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Benzoic acid
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Benzoic acid




Benzoic acid crystals
IUPAC name[hide]
Benzoic acid
Other names[hide]
Carboxybenzene; E210; Dracylic acid; Phenylmethanoic acid;
Benzenecarboxylic acid
Identifiers
CAS number 65-85-0


PubChem 243
ChemSpider 238


UNII 8SKN0B0MIM


EC number 200-618-2
DrugBank DB03793
KEGG D00038


MeSH benzoic+acid
ChEBI CHEBI:30746


ChEMBL CHEMBL541


RTECS number DG0875000
Beilstein Reference 636131
Gmelin Reference 2946
3DMet B00053
Jmol-3D images Image 1
Image 2
SMILES
[show]
InChI
[show]
Properties
Molecular formula C7H6O2
Molar mass 122.12 g mol
1

Appearance Colorless crystalline solid
Odor faint, pleasant odor
Density 1.2659 g/cm
3
(15 C)
1.0749 g/cm
3
(130 C)
[1]

Melting point 122.41 C (252.34 F; 395.56 K)
[5]

Boiling point 249.2 C (480.6 F; 522.3 K)
[6]

370 C (698 F; 643 K)
decomposes
[1]

Solubility in water 1.7 g/L (0 C)
2.7 g/L (18 C)
3.44 g/L (25 C)
5.51 g/L (40 C)
21.45 g/L (75 C)
56.31 g/L (100 C)
[1][2]

Solubility soluble
in acetone, benzene,CCl4, CHCl3, alcohol, ethyl
ether, hexane, phenyls, liquid ammonia, acetates
Solubility inmethanol 30 g/100 g (-18 C)
32.1 g/100 g (-13 C)
71.5 g/100 g (23 C)
[1]

Solubility inethanol 25.4 g/100 g (-18 C)
47.1 g/100 g (15 C)
52.4 g/100 g (19.2 C)
55.9 g/100 g (23 C)
[1]

Solubility inacetone 54.2 g/100 g (20 C)
[1]

Solubility in olive oil 4.22 g/100 g (25 C)
[1]

Solubility in 1,4-
Dioxane
55.3 g/100 g (25 C)
[1]

log P 1.87
Vapor pressure 0.16 Pa (25 C)
0.19 kPa (100 C)
22.6 kPa (200 C)
[3]

Acidity (pKa) 4.202
[4]

Refractive index(nD) 1.5397 (20 C)
1.504 (132 C)
[1]

Viscosity 1.26 mPa (130 C)
Structure
Crystal structure Monoclinic
Molecular shape planar
Dipole moment 1.72 D in Dioxane
Thermochemistry
Specific 146.7 J/mol K
[3]

heat capacity C
Std molar
entropy S
o
298
167.6 J/mol K
[1]

Std enthalpy of
formation fH
o
298
-385.2 kJ/mol
[1]

Std enthalpy of
combustioncH
o
298
3228 kJ/mol
[3]

Hazards
MSDS JT Baker
GHS pictograms
[7]

GHS signal word Danger
GHS hazard
statements
H318, H335
[7]

GHS precautionary
statements
P261, P280,P305+351+338
[7]

EU Index Not listed
EU classification
Xi
R-phrases R37, R41
S-phrases S26, S39
Main hazards Irritant
NFPA 704

1
2
0
Flash point 121.5 C (250.7 F; 394.6 K)
[6]

Autoignition 571 C (1,060 F; 844 K)
[6]

temperature
LD50 1700 mg/kg (rat, oral)
Related compounds
Related carboxylic
acids
Hydroxybenzoic acids
Aminobenzoic acids,
Nitrobenzoic acids,
Phenylacetic acid
Related compounds Benzaldehyde,
Benzyl alcohol,
Benzoyl chloride,
Benzylamine,
Benzamide
Except where noted otherwise, data are given for materials in
their standard state (at 25 C (77 F), 100 kPa)
(verify) (what is: / ?)
Infobox references
Benzoic acid /bnzo.k/, C7H6O2 (or C6H5COOH), is a colorless crystalline solid and a
simple aromatic carboxylic acid. The name is derived from gum benzoin, which was for a long time
its only known source. Benzoic acid occurs naturally in many plants
[8]
and it serves as an
intermediate in the biosynthesis of many secondary metabolites. Salts of benzoic acid are used as
food preservatives and benzoic acid is an important precursor for the industrial synthesis of many
other organic substances. The salts and esters of benzoic acid are known
as benzoates /bnzo.et/.
Contents
[hide]
1 History
2 Production
o 2.1 Industrial preparations
o 2.2 Laboratory synthesis
2.2.1 By hydrolysis
2.2.2 From benzaldehyde
2.2.3 From bromobenzene
2.2.4 From benzyl alcohol
2.2.5 From benzyl chloride
2.2.6 Historical preparation
3 Uses
o 3.1 Precursor to plasticizers
o 3.2 Precursor to sodium benzoate and related preservatives
o 3.3 Medicinal
o 3.4 Benzoyl chloride
o 3.5 Niche and laboratory uses
4 Biology and health effects
5 Reactions
o 5.1 Aromatic ring
o 5.2 Carboxyl group
6 References
7 External links
History[edit]
Benzoic acid was discovered in the sixteenth century. The dry distillation of gum benzoin was first
described by Nostradamus (1556), and then by Alexius Pedemontanus (1560) and Blaise de
Vigenre (1596).
[9]

Pioneer work in 1830 through a variety of experiences based on amygdalin, obtained from bitter
almonds (the fruit of Prunus dulcis) oil by Pierre Robiquet and Antoine Boutron-Charlard, two French
chemists, had produced benzaldehyde
[10]
but they failed in working out a proper interpretation of the
structure of amygdalin that would account for it, and thus missed the identification of
the benzoyl radical C7H5O. This last step was achieved some few months later (1832) by Justus von
Liebig and Friedrich Whler, who determined the composition of benzoic acid.
[11]
These latter also
investigated how hippuric acid is related to benzoic acid.
In 1875 Salkowski discovered the antifungal abilities of benzoic acid, which was used for a long time
in the preservation of benzoate-containing cloudberry fruits.
[12]

It is also one of the chemical compounds found in castoreum. This compound is gathered from the
beaver plant food.
[13]

Production[edit]
Industrial preparations[edit]
Benzoic acid is produced commercially by partial oxidation of toluene with oxygen. The process is
catalyzed by cobalt or manganese naphthenates. The process uses cheap raw materials, and
proceeds in high yield.
[citation needed]


U.S. production capacity is estimated to be 126,000 tonnes per year
(139,000 tons), much of which is consumed domestically to prepare
other industrial chemicals.
Laboratory synthesis[edit]
Benzoic acid is cheap and readily available, so the laboratory
synthesis of benzoic acid is mainly practiced for its pedagogical
value. It is a common undergraduate preparation.
Benzoic acid can be purified by recrystallization from water because
of its high solubility in hot water and poor solubility in cold water.
The avoidance of organic solvents for the recrystallization makes
this experiment particularly safe.
[14]
The solubility of benzoic acid in
over 40 solvents with references to original sources can be found as
part of the Open Notebook Science Challenge
[15]

By hydrolysis[edit]
Like other nitriles and amides, benzonitrile and benzamide can be
hydrolyzed to benzoic acid or its conjugate base in acid or basic
conditions.
From benzaldehyde[edit]
The base-induced disproportionation of benzaldehyde,
the Cannizzaro reaction, affords equal amounts of benzoate
and benzyl alcohol; the latter can be removed by distillation.

From bromobenzene[edit]
Bromobenzene can be converted to benzoic acid by "carbonation"
of the intermediate phenylmagnesium bromide.
[16]
This synthesis
offers a convenient exercise for students to carry out a Grignard
reaction, an important class of carboncarbon bond forming
reaction in organic chemistry.
[17][18]

From benzyl alcohol[edit]
Benzyl alcohol is refluxed with potassium permanganate or other
oxidizing reagents in water. The mixture is hot filtered to remove
manganese dioxide and then allowed to cool to afford benzoic acid.
From benzyl chloride[edit]
Benzoic acid can be prepared by oxidation of benzyl chloride in the
presence of alkaline KMnO4:
C6H5CH2Cl + 2 KOH + 2 [O] C6H5COOH + KCl + H2O
Historical preparation[edit]
The first industrial process involved the reaction
of benzotrichloride (trichloromethyl benzene) with calcium
hydroxide in water, using iron or iron salts as catalyst. The
resulting calcium benzoate is converted to benzoic acid
with hydrochloric acid. The product contains significant amounts
of chlorinated benzoic acid derivatives. For this reason, benzoic
acid for human consumption was obtained by dry distillation of
gum benzoin. Food-grade benzoic acid is now produced
synthetically.
Uses[edit]
Benzoic acid is mainly consumed in the production of phenol by
oxidative decarboxylation at 300400 C:
[19]

C6H5CO2H + 1/2 O2 C6H5OH + CO2
The temperature required can be lowered to 200 C by the
addition of catalytic amounts of copper(II) salts. The phenol
can be converted to cyclohexanol, which is a starting
material for nylon synthesis.
Precursor to plasticizers[edit]
Benzoate plasticizers, such as the glycol-, diethylenegylcol-
, and triethyleneglycol esters, are obtained
by transesterification of methyl benzoate with the
corresponding diol. Alternatively these species arise by
treatment of benzoylchloride with the diol. These
plasticizers are used similarly to those derived
from terephthalic acid ester.
Precursor to sodium benzoate and related
preservatives[edit]
Benzoic acid and its salts are used as a food preservatives,
represented by the E-numbers E210, E211, E212,
and E213. Benzoic acid inhibits the growth
of mold, yeast
[20]
and some bacteria. It is either added
directly or created from reactions with
its sodium, potassium, or calcium salt. The mechanism
starts with the absorption of benzoic acid into the cell. If the
intracellular pH changes to 5 or lower, the anaerobic
fermentation of glucosethrough phosphofructokinase is
decreased by 95%. The efficacy of benzoic acid and
benzoate is thus dependent on the pH of the food.
[21]
Acidic
food and beverage like fruit juice (citric acid), sparkling
drinks (carbon dioxide), soft drinks (phosphoric
acid), pickles (vinegar) or other acidified food are preserved
with benzoic acid and benzoates.
Typical levels of use for benzoic acid as a preservative in
food are between 0.050.1%. Foods in which benzoic acid
may be used and maximum levels for its application are
controlled by international food law.
[22][23]

Concern has been expressed that benzoic acid and its salts
may react with ascorbic acid (vitamin C) in some soft
drinks, forming small quantities of benzene.
[24]

See also: Benzene in soft drinks
Medicinal[edit]
Benzoic acid is a constituent of Whitfield's ointment which is
used for the treatment of fungal skin diseases such
as tinea, ringworm, and athlete's foot.
[25][26]
As the principal
component of benzoin resin, benzoic acid is also a major
ingredient in both tincture of benzoin and Friar's balsam.
Such products have a long history of use as
topical antiseptics and inhalant decongestants.
Benzoic acid was used as an expectorant, analgesic,
and antiseptic in the early 20th century.
[27]

Benzoyl chloride[edit]
Benzoic acid is a precursor to benzoyl chloride, C6H5C(O)Cl
by treatment with thionyl chloride, phosgene or one of
the chlorides of phosphorus. is an important starting
material for several benzoic acid derivates likebenzyl
benzoate, which is used in artificial flavours and insect
repellents.
Niche and laboratory uses[edit]
In teaching laboratories, benzoic acid is a common
standard for calibrating a bomb calorimeter.
[28]

Biology and health effects[edit]
Benzoic acid is relatively nontoxic. It is excreted as hippuric
acid.
[29]
Benzoic acid is metabolized by butyrate-CoA
ligase into an intermediate product, benzoyl-CoA,
[30]
which
is then metabolized by glycine N-acyltransferase into
hippuric acid.
[31]

Benzoic acid occurs naturally as do its esters in many plant
and animal species. Appreciable amounts have been found
in most berries (around 0.05%). Ripe fruits of
several Vaccinium species (e.g., cranberry, V. vitis
macrocarpon; bilberry, V. myrtillus) contain as much as
0.030.13% free benzoic acid. Benzoic acid is also formed
in apples after infection with the fungus Nectria galligena.
Among animals, benzoic acid has been identified primarily
in omnivorous or phytophageous species, e.g., in viscera
and muscles of the Rock Ptarmigan (Lagopus muta) as well
as in gland secretions of male muskoxen (Ovibos
moschatus) or Asian bull elephants (Elephas maximus).
[32]

Gum benzoin contains up to 20% of benzoic acid and 40%
benzoic acid esters.
[33]

Cryptanaerobacter phenolicus is a bacterium species that
produces benzoate from phenol via 4-hydroxybenzoate
[34]

Benzoic acid is present as part of hippuric acid (N-
benzoylglycine) in urine of mammals,
especially herbivores (Gr. hippos = horse; ouron = urine).
Humans produce about 0.44 g/L hippuric acid per day in
their urine, and if the person is exposed to toluene or
benzoic acid, it can rise above that level.
[35]

For humans, the World Health Organization's International
Programme on Chemical Safety (IPCS) suggests a
provisional tolerable intake would be 5 mg/kg body weight
per day.
[32]
Cats have a significantly lower tolerance against
benzoic acid and its salts than ratsand mice. Lethal dose
for cats can be as low as 300 mg/kg body weight.
[36]
The
oral LD50 for rats is 3040 mg/kg, for mice it is 1940
2263 mg/kg.
[32]

In Taipei, Taiwan, a city health survey in 2010 found that
30% of dried and pickled food products had too much
benzoic acid, which may affect the liver and kidney,
[37]
along
with more serious issues like excessive cyclamate.
Reactions[edit]
Reactions of benzoic acid can occur at either the aromatic
ring or at the carboxyl group:
Aromatic ring[edit]

Electrophilic aromatic substitution reaction will take
place mainly in 3-position due to the electron-
withdrawing carboxylic group; i.e. benzoic acid
is meta directing.
The second substitution reaction (on the right) is slower
because the first nitro group is
deactivating.
[38]
Conversely, if an activating group
(electron-donating) was introduced (e.g., alkyl), a
second substitution reaction would occur more readily
than the first and the disubstituted product might
accumulate to a significant extent.
Carboxyl group[edit]
All the reactions mentioned for carboxylic acids are also
possible for benzoic acid.
Benzoic acid esters are the product of the acid
catalysed reaction with alcohols.
Benzoic acid amides are more easily available by
using activated acid derivatives (such as benzoyl
chloride) or by coupling reagents used in peptide
synthesis like DCC and DMAP.
The more active benzoic anhydride is formed by
dehydration using acetic anhydride or phosphorus
pentoxide.
Highly reactive acid derivatives such as acid
halides are easily obtained by mixing
with halogenation agents like phosphorus
chlorides or thionyl chloride.
Orthoesters can be obtained by the reaction of
alcohols under acidic water free conditions
with benzonitrile.
Reduction to benzaldehyde and benzyl alcohol is
possible using DIBAL-H, LiAlH4 or sodium
borohydride.
The copper
catalysed decarboxylation of benzoate to benzene
may be effected by heating in quinoline. Also,
Hunsdiecker decarboxylation can be achieved by
forming the silver salt and heating. Benzoic acid
can also be decarboxylated by heating with an
alkali hydroxide or calcium hydroxide.