Inert atmosphere; | The reaction equation is as follows: Paraiodoanisole (15 g, 0.064 mol) and 6-bromo-2-naphthylamine (3.3 g, 0.015 mol) were dissolved in 120 ml of anhydrous toluene.Add CuI (0.89 g, 4.67 mmol) rapidly under nitrogen atmosphere.1,10-phenanthroline (1.232 g, 6.83 mmol) and sodium tert-butoxide (7 g, 75 mmol) were heated to 120C.After about 48 hours of reaction, the toluene is concentrated and removed.Simultaneously added dichloromethane and distilled water extraction (the volume ratio of dichloromethane and distilled water is 1:1),The organic layer was dried over anhydrous magnesium sulfate.filter,After decompression, concentratePurification by column chromatography (column chromatography with petroleum ether and various volumes of petroleum ether and dichloromethane,The first developing agent was petroleum ether.Subsequent developing agents are petroleum ether and dichloromethane in different volume ratios.The volume of methylene chloride increases sequentially;Finally, develop the petroleum ether in the agent:Dichloromethane = 4:1 (v:v)),A pale yellow solid, Compound 1, was obtained.The yield is about 88% (5.8g); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; In N,N-dimethyl-formamide; at 120℃; under 7500.75 Torr; for 20h;Inert atmosphere; Autoclave; | General procedure: A 12mL vial was charged with MCM-41-2P-Pd(OAc)2 (2molpercent), 2-aminobenzamide (1mmol), aryl iodide (1mmol) (if solid) and a stirring bar. Then, DMF (2mL), aryl iodide (1mmol) (if liquid) and DBU (2mmol) were injected by syringe under an argon atmosphere. The vial was placed in an alloy plate, which was transferred into a 300mL Parr Instruments 4560 series autoclave under an argon atmosphere. After flushing the autoclave three times with CO, a pressure of 10bar CO was fixed at ambient temperature. The autoclave was heated for 20hat 120°C. After completion of the reaction, the autoclave was cooled to room temperature and the pressure was released carefully. The reaction mixture was diluted with ethyl acetate (10mL) and filtered. The palladium catalyst was washed with distilled water (2×5mL) and acetone (2×5mL), and reused in the next run. The filtrate was concentrated in vacuo and the pure product was isolated by either washed with water, ethyl acetate and finally hexane or recrystallization from MeOH. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate; In tetrahydrofuran; at 60℃; for 12h;Inert atmosphere; | [00454] To a reaction flask were added 1-i odo-4- methoxybenz ene (53 g, 226.47 mmol), 3-methylbutan-2-one (59 g, 685.0 mmol), Xantphos (13 g, 22.47 mmol), Pd2(dba)3 (10 g, 10.92 mmoll), t-BuONa (43 g, 447.43 mmol) and tetrahydrofuran (500 mL). The mixture was degassed and filled with nitrogen for three times, then heated to 60 C and stirred for 12 h. The mixture was cooled to rt, filtered, and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (P E /E A (V N) = 30/1) to give the title compound as yellow oil (36g, 187.26 mmol, 83%).MS (ESI, pos.ion) m/z: 193.1[M÷H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With 3 wt% Pd/gamma-Al2O3; silver trifluoroacetate; acetic acid hydrazide; In acetic acid; at 130℃; for 48h; | General procedure: In a typical reaction, o-methyl benzaldehyde(0.10 mmol), iodobenzene (0.30 mmol), acetohydrazide (0.03 mmol), silver trifluoroacetate (0.30 mmol), catalyst(25 mg), and the solvent AcOH : HFIP =3:1 (2.0 mL) were charged in a 25 mL oven dried reaction tube. Reactionwas carried out 130 for 48 h in an oil bath under air condition. After being cooled to room temperature, thereaction solution was evaporated in vacuo. The residue was purified by flash column chromatography (silica gel,ethyl acetate/petroleum ether = 1:15~1:30 as an eluent) to afford the desired product 3. All the products were alsoconfirmed by comparing the 1H NMR and 13C NMR data with authentic samples. |
Tags: 696-62-8 synthesis path| 696-62-8 SDS| 696-62-8 COA| 696-62-8 purity| 696-62-8 application| 696-62-8 NMR| 696-62-8 COA| 696-62-8 structure
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P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
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 |
Sorry,this product has been discontinued.
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