Structure of 4-Hydroxybenzophenone
CAS No.: 1137-42-4
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CAS No. : | 1137-42-4 |
Formula : | C13H10O2 |
M.W : | 198.22 |
SMILES Code : | OC1=CC=C(C=C1)C(=O)C1=CC=CC=C1 |
MDL No. : | MFCD00002355 |
InChI Key : | NPFYZDNDJHZQKY-UHFFFAOYSA-N |
Pubchem ID : | 14347 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
21% | With potassium carbonate; sodium iodide; In acetone;Heating / reflux; | Step 1: {4-[(2-Hydroxyethyl)oxy]phenyl}(phenyl)methanone (5)To a solution of 4-hydroxybenzophenone (6.0 g, 29.7 mmol) in acetone (50 mL) were added K2CO3 (12.3 g, 89.0 mmol) and 2-chloroethanol (4.0 mL, 59.3 mmol), followed by addition of NaI (4.50 g, 29.7 mmol). The reaction mixture was refluxed under nitrogen overnight. The mixture was cooled to room temperature. The white solid was filtered off and washed with acetone (100 mL). The filtrate was concentrated to a brown oil residue with some white solid. EtOAc (200 mL) was added, the white solid was filtered off and then washed with 50 mL of EtOAc. The filtrate was washed with 1 N NaOH, water, brine and dried over Na2SO4. Concentration afforded a pale yellow oil which was further purified by chromatography on a silica gel column eluted with a gradient from hexanes to 60% EtOAc:hexanes to give 5 as a white solid (1.52 g, 21%). 1H NMR (400 MHz, CDCl3): delta 4.00-4.05 (m, 2H), 4.15-4.20 (m, 2H), 6.98 (d, J=8.7 Hz, 2H), 7.45-7.50 (m, 2H), 7.55-7.60 (m, 1H), 7.75 (d, J=7.1 Hz, 2H), 7.83 (d, J=8.8 Hz, 2H). |
Preparation of Compound I; Synthesis of 3-(2-methylaziridin-l-yl)propionic acid 2-(4-benzoylphenoxy)ethyl ester (AZBP); To a 250 mL, one -neck, round bottom flask equipped with a magnetic stirrer were added sodium hydroxide (10.0 g, 0.250 mol) in a water (45 mL)/ethanol (20 mL) solution and 4-hydroxybenzophenone (Alfa Aesar, 50.0 g, 0.250 mol) and the mixture was heated to 55 0C. Chloroethanol (Aldrich, 20.3 g, 0.250 mol) in ethanol (25 mL) was then added dropwise to the reaction flask and the mixture heated to 75 0C for 8 hours then cooled to room temperature. The precipitate was collected by filtration, washed with water and recrystallized three times from ethanol/water to obtain 24.4 g of a white solid (4-(2- hydroxyethoxy)benzophenone). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium iodide; In toluene; at 60℃; for 1.5h;Reflux; | 4-hydroxybenzophenone (262 g, 1.32 mol)NaI (6.5 g, 0.043 mol),Ethylene carbonate (125 g, 1.42 mol) andToluene (10 mL) were added to a 2000 mL three-necked flask,Raise the temperature until the system is clear.Continue to raise the temperature to the reaction system was refluxed for 1.5h,After the TLC test reaction is completed, the heating is stopped,Cooled to 60 C.To the reaction system was added water and ethyl acetate,extraction,The organic phase was dried over anhydrous sodium sulfate,Concentrated to give 304 g of a pale yellow solid,Yield 95%. |
94% | With sodium iodide; In toluene; at 99 - 176℃; for 0.5h;Product distribution / selectivity; | A mixture of ethylene carbonate (124.6 g; 1.07 eq.), sodium iodide (6.3 g; 0.03 eq.), 4-hydroxybenzophenone (262 g; 1 eq.) and toluene (8.1 g) was heated. At99C a clear solution was obtained. The reaction mixture was heated with reflux condenser to 176C over one hour, during which gas evolution occurred. After an additional ½ hour at 176C, the reaction mixture was cooled to 122C and toluene (350 g) and water (24 g) was added. The lower phase was cut and discarded. More water (14 g) was added and the lower phase was again cut and discarded. Water and toluene (95 g in total) was azeotropically removed, reaching a boiling point of 11 1 C. More toluene (1 14 g) was added and the product was isolated by filtration at 8C. In total, 302 g of 4-(2-hydroxyethoxy)benzophenone (94%) was obtained after drying as white crystals (99.8 % chromatographic purity). |
from 4-hydroxy-benzophenone and ethylene carbonate there is obtained 2-(p-benzoylphenoxy)-ethanol, m.p. 78-80 C.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydroxide; In ethanol; water; | EXAMPLE 2 Sodium 2-hydroxy-3-(4-benzoylphenoxy)propane sulphonate A solution of sodium hydroxide (3.3g) in water (5 mls) was added to a solution of sodium 3-chloro-2-hydroxypropane sulphonate (14.73g) in water (30 mls) and the resultant solution added to a solution of 4-hydroxybenzophenone (9.9g) in ethanol (50 mls). After stirring under reflux for 18 hours, the pH of the pale yellow solution was brought to 4 via the addition of 4N. hydrochloric acid and after cooling in an ice bath for several hours the crude title compound was filtered and twice washed with ethanol (20 ml portions) and dried at 50C. giving a pale brown sandy solid (11.58g) of melting point equal to 320-323C. Recrystallisation with charcoaling from a mixture of ethanol (50 mls) and water (15 mls) followed by filtration, washing and drying gave sodium 2-hydroxy-3-(4-benzoylphenoxy) propane sulphonate (9.84g; yield = 55%) as a pale brown sandy solid of melting point equal to 316-318C. Analysis:- Calcd for C16H15NaO6S C 53.63; H 4.22; S 8.95; Na 6.42 Found: C 53.57; H 4.24; S 8.75; Na 6.69 An aqueous solution of this compound has an absorption maximum at 294 nm with an extinction coefficient (1%, 1cm) of 467. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | I a) Ethylene glycol p-benzophenone ether; In a laboratory autoclave having a capacity of 2 L there were placed 520 g of diethylene glycol diethyl ether, 286 g of p-hydroxybenzophenone (>98 wt %), and 0.8 g of powdered potassium hydroxide. A pressure test was then carried out for 30 minutes using dry nitrogen. Following pressure let-down to atmospheric pressure and heating of the reaction mixture under a blanket of nitrogen to 120 C., 95.4 g of ethylene oxide were continuously forced in to give a maximum internal pressure of 4 bar over a period of 1 h. On completion of gassing with ethylene oxide, the reaction mixture was allowed to react, until the pressure remained constant for at least 30 minutes. The reaction mixture was discharged from the autoclave in the hot state, neutralized with 5 wt % strength aqueous hydrochloric acid, and poured into 2 L of ice water, and the reaction product was caused to crystallize by constant agitation. The resulting solid matter was filtered off in vacuo, washed with ice water and dried in vacuo (40 C., 10 mbar absolute). The resulting filtrate was concentrated in a rotary film evaporator to 20% of its volume, the precipitated product filtered off in vacuo, washed with ice water and likewise dried in vacuo. The total yield was 82% of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In acetonitrile; for 24.0h;Reflux; | Synthesis of BP-4; [0146] Synthesis of Acrylic acid 4-[3-(4-benzoyl-phenoxy)-2-hydroxy- propoxy]butyl ester: A reaction mixture containing 4-hydroxybenzophenone (14.9 g, 75 mmol), acetonitrile (40 mL), potassium carbonate (7.8 g, 56,3 mmol) and 4- hydroxybutylacrylate glycidylether (7,5 g, 37,5 mmol) was heated to reflux. The mixture was allowed to stir at reflux temperature for 24 hours. The mixture was cooled to room temperature and filtered to remove the undissolved potassium carbonate. The filtrate was evaporated under reduced pressure, The residua. oil was diluted with ethyl acetate (250 ml) and extracted with a mixture of an aqueous solution of sodium hydroxide (1 N) and distilled water (4/1). The organic layer was separated, dried over MgSO4, filtered and evaporated to provide 15.1 g of a yellow oil. The product was purified on a SVP D40 Merck Np Column using dichloromethane / n-hexane (50/50) as eluent, to afford 5.5 g of a yellow oil. | |
With sodium hydroxide; potassium carbonate; In hexane; dichloromethane; water; acetonitrile; | Synthesis of BP-7 Synthesis of acrylic acid 4-[3-(4-benzoyl-phenoxy)-2-hydroxy-propoxy]butyl ester: A reaction mixture containing 4-hydroxybenzophenone (14.9 g, 75 mmol), acetonitrile (40 mL), potassium carbonate (7.8 g, 56.25 mmol) and 4-hydroxybutylacrylate glycidylether (7.5 g, 37.5 mmol) was heated to reflux. The mixture was allowed to stir at reflux temperature for 24 hours. The mixture was cooled to room temperature and filtered to remove the undissolved potassium carbonate. The filtrate was evaporated under reduced pressure. The residual oil was diluted with ethyl acetate (250 ml) and extracted with a mixture of an aqueous solution of sodium hydroxide (1N) and distilled water (4/1). The organic layer was separated, dried over MgSO4, filtered and evaporated to provide 15.1 g of a yellow oil. The product was purified on a SVP D40 Merck Np Column using dichloromethane/n-hexane (50/50) as eluent, to afford 5.5 g of a yellow oil. | |
5.5 g | With potassium carbonate; In acetonitrile; for 24.0h;Reflux; | Synthesis of acrylic acid 4-[3-(4-benzoyl-phenoxy)-2-hydroxy-propoxy]butyl ester A reaction mixture containing 4-hydroxybenzophenone (14.9 g, 75 mmol), acetonitrile (40 mL), potassium carbonate (7.8 g, 56.25 mmol) and 4-hydroxybutylacrylate glycidylether (7.5 g, 37.5 mmol) was heated to reflux. The mixture was allowed to stir at reflux temperature for 24 hours. The mixture was cooled to room temperature and filtered to remove the undissolved potassium carbonate. The filtrate was evaporated under reduced pressure. The residual oil was diluted with ethyl acetate (250 ml) and extracted with a mixture of an aqueous solution of sodium hydroxide (1N) and distilled water (4/1). The organic layer was separated, dried over MgSO4, filtered and evaporated to provide 15.1 g of a yellow oil. The product was purified on a SVP D40 Merck Np Column using dichloromethane/n-hexane (50/50) as eluent, to afford 5.5 g of a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 24h; | 4-hydroxy benzophenone (9.9 g, 50 mmol), 2-bro-moethanol (7.5 g, 60 mmol) and potassium carbonate (10 g, 75 mmol) were added to N,N-dimethylformamide (DMF, 150 mE), and stirred at 90 C. for one day. A solvent was distilled off, and dichioromethane was added. The mixture extracted with water and saturated saline solution, and dried. A solvent was distilled off to obtain a pale yellow powder (crude yield 12 g). This compound was used in the next reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; water;Flow reactor; | General procedure: For EX-1, the following procedure was carried out using Microreactor B, described above, with the mixing device at ambient temperature. Syringe I contained 15 g BP, 22 g TEA, and 22 g water. Syringe II contained 3 g ACL and 20 g DCM. Each syringe was placed in a separate syringe pump and the pump speeds were controlled to deliver the blends at the flow rates indicated for EX-1 in Table 3 below. The two unused addition ports of the mixing device were sealed with plugs. The molar flow ratios of BP: ACL: TEA pumped to the mixing device were 1: 1.1 :2.9. Separation of aqueous phase and an organic phase was observed in the collection vessel. Analysis of the upper, aqueous phase by NMR indicated approximately 8 mol percent of acrylic acid-TEA salt and approximately 92 mol percent TEA -HQ salt. Analysis of the lower, organic phase by NMR indicated approximately 51 mol percent 4- acryloxybenzophenone (ABP), approximately 0.01 mol percent BP and approximately 42 mol percent of the above mentioned TEA salts. Analysis of the organic layer by GC indicated 95percent Composition of ABP and 2percent of unreacted alcohol. After analysis, the organic layer was washed with water to remove salts and residual TEA. For EX-2 through EX-17, the same procedure was followed but with syringe contents and flow rates as indicated in Table 3. Blend compositions, flow rates, molar flow ratios of BP:ACL:TEA, and percent Composition are provided in Table 3. | |
With triethylamine; sodium hydroxide; In water; ethyl acetate; | For EX-1, the following procedure was carried out using the microreactor described above, with the mixing device at ambient temperature. Container I contained 100 g BP, 50 g TEA, 20 G NaOH, and 147 g water. Container II contained 40 g ACl and 80 g EtOAc. Each container was connected to a pump and the pump speeds were controlled to deliver the mixtures in the containers at the following rates: Container I; 14 mL/min, or 0.022 mol/min of BP; Container II: 7 mL/min, or 0.028 mol/min of ACl. The two unused addition ports of the mixing device were sealed with plugs. The molar flow ratios of BP:NaOH:TEA:ACl pumped to the mixing device were approximately 1 : 1 : 1 : 1.24. Separation of aqueous phase and an organic phase was observed in the collection vessel. The organic phase was observed to have a hazy appearance. The aqueous layer was removed from the collection vessel. Results of analysis of the organic layer by GC and NMR are presented in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; butanone; | Synthesis of 4-acryloyloxy-benzophenone 1.3 g (16.25 mmoli) of NaOH 50percent water solution, were added to a solution of 3 g (15.21 mmol) of 4-hydroxybenzophenone in 20 cc of methyl ethyl ketone. After 30 minutes under stirring, a solution of 1.59 g (15.21 mmol) of methacryloyl chloride in 5 mL of methyl ethyl ketone were added dropwise. After the addition the reaction mixture was stirred for 1 hour, filtered and the solvent was evaporated. The oil residue was purified by flash chromatography on silica gel (eluent CH2Cl2) to obtain 2.74 g of a colourless liquid. 1HNMR (CDCl3): delta (ppm): 2.10 (s, 3H); 5.82 (s, 1H); 6.40 (s, 1H); 7.2-7.3 (m, 2H); 7.45-7.55 (m, 2H); 7.60-7.65 (m, 1H); 7.75-7.85 (m, 2H); 7.85-7.95 (m, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; water;Flow reactor; | General procedure: EX-22 was carried out using Microreactor B. For EX-22, syringe I contained 15 g BP, 33 g TEA, and 33 g water. Syringe II contained 4.2 g 3CPC and 20 g DCM. Each syringe was placed in a separate syringe pump and the pump speeds were controlled to deliver the blends at the flow rates indicated for EX-22 in Table 8 below. The two unused addition ports of the mixing device were sealed with plugs. Separation of aqueous phase and an organic phase was observed in the collection vessel. Analysis of the upper, aqueous phase by NMR indicated approximately 8 mol percent of acrylic acid-TEA salt and approximately 92 mol percent TEA-HC1 salt. Analysis of the lower, organic phase by NMR indicated approximately 51 mol percent ABP, approximately 0.01 mol percent BP and approximately 42 mol percent of the above mentioned TEA salts. Analysis by GC indicated the organic layer was 98percent ABP and 2percent unreacted alcohol. After analysis, the organic layer was washed with water to remove salts and residual TEA. For EX-23 through EX-26, the same procedure was followed as described for EX-22, except that flow rates were as indicated in Table 8. Blend compositions, flow rates, and percent Composition are provided in Table 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate; In acetone; at 55℃; for 20h; | Bromoethane (3.2 g, 30 mmol) and 4-hydroxybenzophenone (4.95 g, 25 mmol) were added to a three-necked flask,After adding 300mL of acetone,Additional potassium carbonate (4.1 g, 30 mmol)Then the temperature was raised to 55 C and stirring was continued for 20h.After the reaction was stopped cooling to room temperature,filter,The filtrate was collected,Rotary evaporation of the solvent gave the crude product,A volume ratio of 50: 1 petroleum ether and ethyl acetate mixture as eluent,SiO2 as the stationary phase,Purification by column chromatography to give 4-n-hexyloxybenzophenone 4.9g,Yield 86%. |
70% | With potassium carbonate; In acetone; for 12h;Reflux; Inert atmosphere; | 4-Hydroxybenzophenone (4.9 g, 25 mmol), anhydrous potassium carbonate (6.9 g, 50 mmol), bromoethane (2.23 mL, 30 mmol) was added to a 250 mL two-necked flask.An appropriate amount of acetone solvent was added and refluxed for 12 hours under a nitrogen atmosphere.The reaction was completely cooled to room temperature, and an appropriate amount of dilute hydrochloric acid solution (2 mol/L) was added until no bubbles were formed.The organic phase is extracted with chloroform and combined to obtain a crude product which is purified by chromatography to obtain a pure product.The yield was 70%, and the structure was characterized by 1H-NMR and 13C-NMR to confirm that the product was a compound of Comparative Example I. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With titanium tetrachloride; zinc; In tetrahydrofuran; at 0 - 70℃; for 36.5h;Inert atmosphere; | A 250 mL round bottom flask was charged with 4-hydroxybenzophenone (1.9 g, 10 mmol)<strong>[27982-06-5]4-ethoxybenzophenone</strong> (2.7 g, 12 mmol),Zn powder (3.9 g, 50 mmol).After evacuating nitrogen for three times,Add 80 mL of tetrahydrofuran.After cooling to 0 C,TiCl4 (5.7 g, 25 mmol) was slowly added,Then stirred for 0.5 h.Then stirred at 70 C for 36 h,After cooling to room temperature,Add 80mL dilute hydrochloric acid (1mol / L),Adjusted to neutral,DCM extraction three times,The organic layer was collected,Dried over anhydrous magnesium sulfate,The solvent is dried to give the crude product,A volume ratio of 50: 1 petroleum ether and ethyl acetate mixture as eluent,SiO2 as the stationary phase,Column chromatography isolated white solid 0.8g,Yield 41%. |
Tags: 1137-42-4 synthesis path| 1137-42-4 SDS| 1137-42-4 COA| 1137-42-4 purity| 1137-42-4 application| 1137-42-4 NMR| 1137-42-4 COA| 1137-42-4 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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