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MANUFACTURE OF
2-PHENYLACETOPHENONE
Submitted in partial fulfillment of the requirements
of the degree of
2-Phenylacetophenone
Synonyms
-
Acetophenone, 2-phenyl
1, 2-Diphenylethan-1-one
1, 2-Diphenylethanone
Benzoin, deoxyBenzyl phenyl ketone
Deoxybenzoin
Desoxybenzoin
Phenyl benzyl ketone
Phenylmethyl phenyl ketone
Phenylacetophenone
NSC 131456; NSC 249236; NSC 6097;
Molecular Structure:
Molecular Formula:
History
2-phenylacetophenone is a ketone also known as benzyl phenyl ketone.Deoxybenzoin is
intermediates in the syntheses of isoflavones and are found in several plants, such as
Glycyrrhiza sp., Trifolium subterraneum and Ononis spinosa, and marine sources Many
deoxybenzoin compounds have shown significant estrogen receptor modulatory, urease
inhibitory, antimicrobial and antiviral properties .As part of our work involving the synthesis
of a series of deoxybenzoin derivatives for urease inhibitory activity screening we report
herein the crystal structure of the title deoxybenzoin .
Since 1925, variations of at least three synthetic approaches have been developed. The early
synthesis of isoflavones were based on the formylation of a substituted deooxybenzoin
(Baker and Robinson, 1928).
Deoxybenzoins undergo a-keto formylation, intramolecular acetal formation, followed by a
facile dehydration to give the pyrone ring C and hence, the isoflavones. Deoxybenzoins have
been synthesized utilizing the following strategies (Chapman and Stephen 1923):
(1) reacting phenyl acetic acid (X=CO2H) with the appropriately substituted phenol in the
presence of ZnCl2,
(2) reacting the acid chloride (X=COCI) with the appropriately substituted phenol in the
presence of AICI3, and
(3) Hoeschs method (Hoesch, 1915) of condensing the nitrile (X=CN) with the phenol to
give an intermediate ketamine hydrochloride, which can be hydrolyzed to the deoxybenzoin
with the case and in high overall yield (92 percent) (Shriner and Hull, 1945).
Selective protection of all phenolic oxygens but the 2-hydroxy group is a prerequisite in order
to prevent ring formylation and subsequent polymerization following the latter strategy using
ethyl formate (as formyl equivalent) in the presence of sodium and benzyl.
Synthesis
1. It is also already known that benzyl phenyl ketone is producible by palladium-catalyzed
coupling of benzoyl chloride with
powder. (Aktiengesellschaft, 1991)
benzyl
chloride
in
the
presence
of
zinc
Applications
2-Phenyl acetophenone finds application mainly in the pharmaceutical and polymerization
industries. It is used as a solvent and an intermediate in the synthesis of pharmaceuticals and
pesticides. In the polymerization processes it is used as a photo-initiator in vinyl
polymerization processes.
1. Manufacture of 1,2-diphenyl ethane
2-Phenylacetophenone is used to produce 1,2-diphenyl ethane which is important drug in
pharmaceutical industry. The reaction occurs with reagent LiAlH 4/P2I4 and solvent benzene with other
condition of heating for 6 hours. The yield is about 62%.
2. Synthesis of Coumestans, Isoflavonoids
2-Phenylacetophenone is used as a key intermediate in total syntheses of Coumestans and
Isoflavonoids such as Coumestrol, Genistein and Daidzein which are phytoestrogens contained in
soybean and black soybean. These compounds are widely used in dietary supplements
Isoflavonoids play an important role in human nutrition as health promoting natural chemicals. They
belong to plant secondary metabolites that mediate diverse biological functions through numerous
pathways. They are structurally similar to estrogens, exerting both estrogenic and anti-estrogenic
properties in various tissues. (Miadokova, Dec, 2009, 2(4))
Coumestans are natural compounds known for large number of biological activities. Many of their
biological effects can be attributed to their action as phytoestrogens and polyphenols. In the last
decade, anticancer effects of these compounds have been described in vitro but there is only limited
number of studies based on models in vivo.
3. Intermediate in Manufacture of Tamoxifen
Tamoxifen citrate has for years been used in clinical treatment of breast cancer, ovarian cancer, in
recent years some hospitals have tried to induce ovulation. Ethylation of deoxybenzoin with either
ethyl bromide or diethyl sulphate, cataylzed by Et 3BuNBr (a phase transfer catalyst or PTC) gives
ethyldeoxybenzoin, an intermediate in the preparation of Tamoxifen, a nonsteroidal antiestrogen drug
used widely in the treatment of breast cancer. (Y. Sasson, 2012)
4. Polymer Industry
Synthetic polymers are used extensively as plastics, rubbers, foams, textiles, and construction
materials; however, the flammability of many polymers is recognized as a safety hazard and an
important challenge in polymer research. Although halogenated small molecule additives have been
proven effective in reducing the flammability of polymer materials, environmental and health
concerns are leading to restricted use of such additives.
Deoxybenzoin-Based Polyarylates and Polyphosphonate can be used as Halogen-Free Fire-Resistant
Polymers. It has properties like flame-resistant, halogen-free, and possess high thermal stability, low
heat release capacities and high char yields. Example is 4,4-bishydroxydeoxybenzoin
polyphosphonate (BHDB-PPN) (Wang, 2010)
Deoxybe
nzoin decomposes in presence of light. Hence, it deoxybenzoin and its derivatives are used as a
photo-initiator in radical polymerization process and also in vinyl polymerization.
5. Initialising Bacteria Culture
A natural bacterial strain, identified as Pseudomonas fluorescens DB-5, was isolated in enrichment
cultures containing 1,2-diphenylethanone as the only source of carbon and energy. On the basis of
characteristic features observed in the mass spectra of degradation intermediates, it is proposed that
metabolism of 1,2-diphenylethanone is initiated by two hydroxylations on the benzyl ring. Phenol,
presumably arising from the benzoyl ring, was transiently detected as a catabolic intermediate.
White to yellow
Crystalline powder or crystals and/or chunks
196.25
1.2
52C to 57C
319C 321C
110C
poor (soluble in hot water)
Stable under ordinary conditions
Oxidizing agents
Thermal decomposition can lead to release of irritating gases
and vapors, Carbon monoxide (CO), Carbon dioxide (CO2)
Engineering Measures
Ensure adequate ventilation, especially in confined areas. Ventilation systems.
Eye/face Protection
Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and
face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin and body protection
Wear appropriate protective gloves and clothing to prevent skin exposure.
Respiratory Protection
Wear a NIOSH/MSHA or European Standard EN 149 approved full-face piece airline respirator in the
positive pressure mode with emergency escape provisions.
White
Crystalline
Floral, Has a sweet honey-like odour when diluted; the
odour of the concentrated solution is suffocating and
unpleasant.
Formula weight
136.15
Specific gravity
1.0809
Melting point
76.5C
Boiling point
265.5C
Flash point
100C
Solubility
Slightly soluble in cold water, freely in hot water; soluble in
alcohol and ether
Vapor Pressure
0.0038 mmHg at 25C
Stability
Stable at room temperature in closed containers under
normal storage and handling conditions
Incompatible Materials
Strong oxidizing agents, strong reducing agents, strong
bases
Hazardous
decomposition Carbon monoxide, carbon dioxide
products
3. Thionyl Chloride
Properties
Appearance (Color)
Appearance (Form)
Odour
Formula weight
Specific gravity
Liquid
Vapor
1.6310
4.1
Melting point
-105C
Boiling point
76C
Viscosity
0.6 cP
Vapor Pressure
119 mmHg at 25C
Solubility
Reacts with water forming sulphur dioxide. Miscible
with benzene, chloroform, carbon tetrachloride
Stability
Reacts violently with water to form the toxic gases hydrogen
chloride and sulphur dioxide.
Incompatible Materials
Water, metals, acids, bases, alcohols, amines, ammonia,
dimethyl sulfoxide, dimethyl formamide, lithium, sodium,
alkalies.
Hazardous
Decomposition Hydrogen chloride, chlorine, oxides of sulphur.
Products
Ingestion
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give
anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If breathing
is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply
artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician
Treat symptomatically and supportively.
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements
or European Standard EN 149 must be followed whenever workplace conditions warrant respirator
use.
4. Benzene
Properties
Appearance (Color)
Appearance (Form)
Formula weight
Specific gravity
Liquid
Vapor
Melting point
Boiling point
Viscosity
Flash point
Vapor Pressure
Solubility in water
Flammable limits in air
Lower
Upper
Clear colorless
Liquid
78
0.8765
2.8
5.5C
80.1C
0.647 mPa.s at 20C
-11C
77 mmHg at 20C
Negligible
1.3% (v/v)
7.9%(v/v)
Auto-ignition Temperature
Stability
498C
Stable under normal temperatures and pressures. Avoid
ignition sources, excess heat and confined spaces.
Incompatible Materials
Strong oxidizing agents
Hazardous
Decomposition Carbon monoxide, carbon dioxide
Products
5. Dimethylformamide
Properties
Appearance (Color)
Appearance (Form)
Formula weight
Specific gravity
Liquid
Vapor
Melting point
Boiling point
Viscosity
Flash point
Vapor Pressure
Solubility in water
Flammable limits in air
Lower
Upper
Auto-ignition Temperature
Stability
Incompatible Materials
Hazardous Decomposition
Products
Clear colorless
Liquid
73.09
0.94
2.5
-61C
153C
0.8 mPa.s at 20C
57C
3.6753 mmHg at 20C
Miscible
2.2%(v/v)
15.2%(v/v)
445C
Stable at room temperature in closed containers under
normal storage and handling conditions. Avoid Ignition
sources, excess heat.
Strong oxidizing agents, ammonia, anhydrides, iron,
phenols, isocyanates, acids (mineral, non-oxidizing, e.g.
hydrochloric acid, hydrofluoric acid, muriatic acid,
phosphoric acid), acids (mineral, oxidizing, e.g. chromic
acid, hypochlorous acid, nitric acid, sulfuric acid), metals
(alkali and alkaline, e.g. cesium, potassium, sodium), metals
and metal compounds (toxic, e.g. beryllium, lead acetate,
nickel carbonyl, tetraethyl lead), reducing agents (strong,
e.g. aluminum carbide, chlorosilane, hydrogen phosphide,
lithium
hydride),
carbontetrachloride,
chlorinated
hydrocarbons, organic materials.
Carbon monoxide, oxides of nitrogen, irritating toxic fumes
and gases, carbon dioxide
6. Aluminium Chloride
Properties
Appearance (Color)
Appearance (Form)
Odour
Formula weight
Specific gravity
Melting point
Boiling point
Flash point
Vapor Pressure
Solubility
White
Solid, anhydrous
Strong acid odour
133.34
2.44
192.6C
Sublimes at 181C
Not combustible
1 mmHg at 100C
Reacts violently with water. Soluble in benzene, canbon
tetrachloride, chloroform
Stability
Stable. Avoid dust generation, exposure to moist air or water
Incompatible Materials
Organic materials, Aluminium chloride reacts violently with
water producing hydrochloric acid and heat.
Hazardous
Decomposition Hydrogen chloride, aluminium oxide.
Products
7. Hydrochloric Acid
Properties
Appearance (Color)
Appearance (Form)
Odour
Formula weight
Specific gravity
Liquid
Vapor
Colorless
Liquid
Pungent
36.46
1.18
1.27
Melting point
Boiling point
Viscosity
Flash point
Vapor Pressure
Solubility in water
Flammable limits in air
Stability
Incompatible Materials
Hazardous
Products
-35C
57C
1.8 mPa.s at 15C
Not flammable
93.7577 mmHg at 20C
Soluble in water.
Not applicable
Stable under normal conditions. Avoid excess heat.
Metals, Strong oxidizing agents, sodium hypochlorite,
Amines, Bases, Fluorine, Cyanides, alkaline
Decomposition Hydrogen chloride gas
8. Methanol
Properties
Appearance (Color)
Appearance (Form)
Formula weight
Specific gravity
Liquid
Vapor
Melting point
Boiling point
Viscosity
Flash point
Closed vessel
Open vessel
Vapor Pressure
Solubility in water
Flammable limits in air
Clear liquid
Colorless
32.04
0.7915 at 20C
1.11
-98C
64.7oC at 760mmHg
0.55 cP at 20C
12C
15.6C
128 mm Hg at 20C
Miscible
Lower
Upper
6% (v/v)
31% (v/v)
Auto-ignition Temperature
455 C
Stability
Stable under normal temperatures and pressures.
Incompatible Materials
Oxidizing agents, reducing agents, acids, alkali metals,
potassium, sodium, metals as powders (e.g. hafnium, raney
nickel), acid anhydrides, acid chlorides, powdered
aluminum, and powdered magnesium.
Hazardous
Decomposition Carbon monoxide, carbon dioxide, formaldehyde.
Products
Inhalation
Methanol is toxic and can very readily form extremely high vapor concentrations at room
temperature. Inhalation is the most common route of occupational exposure. At first, methanol causes
CNS depression with nausea, headache, vomiting, dizziness and incoordination. A time period with no
obvious symptoms follows (typically 8-24 hrs). This latent period is followed by metabolic acidosis
and severe visual effects which may include reduced reactivity and/or increased sensitivity to light,
blurred, doubl and/or snowy vision, and blindness. Depending on the severity of exposure and the
promptness of treatment, survivors may recover completely or may have permanent blindness, vision
disturbances
and/or
nervous
system
effects.
Chronic
Prolonged or repeated skin contact may cause dermatitis. Chronic exposure may cause effects similar
to those of acute exposure. Methanol is only very slowly eliminated from the body. Because of this
slow elimination, methanol should be regarded as a cumulative poison. Though a single exposure may
cause no effect, daily exposures may result in the accumulation of a harmful amount. Methanol has
produced fetotoxicity in rats and teratogenicity in mice exposed by inhalation to high concentrations
that did not produce significant maternal toxicity.
Spills/Leaks
Use water spray to disperse the gas/vapor. Remove all sources of ignition. Absorb spill using an
absorbent, non-combustible material such as earth, sand, or vermiculite. Do not use combustible
materials such as sawdust. Use a spark-proof tool. Provide ventilation. A vapor suppressing foam may
be used to reduce vapors. Water spray may reduce vapor but may not prevent ignition in closed
spaces.
Location
Chandigarh
Mumbai, Maharashtra
Thane, Maharashtra
Thane, Maharashtra
Tamil Nadu
Acros Organic
Manufacturers worldwide
Country
Company
Japan
Japan
Japan
China
China
China
China
Ukraine
Ukrorgsynthesis Ltd
Germany
Germany
France
Netherlands
Interim S.A.
Khatwijk Chemie B. V.
Belgium
Slokovia
United Kingdom
Canada
USA
USA
USA
USA
USA
Chempacific Corporation
USA
IMPORT DATA
Export Data
Process Description
Phenyl Acetic acid, benzene, dimethylformamide, thionyl chloride and aluminium chloride
are fed to the reactor in that order. Before feeding it is ensured that the reactor is clean and
dry. The reactor is heated to a temperature of 50-55C. At this temperature chlorination of
phenyl acetic acid takes place as follows with Dimethylformamide (DMF) as a catalyst.
Benzene acts as a solvent for this reaction.
References
http://www.guidechem.com/cas-451/451-40-1_area-India.html
http://www.guidechem.com/help/risk_safety.html#safety
http://www.chemicalbook.com/ChemicalProductProperty_EN.aspx?CBNumber=CB9425419
http://pubchem.ncbi.nlm.nih.gov/compound/Deoxybenzoin#section=Top
Fisher scientific Safety data sheet
Chemical weekly Dated: 18/08/2015
www.zauba.com/exportanalysis-deoxybenzoin-report.html
www.zauba.com/importanalysis-DEOXYBENZOIN/hs-code-29143990-report.html