Phenol

Last updated
Phenol
Phenol2.svg
Phenol-2.svg
Phenol-3D-balls.png
Phenol-3D-vdW.png
Phenol 2 grams.jpg
Names
Preferred IUPAC name
Phenol [1]
Systematic IUPAC name
Benzenol
Other names
  • Carbolic acid
  • Phenolic acid
  • Phenylic acid
  • Hydroxybenzene
  • Phenic acid
  • Phenyl alcohol
  • Phenyl hydroxide
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.303 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
RTECS number
  • SJ3325000
UNII
UN number 2821 (solution)
2312 (molten)
1671 (solid)
  • InChI=1S/C6H6O/c7-6-4-2-1-3-5-6/h1-5,7H Yes check.svgY
    Key: ISWSIDIOOBJBQZ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H6O/c7-6-4-2-1-3-5-6/h1-5,7H
  • Oc1ccccc1
Properties
C6H6O
Molar mass 94.113 g/mol
AppearanceTransparent crystalline solid
Odor Sweet and tarry
Density 1.07 g/cm3
Melting point 40.5 °C (104.9 °F; 313.6 K)
Boiling point 181.7 °C (359.1 °F; 454.8 K)
8.3 g/100 mL (20 °C)
log P 1.48 [2]
Vapor pressure 0.4 mmHg (20 °C) [3]
Acidity (pKa)
  • 9.95 (in water),
  • 18.0 (in DMSO),
  • 29.1 (in acetonitrile) [4]
Conjugate base Phenoxide
UV-vis (λmax)270.75 nm [5]
1.224  D
Pharmacology
C05BB05 ( WHO ) D08AE03 ( WHO ), N01BX03 ( WHO ), R02AA19 ( WHO )
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg [6]
Danger
H301, H311, H314, H331, H341, H373 [6]
P261, P280, P301+P310, P305+P351+P338, P310 [6]
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
2
0
Flash point 79 °C (174 °F; 352 K)
Explosive limits 1.8–8.6% [3]
Lethal dose or concentration (LD, LC):
  • 317 mg/kg (rat, oral)
  • 270 mg/kg (mouse, oral) [7]
  • 420 mg/kg (rabbit, oral)
  • 500 mg/kg (dog, oral)
  • 80 mg/kg (cat, oral) [7]
  • 19 ppm (mammal)
  • 81 ppm (rat)
  • 69 ppm (mouse) [7]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 5 ppm (19 mg/m3) [skin] [3]
REL (Recommended)
  • TWA 5 ppm (19 mg/m3)
  • C 15.6 ppm (60 mg/m3) [15-minute] [skin] [3]
IDLH (Immediate danger)
250 ppm [3]
Safety data sheet (SDS)
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula C6H5OH. [5] It is a white crystalline solid that is volatile. The molecule consists of a phenyl group (−C6H5) bonded to a hydroxy group (−OH). Mildly acidic, it requires careful handling because it can cause chemical burns. [5]

Contents

Phenol was first extracted from coal tar, but today is produced on a large scale (about 7 million tonnes a year) from petroleum-derived feedstocks. It is an important industrial commodity as a precursor to many materials and useful compounds. [8] It is primarily used to synthesize plastics and related materials. Phenol and its chemical derivatives are essential for production of polycarbonates, epoxies, explosives, Bakelite, nylon, detergents, herbicides such as phenoxy herbicides, and numerous pharmaceutical drugs. [9]

Properties

Phenol is an organic compound appreciably soluble in water, with about 84.2 g dissolving in 1000 ml (0.895 M). Homogeneous mixtures of phenol and water at phenol to water mass ratios of ~2.6 and higher are possible. The sodium salt of phenol, sodium phenoxide, is far more water-soluble. It is a combustible solid (NFPA rating = 2). When heated, phenol produces flammable vapors that are explosive at concentrations of 3 to 10% in air. Carbon dioxide or dry chemical extinguishers should be used to fight phenol fires. [5]

Acidity

Phenol is a weak acid (pH 6.6). In aqueous solution in the pH range ca. 8 - 12 it is in equilibrium with the phenolate anion C6H5O− (also called phenoxide or carbolate): [10]

C6H5OH ⇌ C6H5O− + H+
Resonance structures of the phenoxide anion Phenol-phenolate equilibrium.svg
Resonance structures of the phenoxide anion

Phenol is more acidic than aliphatic alcohols. Its enhanced acidity is attributed to resonance stabilization of phenolate anion. In this way, the negative charge on oxygen is delocalized on to the ortho and para carbon atoms through the pi system. [11] An alternative explanation involves the sigma framework, postulating that the dominant effect is the induction from the more electronegative sp2 hybridised carbons; the comparatively more powerful inductive withdrawal of electron density that is provided by the sp2 system compared to an sp3 system allows for great stabilization of the oxyanion. In support of the second explanation, the pKa of the enol of acetone in water is 10.9, making it only slightly less acidic than phenol (pKa 10.0). [5] Thus, the greater number of resonance structures available to phenoxide compared to acetone enolate seems to contribute little to its stabilization. However, the situation changes when solvation effects are excluded.

Hydrogen bonding

In carbon tetrachloride and in alkane solvents, phenol hydrogen bonds with a wide range of Lewis bases such as pyridine, diethyl ether, and diethyl sulfide. The enthalpies of adduct formation and the −OH IR frequency shifts accompanying adduct formation have been compiled. [12] Phenol is classified as a hard acid. [13] [14]

Tautomerism

Phenol-cyclohexadienone tautomerism Phenol tautomers.svg
Phenol-cyclohexadienone tautomerism

Phenol exhibits keto-enol tautomerism with its unstable keto tautomer cyclohexadienone, but the effect is nearly negligible. The equilibrium constant for enolisation is approximately 10−13, which means only one in every ten trillion molecules is in the keto form at any moment. [15] The small amount of stabilisation gained by exchanging a C=C bond for a C=O bond is more than offset by the large destabilisation resulting from the loss of aromaticity. Phenol therefore exists essentially entirely in the enol form. [16] 4, 4' Substituted cyclohexadienone can undergo a dienone–phenol rearrangement in acid conditions and form stable 3,4‐disubstituted phenol. [17]

For substituted phenols, several factors can favor the keto tautomer: (a) additional hydroxy groups (see resorcinol) (b) annulation as in the formation of naphthols, and (c) deprotonation to give the phenolate. [18]

Phenoxides are enolates stabilised by aromaticity. Under normal circumstances, phenoxide is more reactive at the oxygen position, but the oxygen position is a "hard" nucleophile whereas the alpha-carbon positions tend to be "soft". [19]

Reactions

The Hock process leading to phenol via autoxidation of cumene. Hockpart2.svg
The Hock process leading to phenol via autoxidation of cumene.
Neutral phenol substructure "shape". An image of a computed electrostatic surface of neutral phenol molecule, showing neutral regions in green, electronegative areas in orange-red, and the electropositive phenolic proton in blue. Phenol-elpot-3D-vdW.png
Neutral phenol substructure "shape". An image of a computed electrostatic surface of neutral phenol molecule, showing neutral regions in green, electronegative areas in orange-red, and the electropositive phenolic proton in blue.
Phenol water phase diagram: Certain combinations of phenol and water can make two solutions in one bottle. Phenol in water.PNG
Phenol water phase diagram: Certain combinations of phenol and water can make two solutions in one bottle.

Phenol is highly reactive toward electrophilic aromatic substitution. The enhanced nucleophilicity is attributed to donation pi electron density from O into the ring. Many groups can be attached to the ring, via halogenation, acylation, sulfonation, and related processes.

Phenol is so strongly activated that bromination and chlorination lead readily to polysubstitution. [20] The reaction affords 2- and 4-substituted derivatives. The regiochemistry of halogenation changes in strongly acidic solutions where PhOH2]+ predominates. Phenol reacts with dilute nitric acid at room temperature to give a mixture of 2-nitrophenol and 4-nitrophenol while with concentrated nitric acid, additional nitro groups are introduced, e.g. to give 2,4,6-trinitrophenol. Friedel Crafts alkylations of phenol and its derivatives often proceed without catalysts. Alkylating agents include alkyl halides, alkenes, and ketones. Thus, adamantyl-1-bromide, dicyclopentadiene), and cyclohexanones give respectively 4-adamantylphenol, a bis(2-hydroxyphenyl) derivative, and a 4-cyclohexylphenols. Alcohols and hydroperoxides alkylate phenols in the presence of solid acid catalysts (e.g. certain zeolite). Cresols and cumyl phenols can be produced in that way. [21]

Aqueous solutions of phenol are weakly acidic and turn blue litmus slightly to red. Phenol is neutralized by sodium hydroxide forming sodium phenate or phenolate, but being weaker than carbonic acid, it cannot be neutralized by sodium bicarbonate or sodium carbonate to liberate carbon dioxide.

C6H5OH + NaOH → C6H5ONa + H2O

When a mixture of phenol and benzoyl chloride are shaken in presence of dilute sodium hydroxide solution, phenyl benzoate is formed. This is an example of the Schotten–Baumann reaction:

C6H5COCl + HOC6H5 → C6H5CO2C6H5 + HCl

Phenol is reduced to benzene when it is distilled with zinc dust or when its vapour is passed over granules of zinc at 400 °C: [22]

C6H5OH + Zn → C6H6 + ZnO

When phenol is treated with diazomethane in the presence of boron trifluoride (BF3), anisole is obtained as the main product and nitrogen gas as a byproduct.

C6H5OH + CH2N2 → C6H5OCH3 + N2

Phenol and its derivatives react with iron(III) chloride to give intensely colored solutions containing phenoxide complexes.

Production

Because of phenol's commercial importance, many methods have been developed for its production, but the cumene process is the dominant technology.

Cumene process

Accounting for 95% of production (2003) is the cumene process, also called Hock process. It involves the partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement: [8] Compared to most other processes, the cumene process uses mild conditions and inexpensive raw materials. For the process to be economical, both phenol and the acetone by-product must be in demand. [23] [24] In 2010, worldwide demand for acetone was approximately 6.7 million tonnes, 83 percent of which was satisfied with acetone produced by the cumene process.

A route analogous to the cumene process begins with cyclohexylbenzene. It is oxidized to a hydroperoxide, akin to the production of cumene hydroperoxide. Via the Hock rearrangement, cyclohexylbenzene hydroperoxide cleaves to give phenol and cyclohexanone. Cyclohexanone is an important precursor to some nylons. [25]

Oxidation of benzene, toluene, cyclohexylbenzene

The direct oxidation of benzene (C6H6) to phenol is possible, but it has not been commercialized:

C6H6 + O → C6H5OH

Nitrous oxide is a potentially "green" oxidant that is a more potent oxidant than O2. Routes for the generation of nitrous oxide however remain uncompetitive. [26] [23] [25]

An electrosynthesis employing alternating current gives phenol from benzene. [27]

The oxidation of toluene, as developed by Dow Chemical, involves copper-catalyzed reaction of molten sodium benzoate with air:

C6H5CH3 + 2 O2 → C6H5OH + CO2 + H2O

The reaction is proposed to proceed via formation of benzyoylsalicylate. [8]

Autoxidation of cyclohexylbenzene give the hydroperoxide. Decomposition of this hydroperoxide affords cyclohexanone and phenol. [8]

Older methods

Early methods relied on extraction of phenol from coal derivatives or the hydrolysis of benzene derivatives.

Hydrolysis of benzenesulfonic acid

The original commercial route was developed by Bayer and Monsanto in the early 1900s, based on discoveries by Wurtz and Kekule. The method involves the reaction of strong base with benzenesulfonic acid, proceeding by the reaction of hydroxide with sodium benzenesulfonate to give sodium phenoxide. Acidification of the latter gives phenol. The net conversion is: [28]

C6H5SO3H + 2 NaOH → C6H5OH + Na2SO3 + H2O

Hydrolysis of chlorobenzene

Chlorobenzene can be hydrolyzed to phenol using base (Dow process) or steam (Raschig–Hooker process): [24] [25] [29]

C6H5Cl + NaOH → C6H5OH + NaCl
C6H5Cl + H2O → C6H5OH + HCl

These methods suffer from the cost of the chlorobenzene and the need to dispose of the chloride byproduct.

Coal pyrolysis

Phenol is also a recoverable byproduct of coal pyrolysis. [29] In the Lummus process, the oxidation of toluene to benzoic acid is conducted separately.

Miscellaneous methods

Amine to phenol Amine to Phenol .jpg
Amine to phenol

Phenyldiazonium salts hydrolyze to phenol. The method is of no commercial interest since the precursor is expensive. [30]

C6H5NH2 + HCl + NaNO2 → C6H5OH + N2 + H2O + NaCl

Salicylic acid decarboxylates to phenol. [31]

Uses

The major uses of phenol, consuming two thirds of its production, involve its conversion to precursors for plastics. Condensation with acetone gives bisphenol-A, a key precursor to polycarbonates and epoxide resins. Condensation of phenol, alkylphenols[ citation needed ], or diphenols [ citation needed ] with formaldehyde gives phenolic resins, a famous example of which is Bakelite. Partial hydrogenation of phenol gives cyclohexanone, [32] a precursor to nylon. Nonionic detergents are produced by alkylation of phenol to give the alkylphenols, e.g., nonylphenol, which are then subjected to ethoxylation. [8]

Phenol is also a versatile precursor to a large collection of drugs, most notably aspirin but also many herbicides and pharmaceutical drugs. Phenol is a component in liquid–liquid phenol–chloroform extraction technique used in molecular biology for obtaining nucleic acids from tissues or cell culture samples. Depending on the pH of the solution either DNA or RNA can be extracted.

Phenol is so inexpensive that it also attracts many small-scale uses. It is a component of industrial paint strippers used in the aviation industry for the removal of epoxy, polyurethane and other chemically resistant coatings. [33] Due to safety concerns, phenol is banned from use in cosmetic products in the European Union [34] [35] and Canada. [36] [37]

Medical

Phenol was widely used as an antiseptic, and it is used in the production of carbolic soap. Concentrated phenol liquids are used for permanent treatment of ingrown toe and finger nails, a procedure known as a chemical matrixectomy. The procedure was first described by Otto Boll in 1945. Since that time phenol has become the chemical of choice for chemical matrixectomies performed by podiatrists.

Concentrated liquid phenol can be used topically as a local anesthetic for otology procedures, such as myringotomy and tympanotomy tube placement, as an alternative to general anesthesia or other local anesthetics. It also has hemostatic and antiseptic qualities that make it ideal for this use. Phenol spray, usually at 1.4% phenol as an active ingredient, is used medically to treat sore throat. [38] It is the active ingredient in some oral analgesics such as Chloraseptic spray, TCP and Carmex. [39]

History

Bottle of Calvert's phenol antiseptic, Thackray Museum of Medicine Bottle of Phenol.jpg
Bottle of Calvert's phenol antiseptic, Thackray Museum of Medicine

Phenol was discovered in 1834 by Friedlieb Ferdinand Runge, who extracted it (in impure form) from coal tar. [41] Runge called phenol "Karbolsäure" (coal-oil-acid, carbolic acid). Coal tar remained the primary source until the development of the petrochemical industry. French chemist Auguste Laurent extracted phenol in its pure form, as a derivative of benzene, in 1841. [42] In 1836, Auguste Laurent coined the name "phène" for benzene; [43] this is the root of the word "phenol" and "phenyl". In 1843, French chemist Charles Gerhardt coined the name "phénol". [44]

The antiseptic properties of phenol were used by Sir Joseph Lister in his pioneering technique of antiseptic surgery. Lister decided that the wounds had to be thoroughly cleaned. He then covered the wounds with a piece of rag or lint [45] covered in phenol. The skin irritation caused by continual exposure to phenol eventually led to the introduction of aseptic (germ-free) techniques in surgery. Lister's work was inspired by the works and experiments of his contemporary Louis Pasteur in sterilizing various biological media. He theorized that if germs could be killed or prevented, no infection would occur. Lister reasoned that a chemical could be used to destroy the micro-organisms that cause infection. [46]

Meanwhile, in Carlisle, England, officials were experimenting with sewage treatment using carbolic acid to reduce the smell of sewage cesspools. Having heard of these developments, and having previously experimented with other chemicals for antiseptic purposes without much success, Lister decided to try carbolic acid as a wound antiseptic. He had his first chance on August 12, 1865, when he received a patient: an eleven-year-old boy with a tibia bone fracture which pierced the skin of his lower leg. Ordinarily, amputation would be the only solution. However, Lister decided to try carbolic acid. After setting the bone and supporting the leg with splints, he soaked clean cotton towels in undiluted carbolic acid and applied them to the wound, covered with a layer of tin foil, leaving them for four days. When he checked the wound, Lister was pleasantly surprised to find no signs of infection, just redness near the edges of the wound from mild burning by the carbolic acid. Reapplying fresh bandages with diluted carbolic acid, the boy was able to walk home after about six weeks of treatment. [47]

By 16 March 1867, when the first results of Lister's work were published in the Lancet, he had treated a total of eleven patients using his new antiseptic method. Of those, only one had died, and that was through a complication that was nothing to do with Lister's wound-dressing technique. Now, for the first time, patients with compound fractures were likely to leave the hospital with all their limbs intact

— Richard Hollingham, Blood and Guts: A History of Surgery, p. 62 [47]

Before antiseptic operations were introduced at the hospital, there were sixteen deaths in thirty-five surgical cases. Almost one in every two patients died. After antiseptic surgery was introduced in the summer of 1865, there were only six deaths in forty cases. The mortality rate had dropped from almost 50 per cent to around 15 per cent. It was a remarkable achievement

— Richard Hollingham, Blood and Guts: A History of Surgery, p. 63 [48]

Phenol was the main ingredient of the "carbolic smoke ball," an ineffective device marketed in London in the 19th century as protection against influenza and other ailments, and the subject of the famous law case Carlill v Carbolic Smoke Ball Company . In the tort law case of Roe v Minister of Health , phenol was used to sterilize anaesthetic packed in ampoules, in which it contaminated the anaesthetic through invisible micro-cracks and caused paraplegia to the plaintiffs.

Second World War

The toxic effect of phenol on the central nervous system causes sudden collapse and loss of consciousness in both humans and animals; a state of cramping precedes these symptoms because of the motor activity controlled by the central nervous system. [49] Injections of phenol were used as a means of individual execution by Nazi Germany during the Second World War. [50] It was originally used by the Nazis in 1939 as part of the mass-murder of disabled people under Aktion T4 . [51] The Germans learned that extermination of smaller groups was more economical by injection of each victim with phenol. Phenol injections were given to thousands of people. Maximilian Kolbe was also murdered with a phenol injection after surviving two weeks of dehydration and starvation in Auschwitz when he volunteered to die in place of a stranger. Approximately one gram is sufficient to cause death. [52]

Occurrences

Phenol is a normal metabolic product, excreted in quantities up to 40 mg/L in human urine. [49] The temporal gland secretion of male elephants showed the presence of phenol and 4-methylphenol during musth. [53] [54] It is also one of the chemical compounds found in castoreum. This compound is ingested from the plants the beaver eats. [55]

Phenol is a measurable component in the aroma and taste of the distinctive Islay scotch whisky, [56] generally ~30 ppm, but it can be over 160ppm in the malted barley used to produce whisky. [57] This amount is different from and presumably higher than the amount in the distillate. [56]

Biodegradation

Cryptanaerobacter phenolicus is a bacterium species that produces benzoate from phenol via 4-hydroxybenzoate. [58] Rhodococcus phenolicus is a bacterium species able to degrade phenol as sole carbon source. [59]

Toxicity

Phenol and its vapors are corrosive to the eyes, the skin, and the respiratory tract. [60] Its corrosive effect on skin and mucous membranes is due to a protein-degenerating effect. [49] Repeated or prolonged skin contact with phenol may cause dermatitis, or even second and third-degree burns. [61] Inhalation of phenol vapor may cause lung edema. [60] The substance may cause harmful effects on the central nervous system and heart, resulting in dysrhythmia, seizures, and coma. [62] The kidneys may be affected as well. Long-term or repeated exposure of the substance may have harmful effects on the liver and kidneys. [63] There is no evidence that phenol causes cancer in humans. [64] Besides its hydrophobic effects, another mechanism for the toxicity of phenol may be the formation of phenoxyl radicals. [65]

Since phenol is absorbed through the skin relatively quickly, systemic poisoning can occur in addition to the local caustic burns. [49] Resorptive poisoning by a large quantity of phenol can occur even with only a small area of skin, rapidly leading to paralysis of the central nervous system and a severe drop in body temperature. The LD50 for oral toxicity is less than 500 mg/kg for dogs, rabbits, or mice; the minimum lethal human dose was cited as 140 mg/kg. [49] The Agency for Toxic Substances and Disease Registry (ATSDR), U.S. Department of Health and Human Services states the fatal dose for ingestion of phenol is from 1 to 32 g. [66]

Chemical burns from skin exposures can be decontaminated by washing with polyethylene glycol, [67] isopropyl alcohol, [68] or perhaps even copious amounts of water. [69] Removal of contaminated clothing is required, as well as immediate hospital treatment for large splashes. This is particularly important if the phenol is mixed with chloroform (a commonly used mixture in molecular biology for DNA and RNA purification).[ citation needed ] Phenol is also a reproductive toxin causing increased risk of miscarriage and low birth weight indicating retarded development in utero. [5]

Phenols

The word phenol is also used to refer to any compound that contains a six-membered aromatic ring, bonded directly to a hydroxyl group (-OH). Thus, phenols are a class of organic compounds of which the phenol discussed in this article is the simplest member.

See also

Related Research Articles

<span class="mw-page-title-main">Phenols</span> Chemical compounds in which hydroxyl group is attached directly to an aromatic ring

In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of one or more hydroxyl groups bonded directly to an aromatic hydrocarbon group. The simplest is phenol, C
6H
5OH. Phenolic compounds are classified as simple phenols or polyphenols based on the number of phenol units in the molecule.

<span class="mw-page-title-main">Phenyl group</span> Cyclic chemical group (–C₆H₅)

In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6H5, and is often represented by the symbol Ph or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen, which may be replaced by some other element or compound to serve as a functional group. A phenyl group has six carbon atoms bonded together in a hexagonal planar ring, five of which are bonded to individual hydrogen atoms, with the remaining carbon bonded to a substituent. Phenyl groups are commonplace in organic chemistry. Although often depicted with alternating double and single bonds, the phenyl group is chemically aromatic and has equal bond lengths between carbon atoms in the ring.

<span class="mw-page-title-main">Acetophenone</span> Chemical compound

Acetophenone is the organic compound with the formula C6H5C(O)CH3. It is the simplest aromatic ketone. This colorless, viscous liquid is a precursor to useful resins and fragrances.

<span class="mw-page-title-main">Cumene process</span> Industrial process

The cumene process is an industrial process for synthesizing phenol and acetone from benzene and propylene. The term stems from cumene, the intermediate material during the process. It was invented by R. Ūdris and P. Sergeyev in 1942 (USSR), and independently by Heinrich Hock in 1944.

<span class="mw-page-title-main">Oxime</span> Organic compounds of the form >C=N–OH

In organic chemistry, an oxime is an organic compound belonging to the imines, with the general formula RR’C=N−OH, where R is an organic side-chain and R' may be hydrogen, forming an aldoxime, or another organic group, forming a ketoxime. O-substituted oximes form a closely related family of compounds. Amidoximes are oximes of amides with general structure R1C(=NOH)NR2R3.

The Friedel–Crafts reactions are a set of reactions developed by Charles Friedel and James Crafts in 1877 to attach substituents to an aromatic ring. Friedel–Crafts reactions are of two main types: alkylation reactions and acylation reactions. Both proceed by electrophilic aromatic substitution.

<span class="mw-page-title-main">Cyclohexanol</span> Chemical compound

Cyclohexanol is the organic compound with the formula HOCH(CH2)5. The molecule is related to cyclohexane by replacement of one hydrogen atom by a hydroxyl group. This compound exists as a deliquescent colorless solid with a camphor-like odor, which, when very pure, melts near room temperature. Millions of tonnes are produced annually, mainly as a precursor to nylon.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<span class="mw-page-title-main">Hydroquinone</span> Chemical compound

Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a para position. It is a white granular solid. Substituted derivatives of this parent compound are also referred to as hydroquinones. The name "hydroquinone" was coined by Friedrich Wöhler in 1843.

<span class="mw-page-title-main">Cyclohexanone</span> Chemical compound

Cyclohexanone is the organic compound with the formula (CH2)5CO. The molecule consists of six-carbon cyclic molecule with a ketone functional group. This colorless oily liquid has a sweet odor reminiscent of benzaldehyde. Over time, samples of cyclohexanone assume a pale yellow color.

<span class="mw-page-title-main">Organic peroxides</span> Organic compounds of the form R–O–O–R’

In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group. If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily breaks, producing free radicals of the form RO•. Thus, organic peroxides are useful as initiators for some types of polymerization, such as the acrylic, unsaturated polyester, and vinyl ester resins used in glass-reinforced plastics. MEKP and benzoyl peroxide are commonly used for this purpose. However, the same property also means that organic peroxides can explosively combust. Organic peroxides, like their inorganic counterparts, are often powerful bleaching agents.

<span class="mw-page-title-main">Cumene</span> Chemical compound

Cumene (isopropylbenzene) is an organic compound that contains a benzene ring with an isopropyl substituent. It is a constituent of crude oil and refined fuels. It is a flammable colorless liquid that has a boiling point of 152 °C. Nearly all the cumene that is produced as a pure compound on an industrial scale is converted to cumene hydroperoxide, which is an intermediate in the synthesis of other industrially important chemicals, primarily phenol and acetone.

<span class="mw-page-title-main">Hydroperoxide</span> Class of chemical compounds

Hydroperoxides or peroxols are compounds of the form ROOH, where R stands for any group, typically organic, which contain the hydroperoxy functional group. Hydroperoxide also refers to the hydroperoxide anion and its salts, and the neutral hydroperoxyl radical (•OOH) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.

<span class="mw-page-title-main">Dakin oxidation</span> Organic redox reaction that converts hydroxyphenyl aldehydes or ketones into benzenediols

The Dakin oxidation (or Dakin reaction) is an organic redox reaction in which an ortho- or para-hydroxylated phenyl aldehyde (2-hydroxybenzaldehyde or 4-hydroxybenzaldehyde) or ketone reacts with hydrogen peroxide (H2O2) in base to form a benzenediol and a carboxylate. Overall, the carbonyl group is oxidised, whereas the H2O2 is reduced.

Huntsman Chemical Company of Australia Pty Ltd (HCCA) operated a complex chemical manufacturing plant in Somerville Rd Brooklyn in Melbourne. The site is 35 hectares in size and is located in the City of Brimbank. HCCA was partially owned by the Huntsman Corporation.

<span class="mw-page-title-main">Sodium phenoxide</span> Chemical Compound

Sodium phenoxide (sodium phenolate) is an organic compound with the formula NaOC6H5. It is a white crystalline solid. Its anion, phenoxide, also known as phenolate, is the conjugate base of phenol. It is used as a precursor to many other organic compounds, such as aryl ethers.

<span class="mw-page-title-main">Cumene hydroperoxide</span> Aromatic organic chemical compound

Cumene hydroperoxide is the organic compound with the formula C6H5C(CH3)2OOH; this oily liquid is classified as an organic hydroperoxide. Products of decomposition of cumene hydroperoxide are methylstyrene, acetophenone, and 2-phenylpropan-2-ol.

<span class="mw-page-title-main">Benzenesulfonic acid</span> Chemical compound

Benzenesulfonic acid (conjugate base benzenesulfonate) is an organosulfur compound with the formula C6H6O3S. It is the simplest aromatic sulfonic acid. It forms white deliquescent sheet crystals or a white waxy solid that is soluble in water and ethanol, slightly soluble in benzene and insoluble in nonpolar solvents like diethyl ether. It is often stored in the form of alkali metal salts. Its aqueous solution is strongly acidic.

The Raschig–Hooker process is a chemical process for the production of chlorobenzene and phenol.

<span class="mw-page-title-main">Cyclohexylbenzene</span> Chemical compound

Cyclohexylbenzene is the organic compound with the structural formula C6H5−C6H11. It is a derivative of benzene with a cyclohexyl substituent (C6H11). It is a colorless liquid.

References

  1. ↑ "Front Matter". Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 690. doi:10.1039/9781849733069-FP001. ISBN   978-0-85404-182-4. Only one name is retained, phenol, for C6H5-OH, both as a preferred name and for general nomenclature.
  2. ↑ "Phenol_msds".
  3. 1 2 3 4 5 NIOSH Pocket Guide to Chemical Hazards. "#0493". National Institute for Occupational Safety and Health (NIOSH).
  4. ↑ Kütt, Agnes; Movchun, Valeria; Rodima, Toomas; et al. (2008). "Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and Electron-withdrawing Group: Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, -phenol, and -aniline". The Journal of Organic Chemistry. 73 (7): 2607–20. doi:10.1021/jo702513w. PMID   18324831.
  5. 1 2 3 4 5 6 "Phenol". PubChem, US National Library of Medicine. 10 June 2023. Retrieved 12 June 2023.
  6. 1 2 3 Sigma-Aldrich Co., Phenol. Retrieved on 2022-02-15.
  7. 1 2 3 "Phenol". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  8. 1 2 3 4 5 Weber, Manfred; Weber, Markus; Kleine-Boymann, Michael (2004). "Phenol". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_299.pub3. ISBN   978-3-527-30673-2.
  9. ↑ Zvi Rappoport, ed. (2003). The Chemistry of Phenols. PATAI'S Chemistry of Functional Groups. John Wiley & Sons. doi:10.1002/0470857277. ISBN   9780470857274.
  10. ↑ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN   978-0-471-72091-1
  11. ↑ Organic Chemistry 2nd Ed. John McMurry ISBN   0-534-07968-7
  12. ↑ Drago, R S. Physical Methods For Chemists, (Saunders College Publishing 1992), ISBN 0-03-075176-4
  13. ↑ Laurence, C. and Gal, J-F. Lewis Basicity and Affinity Scales, Data and Measurement, (Wiley 2010) pp 50-51 ISBN 978-0-470-74957-9
  14. ↑ Cramer, R. E.; Bopp, T. T. (1977). "Graphical display of the enthalpies of adduct formation for Lewis acids and bases". Journal of Chemical Education. 54: 612–613. doi:10.1021/ed054p612. The plots shown in this paper used older parameters. Improved E&C parameters are listed in ECW model.
  15. ↑ Capponi, Marco; Gut, Ivo G.; Hellrung, Bruno; Persy, Gaby; Wirz, Jakob (1999). "Ketonization equilibria of phenol in aqueous solution". Can. J. Chem. 77 (5–6): 605–613. doi:10.1139/cjc-77-5-6-605.
  16. ↑ Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford University Press. p. 531. ISBN   978-0-19-850346-0.
  17. ↑ Arnold, Richard T.; Buckley, Jay S. (1 May 1949). "The Dienone-Phenol Rearrangement. II. Rearrangement of 1-Keto-4-methyl-4-phenyl-1,4-dihydronaphthalene". J. Am. Chem. Soc. 71 (5): 1781. doi:10.1021/ja01173a071.
  18. ↑ Sergei M. Lukyanov, Alla V. Koblik (2003). "Tautomeric Equilibria and Rearrangements Involving Phenols". In Zvi Rappoport (ed.). The Chemistry of Phenols. PATAI'S Chemistry of Functional Groups. John Wiley & Sons. pp. 713–838. doi:10.1002/0470857277.ch11. ISBN   0471497371.
  19. ↑ David Y. Curtin & Allan R. Stein (1966). "2,6,6-Trimethyl-2,4-Cyclohexadione". Organic Syntheses . 46: 115. doi:10.15227/orgsyn.046.0115. Archived from the original on 2011-06-05. Retrieved 2010-03-31.
  20. ↑ Muller F, Caillard L (2011). "Chlorophenols". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a07_001.pub2. ISBN   978-3-527-30673-2.
  21. ↑ V. Prakash Reddy. G. K. Surya Prakash (2003). "Electrophilic reactions of phenols". In Zvi Rappoport (ed.). The Chemistry of Phenols. PATAI'S Chemistry of Functional Groups. John Wiley & Sons. pp. 605–660. doi:10.1002/0470857277.ch9. ISBN   0471497371.
  22. ↑ Roscoe, Henry (1891). A treatise on chemistry, Volume 3, Part 3. London: Macmillan & Co. p. 23.
  23. 1 2 "Phenol -- The essential chemical industry online". 2017-01-11. Retrieved 2018-01-02.
  24. 1 2 "Direct Routes to Phenol". Archived from the original on 2007-04-09. Retrieved 2007-04-09.
  25. 1 2 3 Plotkin, Jeffrey S. (2016-03-21). "What's New in Phenol Production?". American Chemical Society. Archived from the original on 2019-10-27. Retrieved 2018-01-02.
  26. ↑ Parmon, V. N.; Panov, G. I.; Uriarte, A.; Noskov, A. S. (2005). "Nitrous oxide in oxidation chemistry and catalysis application and production". Catalysis Today. 100 (2005): 115–131. doi:10.1016/j.cattod.2004.12.012.
  27. ↑ Lee, Byungik; Naito, Hiroto; Nagao, Masahiro; Hibino, Takashi (9 July 2012). "Alternating-Current Electrolysis for the Production of Phenol from Benzene". Angewandte Chemie International Edition. 51 (28): 6961–6965. doi:10.1002/anie.201202159. PMID   22684819.
  28. ↑ Wittcoff, H.A., Reuben, B.G. Industrial Organic Chemicals in Perspective. Part One: Raw Materials and Manufacture. Wiley-Interscience, New York. 1980.
  29. 1 2 Franck, H.-G., Stadelhofer, J.W. Industrial Aromatic Chemistry. Springer-Verlag, New York. 1988. pp. 148-155.
  30. 1 2 Kazem-Rostami, Masoud (2017). "Amine to phenol conversion". Synlett. 28 (13): 1641–1645. doi:10.1055/s-0036-1588180. S2CID   99294625.
  31. ↑ Kaeding, Warren W. (1 September 1964). "Oxidation of Aromatic Acids. IV. Decarboxylation of Salicylic Acids". The Journal of Organic Chemistry. 29 (9): 2556–2559. doi:10.1021/jo01032a016.
  32. ↑ Musser, Michael T. "Cyclohexanol and Cyclohexanone". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_217.pub2. ISBN   978-3-527-30673-2.
  33. ↑ "CH207 Aircraft paintstripper, phenolic, acid" (PDF). Callington. 14 October 2009. Archived from the original (PDF) on 23 September 2015. Retrieved 25 August 2015.
  34. ↑ "Prohibited substances in cosmetic product (Annex II, #1175, Phenol) - European Commission". ec.europa.eu. Retrieved 2018-07-06.
  35. ↑ "CosIng - Cosmetics - GROWTH - European Commission". ec.europa.eu. Retrieved 2018-07-06.
  36. ↑ Canada, Health (2004-06-18). "Cosmetic Ingredient Hotlist - Canada.ca". www.canada.ca. Retrieved 2018-07-06.
  37. ↑ Canada, Health (2004-06-18). "Cosmetic Ingredient Hotlist: Prohibited and Restricted Ingredients - Canada.ca". www.canada.ca. Retrieved 2018-07-06.
  38. ↑ "Phenol spray". drugs.com.
  39. ↑ "How Does Our Lip Balm Work". Carmex. Archived from the original on 18 February 2015. Retrieved 18 February 2015.
  40. ↑ "182.095 | Collections Online". collections.thackraymuseum.co.uk. Retrieved 2024-05-30.
  41. ↑ F. F. Runge (1834) "Ueber einige Produkte der Steinkohlendestillation" (On some products of coal distillation), Annalen der Physik und Chemie, 31: 65-78. On page 69 of volume 31, Runge names phenol "Karbolsäure" (coal-oil-acid, carbolic acid). Runge characterizes phenol in: F. F. Runge (1834) "Ueber einige Produkte der Steinkohlendestillation," Annalen der Physik und Chemie, 31: 308-328.
  42. ↑ Auguste Laurent (1841) "Mémoire sur le phényle et ses dérivés" (Memoir on benzene and its derivatives), Annales de Chimie et de Physique, series 3, 3: 195-228. On page 198, Laurent names phenol "hydrate de phényle" and "l'acide phénique".
  43. ↑ Auguste Laurent (1836) "Sur la chlorophénise et les acides chlorophénisique et chlorophénèsique," Annales de Chemie et de Physique, vol. 63, pp. 27–45, see p. 44: Je donne le nom de phène au radical fondamental des acides précédens (φαινω, j'éclaire), puisque la benzine se trouve dans le gaz de l'éclairage. (I give the name of "phène" (φαινω, I illuminate) to the fundamental radical of the preceding acid, because benzene is found in illuminating gas.)
  44. ↑ Gerhardt, Charles (1843) "Recherches sur la salicine," Annales de Chimie et de Physique, series 3, 7: 215-229. Gerhardt coins the name "phénol" on page 221.
  45. ↑ Lister, Joseph (1867). "Antiseptic Principle Of The Practice Of Surgery".
  46. ↑ Hollingham, Richard (2008). Blood and Guts: A History of Surgery. BBC Books - Random House. p. 61. ISBN   9781407024530.
  47. 1 2 Hollingham, Richard (2008). Blood and Guts: A History of Surgery. BBC Books - Random House. p. 62. ISBN   9781407024530.
  48. ↑ Hollingham, Richard (2008). Blood and Guts: A History of Surgery. BBC Books - Randomhouse. p. 63. ISBN   9781407024530.
  49. 1 2 3 4 5 "Phenol". Ullmann's Encyclopedia of Industrial Chemistry. Vol. 25. Wiley-VCH. 2003. pp. 589–604.
  50. ↑ The Experiments by Peter Tyson. NOVA
  51. ↑ The Nazi Doctors Archived 2017-10-22 at the Wayback Machine , Chapter 14, Killing with Syringes: Phenol Injections. By Dr. Robert Jay Lifton
  52. ↑ "Killing through phenol injection". Auschwitz: Final Station Extermination. Linz, Austria: Johannes Kepler University. Archived from the original on 2006-11-12.
  53. ↑ Rasmussen, L.E.L; Perrin, Thomas E (1999). "Physiological Correlates of Musth". Physiology & Behavior. 67 (4): 539–49. doi:10.1016/S0031-9384(99)00114-6. PMID   10549891. S2CID   21368454.
  54. ↑ Musth in elephants. Deepa Ananth, Zoo's print journal, 15(5), pages 259-262 (article)
  55. ↑ The Beaver: Its Life and Impact. Dietland Muller-Schwarze, 2003, page 43 (book at google books)
  56. 1 2 "Peat, Phenol and PPM, by Dr P. Brossard" (PDF). Retrieved 2008-05-27.
  57. ↑ "Bruichladdich". Bruichladdich. BDCL. Archived from the original on 21 April 2016. Retrieved 8 August 2015.
  58. ↑ Juteau, P.; Côté, V; Duckett, MF; Beaudet, R; Lépine, F; Villemur, R; Bisaillon, JG (2005). "Cryptanaerobacter phenolicus gen. nov., sp. nov., an anaerobe that transforms phenol into benzoate via 4-hydroxybenzoate". International Journal of Systematic and Evolutionary Microbiology. 55 (Pt 1): 245–50. doi: 10.1099/ijs.0.02914-0 . PMID   15653882.
  59. ↑ Rehfuss, Marc; Urban, James (2005). "Rhodococcus phenolicus sp. nov., a novel bioprocessor isolated actinomycete with the ability to degrade chlorobenzene, dichlorobenzene and phenol as sole carbon sources". Systematic and Applied Microbiology. 28 (8): 695–701. Bibcode:2005SyApM..28..695R. doi:10.1016/j.syapm.2005.05.011. PMID   16261859.
  60. 1 2 Budavari, S, ed. (1996). The Merck Index: An Encyclopedia of Chemical, Drugs, and Biologicals. Whitehouse Station, NJ: Merck.
  61. ↑ Lin TM, Lee SS, Lai CS, Lin SD (June 2006). "Phenol burn". Burns: Journal of the International Society for Burn Injuries. 32 (4): 517–21. doi:10.1016/j.burns.2005.12.016. PMID   16621299.
  62. ↑ Warner, MA; Harper, JV (1985). "Cardiac dysrhythmias associated with chemical peeling with phenol". Anesthesiology. 62 (3): 366–7. doi: 10.1097/00000542-198503000-00030 . PMID   2579602.
  63. ↑ World Health Organization/International Labour Organization: International Chemical Safety Cards, http://www.inchem.org/documents/icsc/icsc/eics0070.htm
  64. ↑ U.S. Department of Health and Human Services. "How can phenol affect my health?" (PDF). Toxicological Profile for Phenol: 24.
  65. ↑ Hanscha, Corwin; McKarns, Susan C; Smith, Carr J; Doolittle, David J (June 15, 2000). "Comparative QSAR evidence for a free-radical mechanism of phenol-induced toxicity". Chemico-Biological Interactions. 127 (1): 61–72. Bibcode:2000CBI...127...61H. doi:10.1016/S0009-2797(00)00171-X. PMID   10903419.
  66. ↑ "Medical Management Guidelines for Phenol (C6H6O)". Agency for Toxic Substances and Disease Registry. U.S. Department of Health and Human Services. October 21, 2014. Retrieved 8 August 2015.
  67. ↑ Brown, VKH; Box, VL; Simpson, BJ (1975). "Decontamination procedures for skin exposed to phenolic substances". Archives of Environmental Health. 30 (1): 1–6. doi:10.1080/00039896.1975.10666623. PMID   1109265.
  68. ↑ Hunter, DM; Timerding, BL; Leonard, RB; McCalmont, TH; Schwartz, E (1992). "Effects of isopropyl alcohol, ethanol, and polyethylene glycol/industrial methylated spirits in the treatment of acute phenol burns". Annals of Emergency Medicine . 21 (11): 1303–7. doi:10.1016/S0196-0644(05)81891-8. PMID   1416322.
  69. ↑ Pullin, TG; Pinkerton, MN; Johnston, RV; Kilian, DJ (1978). "Decontamination of the skin of swine following phenol exposure: a comparison of the relative efficacy of water versus polyethylene glycol/industrial methylated spirits". Toxicol Appl Pharmacol. 43 (1): 199–206. Bibcode:1978ToxAP..43..199P. doi:10.1016/S0041-008X(78)80044-1. PMID   625760.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.