1137-42-4

Basic information

• Product Name: 4-Hydroxybenzophenone
• Synonyms: (4-hydroxyphenyl)phenyl-methanon;4-hydroxy-benzophenon;4-Hydroxydiphenylketone;4-Hydroxyphenylphenylketone;Benzophenone, 4-hydroxy-;benzoylphenol;P-BENZOYLPHENOL;POB
• CAS NO: 1137-42-4
• Molecular Formula: C₁₃H₁₀O₂
• Molecular Weight: 198.22
• EINECS: 214-507-1
• Product Categories: FINE Chemical & INTERMEDIATES;Aromatic Benzophenones & Derivatives (substituted);Organic Photoinitiators;Benzophenone;Polymerization Initiators;Aromatics;Metabolites & Impurities;Aromatics, Metabolites & Impurities
• Mol File: 1137-42-4.mol
• Article Data: 104

Chemical Properties

• Melting Point: 132-135 °C(lit.)
• Boiling Point: 260-262°C 42mm
• Flash Point: 260-262°C/24mm
• Appearance: White to beige to brown/Powder
• Density: 1.1184 (rough estimate)
• Vapor Pressure: 6.5E-06mmHg at 25°C
• Refractive Index: 1.5954 (estimate)
• Storage Temp.: Refrigerator
• Solubility: Chloroform (Slightly), DMSO (Slightly), Methanol (Slightly)
• PKA: 8.14±0.13(Predicted)
• Water Solubility: Insoluble in water.
• BRN: 777776
• CAS DataBase Reference: 4-Hydroxybenzophenone(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Hydroxybenzophenone(1137-42-4)
• EPA Substance Registry System: 4-Hydroxybenzophenone(1137-42-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36/37-24/25-36
• WGK Germany: 2
• RTECS: PC4959775
• TSCA: Yes
• Hazardous Substances Data: 1137-42-4(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
4-Hydroxybenzophenone is used as a pharmaceutical intermediate for the synthesis of clomifene citrate, a medication primarily used to treat infertility in women by inducing ovulation.
Used in Organic Synthesis:
In the field of organic synthesis, 4-Hydroxybenzophenone serves as a versatile intermediate for the production of various organic compounds, including pharmaceuticals, agrochemicals, and other specialty chemicals. Its chemical properties, such as the presence of a hydroxyl group and a ketone group, make it a valuable building block for the synthesis of complex molecules.

Preparation

Preparation by condensation of benzotrichloride, ? with phenol in the presence of aluminium chloride in carbon disulfide at 0° (90%) or in the presence of zinc oxide in a water bath; ? with p-bromophenol in 30% sodium hydroxide solution at 80–85° (81%). There is substitution of the bromine atom by the benzoyl group.

Synthesis Reference(s)

Journal of the American Chemical Society, 77, p. 4674, 1955 DOI: 10.1021/ja01622a074The Journal of Organic Chemistry, 19, p. 978, 1954 DOI: 10.1021/jo01371a016Tetrahedron Letters, 31, p. 3943, 1990 DOI: 10.1016/S0040-4039(00)97513-0

Flammability and Explosibility

Notclassified

Purification Methods

Dissolve p-benzoylphenol in hot EtOH (charcoal), filter and cool. Alternatively crystallise it once from EtOH/H2O and twice from *benzene [Grunwald J Am Chem Soc 73 4934 1951, Dryland & Sheppard J Chem Soc Perkin Trans 1 125 1986]. [Beilstein 8 IV 1263.]

InChI:InChI=1/C13H10O2/c14-12-8-6-11(7-9-12)13(15)10-4-2-1-3-5-10/h1-9,14H

Upstream product

• 119-61-9 benzophenone 
• 64-17-5 ethanol 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 569-60-8 benzaurine 
• 106-41-2 4-bromo-phenol 
• 98-07-7 Benzotrichlorid 
• 76-93-7 Benzilic acid 
• 93-99-2 benzoic acid phenyl ester 
• 123-08-0 4-hydroxy-benzaldehyde 
• 7647-01-0 hydrogenchloride 
• 100-52-7 benzaldehyde 
• 108-95-2 phenol 
• 75-15-0 carbon disulfide 
• 7446-70-0 aluminium trichloride 

Downstream Products

• 16513-74-9 <4-(Benzoyloxy)phenyl>phenylketon 
• 38459-64-2 (4-(2-bromoethoxy)phenyl)(phenyl)methanone 
• 5410-01-5 4,4''-ethanediyldioxy-di-benzophenone 
• 51777-15-2 (4-(2-(dimethylamino)ethoxy)phenyl)(phenyl)methanone 
• 27925-37-7 3-Hydroxy-3-(4-hydroxy-phenyl)-2,2-dimethyl-3-phenyl-propionic acid 
• 3705-10-0 4--benzophenon 
• 56430-95-6 4-hydroxy-α-vinyl-benzhydrol 
• 55191-20-3 (3-chloro-4-hydroxyphenyl)(phenyl)methanone 
• 112005-16-0 Cyclohexanecarboxylic acid 4-benzoyl-phenyl ester 
• 42403-76-9 4-(crotyloxy)benzophenone 
• 112005-05-7 4-<(2-methyl-2-carboxypropionyl)oxy>benzophenone 
• 112005-08-0 4-(methallyloxy)benzophenone 
• 56467-43-7 4-hydroxybenzophenone ester of metacrylic acid 
• 322-20-3 4-(2-chloro-1,1,2-trifluoro-ethoxy)-benzophenone 

Relevant articles and documents

Application of Ionic Liquid Halide Nucleophilicity for the Cleavage of Ethers: A Green Protocol for the Regeneration of Phenols from Ethers

We have used the high nucleophilicity of bromide ion in the form of the ionic liquid, 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]), for the nucleophilic displacement of an alkyl group to regenerate a phenol from the corresponding aryl alkyl ether. Using 2-methoxynaphthalene (1) as a model compound, we found that the combination of ionic liquid [bmim][Br] and p-toluenesulfonic acid with warming effected demethylation in 14 h, affording the desired product 2-naphthol (2) in good yield (97%). Various other protic acids (MsOH, hydrochloric acid (35%), dilute sulfuric acid (50%)) could be used as a proton source in this demethylation reaction. Under the same conditions, cleavage of alkyl alkyl ether 2-(3-methoxypropyl)naphthalene yielded mixture of corresponding 2-(3-bromopropyl)naphthalene and 2-(3-hydroxypropyl)naphthalene. Dealkylation of various aryl alkyl ethers could also be achieved using significantly reduced (i.e., stoichiometric) amounts of concentrated hydrobromic acid (47%) in the ionic liquid. Both procedures afforded the desired products in moderate to good yield; however, cleavage of aryl alkyl cyclic ether, 2,3-dihydrobenzofuran, resulted in low yield of the desired product o-2-bromoethylphenol. The convenience of this method for ether cleavage and its effectiveness using only a moderate excess of hydrobromic acid make it attractive as a green chemical method.

Suspension Ring-Opening Metathesis Polymerization: The Preparation of Norbornene-Based Resins for Application in Organic Synthesis

A series of norbornene-based resin beads were obtained by aqueous suspension ring-opening metathesis polymerization (ROMP) and used as polymeric supports for organic synthesis. These resins were prepared from norbornene, norborn-2-ene-5-methanol, and cross-linkers such as bis(norborn-2-ene-5-methoxy)alkanes, di(norborn-2-ene-5-methyl)ether, and 1,3-di(norborn-2-ene-5-methoxy)benzene. The resulting unsaturated ROMP (U-ROMP) resins containing olefin repeat units were chemically modified using hydrogenation, hydrofluorination, chlorination, and bromination reactions to produce saturated ROMP resins with different chemical and physical properties. The hydrogenated ROMP (H-ROMP) resin was found to be highly resistant to acidic, basic, Lewis acid, and Birch reduction conditions and was assessed as a polymeric support in a series of solid-phase synthetic applications. The H-ROMP resin was found to have superior performance compared to polystyrene-divinylbenzene (PS-DVB) copolymers in aromatic nitration and acylation reactions. In a conventional five-step solid-phase synthesis of a hydantoin, similar results were obtained for both the H-ROMP and PS-DVB resins. The U-ROMP resin was also shown to be effective in the solid-phase syntheses of benzimidazoles and benzimidazolones.

Modulation of reactivity of singlet radical pair in continuous flow: Photo-Fries rearrangement

Photo-Fries rearrangement of phenyl benzoate is studied using continuous flow for modulating the reactivity of singlet radical pair by changing the viscosity of the solvent. The effect of flow and proximity of the reactants with the light source on the reactivity of radical pair, formed from singlet excited state was investigated in details. In non-viscous solvent, the results from flow synthesis were comparable to batch reactor. In viscous solvents, selectivity of ortho- and para-isomers (o-/p- isomer) of the product could be controlled by changing viscosity as well as the flow rate. Using flow synthesis, ortho- and para-isomer ratio was obtained as high as 8.45 which are twice as compared to batch experiment with in fraction of residence time.

Synthesis of benzophenones from geminal biaryl ethenes using m-chloroperbenzoic acid

The oxidation of geminal biaryl ethenes 3 and 1,3-enynes 5 using m-chloroperbenzoic acid in dichloromethane at room temperature presents a catalyst-free approach for the synthesis of functionalized benzophenones 4 and ynones 6, respectively.

Panel of New Thermostable CYP116B Self-Sufficient Cytochrome P450 Monooxygenases that Catalyze C?H Activation with a Diverse Substrate Scope

The ability of cytochrome P450 monooxygenases to catalyse a wide variety of synthetically challenging C?H activation reactions makes them highly desirable biocatalysts both for the synthesis of chiral intermediates and for late-stage functionalisations. However, P450s are plagued by issues associated with poor expression, solubility and stability. Catalytically self-sufficient P450s, in which the haem and reductase domains are fused in a single protein, obviate the need for additional redox partners and are attractive as biocatalysts. Here we present a panel of natural self-sufficient P450s from thermophilic organisms (CYP116B65 from A. thermoflava, CYP116B64 from A. xiamenense, CYP116B63 from J. thermophila, CYP116B29 from T. bispora and CYP116B46 from T. thermophilus). These P450s display enhanced expression and stability over their mesophilic homologues. Activity profiling of these enzymes revealed that each P450 displayed a different fingerprint in terms of substrate range and reactivity that cover reactions as diverse as hydroxylation, demethylation, epoxidation and sulfoxidation. The productivity of the bio-transformation of diclofenac to produce the 5-hydroxy metabolite increased 42-fold using the thermostable P450-AX (>0.5 g L?1 h?1) compared to the P450-RhF system reported previously. In conclusion, we have generated a toolkit of thermostable self-sufficient P450 biocatalysts with a broad substrate range and reactivity.

Benzoylation in room temperature ionic liquids

Aromatic substrates were efficiently benzoylated with benzotrichloride using ionic liquid as the reaction medium.

Integrative Photoreduction of CO2 with Subsequent Carbonylation: Photocatalysis for Reductive Functionalization of CO2

Efficient conversion of CO2 into fuels and chemicals with solar energy would be promising, but also faces great challenge. In this context, we describe the photoreductive functionalization of CO2 to construct new C?C, C?N, and C?O bonds through the respective Pd-catalyzed Suzuki carbonylation, aminocarbonylation, and alkoxycarbonylation of aryl iodides with CO in situ generated through the photoreduction of CO2. This protocol opens up an alternative avenue for CO2 utilization by harnessing solar energy.

Synthesis of 5-(4′-aroyl)-aryloxy methyl-4H-(1,2,4)-triazolin-3-thiol and their biological activity

5-(4′-aroyl)-aryloxy methyl-4H-1,2, 4)-triazolin-3-thiols were synthesized by using substituted phenyl benzoates as the starting material. Phenyl benzoates on Fries rearrangement gave p-hydroxy benzophenones which on treatment with ethyl bromoacetate in presence of anhydrous potassium carbonate and dry acetone gave corresponding benzoyl phenyloxy esters in excellent yield. Esters were refluxed with thiosemicarbazide in presence of acetic anhydride gave cyclized title compounds. Supports for the structures of the synthesized compounds have been provided by their elemental analysis and spectral data. The newly synthesized compounds were screened for antibacterial and antifungal activities.

Photochemical rearrangement of phenyl benzoate in the presence of cyclodextrins and amylose

The photorearrangement of phenyl benzoate in aqueous medium is changed in the presence of cyclodextrins or amylose; the ortho/para migration ratio is altered in favor of the para position.

One-step reaction of friedel-crafts acylation and demethylation of aryl-methyl ethers catalyzed by ytterbium(III) triflate

Catalytic amount of ytterbium(III) inflate [Yb(OTf)3] has been used to catalyze Friedel-Crafts acylation and demethylation of aryl-methyl ethers in one-step reaction to produce hydroxyacylphenones with moderate yields under mild conditions.