Benzoic Acid and Derivatives 1

Benzoic Acid and Derivatives

Takao Maki, Dia Research Martech Inc., Yokohama, Japan (Chaps. 1 – 8)
Kazuo Takeda, Mitsubishi Chemical Safety Institute Ltd., Yokohama, Japan (Chap. 9)

1. Introduction . . . . . . . . . . . . . . . . 1 8.3. Benzoyl Chloride . . . . . . . . . . . . . 6

2. Physical Properties . . . . . . . . . . . 1 8.4. Benzonitrile . . . . . . . . . . . . . . . . 7
3. Chemical Properties . . . . . . . . . . . 2 8.5. Alkyl and Acyl Analogues . . . . . . . 7
4. Production . . . . . . . . . . . . . . . . . 2 8.6. Chlorobenzoic Acids . . . . . . . . . . 9
5. Quality Specifications . . . . . . . . . . 3 8.7. Aminobenzoic Acids . . . . . . . . . . . 10
6. Storage, Transportation and Legal
8.8. Nitrobenzoic Acids . . . . . . . . . . . . 12
Aspects . . . . . . . . . . . . . . . . . . . 3
8.9. 3-Sulfobenzoic Acid . . . . . . . . . . . 13
7. Uses and Economic Aspects . . . . . . 4
8. Derivatives of Benzoic Acid . . . . . . 5 8.10. Hexahydrobenzoic Acid . . . . . . . . 13
8.1. Salts of Benzoic Acid . . . . . . . . . . 5 9. Toxicology . . . . . . . . . . . . . . . . . 13
8.2. Esters of Benzoic Acid . . . . . . . . . 5 10. References . . . . . . . . . . . . . . . . . 13

1. Introduction azeotropes with biphenyl, butyl benzoate, cat-

echol, diphenyl ether, diphenylmethane, and
Benzoic acid [65-85-0], C7 H6 O2 . The name naphthalene. At 89.7 ◦ C, a mixture of excess
benzoic acid originates from gum benzoin, a bal- benzoic acid and water forms two stable liquid
samic resin obtained from a South Asian plant phases. The water content of the benzoic acid
called styrax. The extraction of benzoic acid phase is 26.5 wt %. The two phases become ho-
was carried out by Scheele in 1775. Its struc- mogeneous at 117.2 ◦ C. The mixture then con-
ture was determined by Liebig and Wöhler in tains 32.34 % benzoic acid and 67.66 % water.
1832. The initial production methods were de- Some physical properties of benzoic acid are
veloped in the late 1800s. They were based on listed in the following:
the hydrolysis of benzotrichloride or the decar-
Solubility in water, g/100 g
boxylation of phthalic anhydride. Today, ben- at 0 ◦ C 0.17
zoic acid is produced by oxidation of toluene at 20 ◦ C 0.29
with air, which has displaced dichromate and at 40 ◦ C 0.60
at 60 ◦ C 1.20
nitric acid oxidation processes. at 80 ◦ C 2.75
at 95 ◦ C 6.85
Solubility in organic solvents at
Occurrence. Benzoic acid and its derivatives 25 ◦ C, g/100 g
are widely distributed in nature. Gum benzoin Acetone 55.60
contains from 12 – 18 % benzoic acid in free and Benzene 12.17
Tetrachloromethane 4.14
esterified forms. Other natural products contain- Ethanol (absolute) 58.40
ing benzoic acid are the bark, foliage, fruits, and Hexane 0.94 (at 17 ◦ C)
Methanol 71.50 (at 23 ◦ C)
seeds of various plants, including cherries and Toluene 10.60
prunes. Hippuric acid, found in the urine of her- Vapor pressure, kPa
bivores, is a glycine derivative of benzoic acid. at 96 ◦ C 0.133
at 132 ◦ C 1.33
at 186 ◦ C 13.3
Vapor density relative to air 4.2
Refractive index
2. Physical Properties n15
D 1.53974
n131.9
D 1.504
Benzoic acid, benzenecarboxlic acid, M r Relative density
d 20 1.321
122.12, mp 122 ◦ C, bp 250 ◦ C, forms white 4
d 122.375
4 1.0819
monoclinic crystals that begin to sublime at d 180
4 1.02942
about 100 ◦ C. It is volatile in steam and forms

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a03 555
2 Benzoic Acid and Derivatives

Specific heat
3-chlorobenzoic acid [6]. Nitration forms 3-
solid (20 – 122 ◦ C) 1.204 J g−1 K−1 nitrobenzoic acid [7], and sulfonation forms 3-
liquid (122 – 322 ◦ C) 1.775 J g−1 K−1 sulfobenzoic acid.
Heat of fusion 18 kJ/mol
Heat of sublimation at 110 ◦ C 86.2 kJ/mol
Heat of vaporization at 150 ◦ C 68.2 kJ/mol
Heat of formation − 384.9 kJ/mol
Heat of combustion at 25 ◦ C 3227 kJ/mol 4. Production
Free energy
solid − 251 kJ/mol
liquid − 247 kJ/mol
Liquid-Phase Oxidation of Toluene with
aqueous solution − 242 kJ/mol Molecular Oxygen. This process was devel-
Flash point 121.1 ◦ C oped by I.G. Farbenindustrie in Germany dur-
Ignition temperature
in air 573 ◦ C ing World War II and was operated until the end
in oxygen 556 ◦ C of the war [8]. The plant consisted of a bubble-
Dissociation constant at 25 ◦ C, Ka 6.335×10−5 column oxidation reactor made of aluminum-
pH of the saturated solution at 25 ◦ C 2.8
Change in volume upon freezing − 0.138 cm3 /g lined steel and equipped with an air inlet tube,
log POW ∗ 1.870 a separator, and an absorber to recover toluene.
∗ Bioaccumulation factor
The reactor contained heat-exchange coils to re-
(octanol/water partition factor) move the great amount of heat generated in the
reaction. The purity of the toluene was criti-
cal because sulfur compounds, nitrogen com-
pounds, phenols, and olefins inhibit the oxida-
3. Chemical Properties tion reaction. The reaction was carried out at
140 ◦ C and ca. 0.2 MPa with a cobalt naphthen-
Benzoic acid is stable towards common oxidiz- ate catalyst (0.1 %) for 30 h. About 50 % con-
ing agents. Air, permanganate, chromic acid, version of toluene was achieved, 80 % of which
hypochlorite, and dilute nitric acid do not af- formed benzoic acid. Other oil-soluble cobalt
fect it. However, above 220 ◦ C it reacts with salts were also used as catalysts. The crude oxi-
copper(II) salts to form phenol and its deriva- dation product was neutralized with sodium car-
tives [1]. This reaction, followed by regenera- bonate to produce sodium benzoate. Unreacted
tion of the copper(II) with molecular oxygen, is toluene was recovered from the spent oil phase
the basis for the commercial production of phe- by distillation.
nol from benzoic acid [2] (→ Phenol). Benzoic The elemental mechanism of this oxidation is
acid reacts with ammonia under similar condi- a free-radical chain process [9]. The cobalt cata-
tions to form aniline [3]. Upon heating to 150 ◦ C, lyst shortens the induction period of the reaction
some dehydration takes place to form benzoic and retards the accumulation of inhibitors. Per-
anhydride. Decarboxylation occurs when ben- oxides are reaction intermediates. Manganese
zoic acid is heated above 370 ◦ C or as low as behaves similarly to cobalt as a catalyst, but its
245 ◦ C in the presence of catalysts [4]. Benzene performance is weaker. Copper adversely affects
and a small amount of phenol are formed. Cop- the oxidation. High pressures retard the reac-
per and cadmium powder accelerate the decar- tion, especially at lower catalyst concentrations.
boxylation. When potassium benzoate is heated Above 130 ◦ C, the reaction rate is determined by
in carbon dioxide, it disproportionates to tereph- the diffusion of oxygen. Phenolic compounds
thalate and benzene. Cadmium and zinc salts gradually accumulate during the reaction and
catalyze this reaction. Benzoic acid is converted eventually inhibit it.
into hydroxybenzoic acids by fused potassium In a typical modern process the oxidation is
hydroxide [5]. conducted at 165 ◦ C and 0.9 MPa. The reaction
Benzoic acid can be directly hydrogenated heat is removed by external circulation of the
with molecular hydrogen to afford benzalde- contents of the reactor. The pressure of the liq-
hyde in quantitative yield. Zirconium and uid discharged form the reactor is reduced to at-
other metal oxides catalyze the reaction mospheric, and unreacted toluene is recovered.
[31]. Hydrogenation on noble metal cata- Benzoic acid is purified by rectification. The bot-
lysts gives cyclohexanecarboxylic acid (hexa- tom residue is extracted to recover the cobalt
hydrobenzoic acid). Chlorination yields chiefly

catalyst. The exhaust gas is cooled to recover
most of the toluene, purified, and vented. The
oxidation reactor can be a bubble column or a
stirred tank. Stainless steel is generally used as
the construction material. Heat removal is still a
serious problem, and air distribution within the
reactor is critical to prevent a runaway reaction.
The oxygen content of the exhaust gas should be
strictly monitored to avoid an explosion.
The oxidation produces several byproducts.
Benzaldehyde is formed in fairly large amounts,
especially at lower conversions. It can be recov-
ered by distillation. A limited amount of benzyl
alcohol is formed, but its recovery is impractical
because of the unavoidable esterification with
benzoic acid. Benzyl benzoate can be recovered
from the bottoms of the benzoic acid column
[10]. Other esters, including benzyl formate and
benzyl acetate, are also present. Biphenyl and
methylbiphenyls are formed in smaller amounts.
Because their vapor pressures are close to that
of benzoic acid, they play a role in the rectifi-
cation of benzoic acid. The product is contami-
nated by small amounts of phthalic acid. Carbon
monoxide and carbon dioxide are detected in the
exhaust gas. The yield of benzoic acid is about
90 %, but it varies with toluene conversion. At
lower conversions, the selectivity for benzalde-
hyde and benzyl alcohol exceeds 10 %.
Conventional technical-grade benzoic acid is
usually of as-rectified quality. Further process-
ing is necessary for higher grade products. Subli-
mation, recrystallization, and neutralization pro-
cesses have been proposed. Thermal treatment
in an inert atmosphere is attempted [11]. To re-
move phthalic acid, whose presence is not al-
lowed for food or pharmaceutical uses, treatment
with amines [32] and rinsing [33] methods have
been reported. Methylbiphenyls are responsible
for the odor of the product. For their removal, ex-
traction [34] and treatment in an inert gas stream
[35] have been proposed.
The oxidation reactions of alkylaromatic hy-
drocarbons are dramatically enhanced by adding
bromine compounds to the cobalt catalyst in
acetic acid [12]. This method is now widely
used in the production of terephthalic acid and is
also applicable to the benzoic acid process. Un-
der certain conditions, benzoic acid itself can
be used as a solvent. Manganese has synergistic
effect on the cobalt catalyst. This process can re-
alize high reaction rates and better toluene con-
Benzoic Acid and Derivatives 3
version, as well as eliminating reaction inhibi-
tion. However, to avoid corrosion, the equipment
must be constructed of expensive titanium.
Another type of cobalt catalyst activator is a
readily oxidizable carbonyl compound such as
methyl ethyl ketone or acetaldehyde. These ad-
ditives permit a considerable reduction in reac-
tion temperature, but because of the high con-
sumption of these activators, this technology
does not seem to be practical.
The catalytic oxidation of toluene in aqueous
sodium hydroxide directly affords sodium ben-
zoate. This process has been tried since 1940s,
but satisfactory yields have not been achieved.
Vapor-phase oxidation of toluene at
higher temperatures is another potential pro-
cess. Various catalysts (vanadium, tungsten,
uranium, molybdenum, silver, etc.) have been
investigated, but yields were not comparable to
those of the liquid-phase process. However, a
patent claims a significant improvement in yield
by using complex vanadia catalysts [36].
5. Quality Specifications
Quality specifications for benzoic acid are listed
in Tables 1 and 2. An EU guideline for the use of
benzoic acid and its derivatives has been issued
[37].
6. Storage, Transportation and Legal
Aspects
Benzoic acid is commercially handled as flakes
packed in 25 kg paper bags or in 500 kg flexi-
ble containers. Bulk quantities are transported
as molten liquid in stainless steel vessels. For
transport, benzoic acid is not regulated as a haz-
ardous material (IMO, IATA, ADR/SDR, and
RID/SDR). There is no IMDG code. The re-
portable quantity in USA is 2270 kg (40 CFR
355.40). The European hazard-labeling symbol
is Xn (harmful). The MSDN is available on the
Internet [38], [39].
Benzoic acid can be stored without deterio-
ration, but the low-grade product tends to so-
lidify on storage. Precautions should be taken
against dust during handling since it irritates the
4 Benzoic Acid and Derivatives
Table 1. Quality specifications for technical-grade benzoic acid

Items Specifications Specifications for commercial products

Japan Japan USA Europe

(JIS K 4127, 1995) Commercial Industrial Technical Commercial

grade grade grade grade

mp, ◦ C 120 – 123 121 – 123 121 – 123 121.5 – 123 122 – 122.5
Assay, % min. 99.0 (by glc) 99.6 97.5 99.0 99.5
Moisture, 0.3 (by titration)
% max.
Low-boiling 0.5 (by glc)
substances,
% max.
High-boiling 0.5 (by glc)
substances,
% max.
Heavy metals, 10 10
ppm max.
Phthalic acid, 0.5 (by glc)
% max.
Ignition 0.1 0.1 0.1 0.1 0.1
residue,
% max.
Appearance white off-white brownish white white

Table 2. Quality specifications of pharmaceutical- and food-grade benzoic acid

Pharmaceutical Food additive

Japan USA Germany Japan USA

(JP12 1993) (USP23 1995) (Official) (FCC 1996)

Identification pass test pass test pass test

mp, ◦ C 121 – 124 121 – 123 121 – 124 121 – 123 121 – 123
(fp) (fp)
Assay, % min. (by titration) 99.5 99.5 – 100.5 99.0 – 100.5 99.5 99.5 – 100.5
Moisture, % max. 0.5 0.7 0.5 0.7
(by weight loss) (by titration)
Heavy metals, ppm max. 20 10 10 10 10
Arsenic, ppm max. 3 4
Readily oxidizable substances pass test pass test pass test pass test
(by permanganate)
Readily carbonizable substances pass test pass test pass test pass test
(by sulfuric acid)
Phthalic acid pass test pass test
(by fluorescence)
Halogen compounds pass test pass test 0.014 % max.
Ignition residue, % max. 0.05 0.05 0.1 0.05
Solubility pass test

eyes and skin. Dust/air mixtures can be explosive
above the flash point (121◦ C). The explosion
limit of the vapor/air mixture is 0.085-0.99g/m3 .
Benzoic acid has the following registry
number for the legal control: TSCA 65-85-
0, EINECS (European Inventory of Existing
Chemical substances) 200-618-2, ECNS (Japan)
(3)-1397, RTECS DG0875000.
7. Uses and Economic Aspects
The majority of the benzoic acid is utilized cap-
tively to produce phenol. The rest comes onto
the market. The benzoic acid market in the USA
and Japan is summarized in Table 3. Major pro-
ducers are listed in Table 4.
Glycol esters of benzoic acid are used as plas-
ticizers for vinyl resins. Demand has increased
in the USA as a replacement for butyl benzyl
 Benzoic Acid and Derivatives 5

phthalate in poly(vinyl acetate) emulsion adhe- its dust is dispersed in air. It absorbs moisture
sives [40]. Another major market is sodium ben- from air to some extent. Upon heating in an in-
zoate for preservatives and anticorrosives. Ben- ert atmosphere, sodium benzoate carbonizes and
zoic acid is used in modified alkyd resins for forms sodium carbonate. In the presence of air,
automotive refinishing enamels to improve sur- it burns to give carbon dioxide and sodium car-
face properties. Benzoic acid is also used as an bonate. Sodium benzoate reacts with benzoyl
intermediate for perfumes, pharmaceuticals, and chloride to form benzoic anhydride [93-97-0].
cosmetics. The market in USA has experienced Other salts of benzoic acid can be prepared by
growth rate of 4 % per annum [42]. metathesis reactions with the salts of particu-
lar cations. Sodium benzoate is produced by the
Table 3. Benzoic acid consumption (in %)
neutralization of benzoic acid with sodium hy-
Item USA Japan droxide. Direct oxidation of toluene in sodium
1991 1991 hydroxide solution is not currently in use.
Plasticizers 50 0 The principal use of sodium benzoate is an
Sodium benzoate 25 55 anticorrosive. The expansion of the motor in-
Benzoyl chloride 10 15
Alkyd resins 5 10
dustry has increased demand. It is added mainly
Others 10 20 to antifreeze coolants. It is also used as a preser-
vative for foods and cosmetics. Specifications
for food-grade sodium benzoate are listed in Ta-
Table 4. Major benzoic acid producers ble 5. The CFR GRAS level is 0.1 % max., and
Company Capacity, 103 t/a
its use below pH 4.5 is recommended [41].

Kalama Chemical (USA) 95 Table 5. Specifications for food-grade sodium benzoate

Velsicol Chemical (USA) 30
DSM (NL) 120 Japan USA
Chimica del Fruita (IT) 30 (FCC, 1996)
Velsicol Eesti (Estonia) 30
Liquid Quimica (E) 5 Appearance pass test pass test
Mitsubishi Chemical (JP) 10 Solubility pass test
Nippon Steel Chemical (JP) captive Assay, % min. (by titration) 99.0 99.0 – 100.5
Moisture, % max. (by weight 1.5 1.5
loss)
Free alkali, % max. (as NaOH) pass test 0.04
Free acid pass test
Heavy metals, ppm max. (as Pb) 10 10
8. Derivatives of Benzoic Acid Arsenic, ppm max. 4
Readily oxidizable substances pass test
(by permanganate)
8.1. Salts of Benzoic Acid Phthalic acid (by fluorescence) pass test
Halogen compounds, % max. 0.014
(by Ag)
Sodium benzoate [532-32-1], C7 H5 O2 Na, Sulfate, % max. 0.3
M r 144.11, forms white granules, flakes, or a
crystalline powder with a sweetish taste. One
gram dissolves in 2 mL of water. Between 0 ◦ C
Potassium benzoate [582-25-2], C7 H5 O2 K,
and 50 ◦ C the solubility in water is nearly con-
M r 160.22. At 17.5 ◦ C, a saturated aqueous so-
stant, but at higher temperature it increases
lution contains 41.1 wt % of the salt. It has
sharply. At −13.5 ◦ C, the eutectic mixture with
similar properties to the sodium salt. It is used
water consists of 44.9 g of the salt and 100 g of
in the food industries where the presence of
water. The aqueous solution is slightly alkaline
sodium is undesirable.
(pH ca. 8). Sodium benzoate is soluble to the
extent of 0.8 g in 100 mL of ethanol, 8.2 g in
100 mL of methanol, and over 20 g in 100 mL
of ethylene glycol. Aqueous and alcoholic solu- 8.2. Esters of Benzoic Acid
tions of sodium benzoate passivate the surfaces
of metals and alloys. Methyl benzoate [93-58-3], C8 H8 O2 , M r
Dry sodium benzoate is electrically charged 136.15, mp −12.21 ◦ C, bp 199.5 ◦ C, colorless
by friction and forms an explosive mixture when liquid with a pleasant odor, n20
D 1.516, d 4
15
6 Benzoic Acid and Derivatives
1.09334, solubility in water at 20 ◦ C 0.15 wt %,
miscible with common organic solvents, va-
por pressure 0.133 kPa at 39 ◦ C, 13.3 kPa at
130.8 ◦ C, flash point 83 ◦ C, ignition point
505 ◦ C, heat of combustion 3950 kJ/mol. Methyl
benzoate forms an azeotrope (20.8 wt % ester)
with water, bp 99.08 ◦ C. Stable against oxida-
tion and easily saponified by strong base.
Methyl benzoate is prepared by reacting
methanol with benzoic acid. It is used as a per-
fume and as an intermediate in the production
of other benzoic esters.
n-Butyl benzoate [136-60-7], C11 H14 O2 ,
M r 178.23, mp −22.4 ◦ C, bp 250.3 ◦ C, d 20
4
1.0061, flash point 111 ◦ C; autoignition tem-
perature 440 ± 5 ◦ C, heat of combustion
5828 kJ/mol. Butyl benzoate forms an azeotrope
(6 wt % ester) with water, bp 99.8 ◦ C. Butyl ben-
zoate is widely used as a dye carrier in polyester
fibers.
Glycol Benzoates. Diethylene glycol diben-
zoate [120-55-8], C18 H18 O5 , M r 314.34, mp
−28 ◦ C, bp 240 ◦ C at 0.7 kPa, d 20
4 1.178, nD
25
◦ acts violently with water to give benzoic acid and
1.5424, flash point 232 C.
Propylene glycol dibenzoate [19224-26-1],
C17 H16 O4 , Mr 284.31, fp -3 ◦ C, bp 232 ◦ C at
1.6 kPa.
Dipropylene glycol dibenzoate [27138-31-4],
C20 H22 O5 , M r 342.40, mp −40 ◦ C, bp 232 ◦ C
at 0.7 kPa, d 20 25
4 1.129, nD 1.5282, flash point
◦ and Schotten – Baumann reaction conditions.
212 C.
Glycerine tribenzoate [614-33-5].
The glycol benzoates are used as plasticizers
in poly(vinyl chloride), poly(vinyl acetate), and
polacrylate resins.
Phenyl benzoate [93-99-2], C13 H10 O2 , M r
198.21; monoclinic crystals, mp 70 ◦ C; bp
314 ◦ C, d 20
4 1.235, slightly soluble in water, sol-
uble in hot ethanol. Phenyl benzoate is an inter-
mediate in the production of phenol from ben-
zoic acid.
Benzyl benzoate [120-51-4], C14 H12 O2 ,
M r 212.25, leaflets or oily liquid, aromatic odor,
mp 21 ◦ C, bp 323 – 324 ◦ C, bp 189 – 191 ◦ C at
2.13 kPa, bp 156 ◦ C at 0.6 kPa. It decomposes
above 200 ◦ C and is slightly volatile in steam
and insoluble in water.
Benzyl benzoate is produced by esterifying
dry sodium benzoate with benzyl chloride [13]
or by the dimerization of benzaldehyde [14]. It is
also obtained from the bottoms of benzoic acid
rectification plants (see page 2).
Benzyl benzoate is used as a dye carrier.
Other uses include solvents for cellulose deriva-
tives, plasticizers, and fixatives in the perfume
industry.
8.3. Benzoyl Chloride
Physical Properties. Benzoyl chloride
[98-88-4], C7 H5 ClO, M r 140.57, mp −0.6 ◦ C,
bp 198.3 ◦ C, vapor pressure 0.133 kPa at
32.1 ◦ C, 1.33 kPa at 73.8 ◦ C, 13.3 kPa at 128 ◦ C,
colorless liquid with a penetrating odor, lachry-
matory, fumes on exposure to air, n20 D 1.55369,
d 20
4 1.2113, decomposes in water and alcohols,
miscible with benzene, flash point 102 ◦ C, au-
toignition temperature 600 ◦ C, heat of combus-
tion 3282 kJ/mol.
Chemical Properties. Benzoyl chloride re-
hydrochloric acid. If the amount of water is lim-
ited, benzoic anhydride is formed. Reaction with
ammonia forms benzamide [55-21-0]. Benzoyl
chloride is an excellent benzoylation reagent for
compounds with active hydrogen, such as alco-
hols, phenols, or amines, under Friedel – Crafts
Production. Benzoyl chloride is produced
commercially from benzotrichloride [98-07-7],
which is available by the chlorination of toluene.
The chlorination reaction proceeds stepwise via
benzyl chloride [100-44-7] and benzal chloride
[98-87-3].
C6 H5 CH3 + Cl2 −→ C6 H5 CH2 Cl + HCl
C6 H5 CH2 Cl + Cl2 −→ C6 H5 CHCl2 + HCl
C6 H5 CHCl2 + Cl2 −→ C6 H5 CCl3 + HCl
The benzotrichloride is then partially hy-
drolyzed with a limited amount of water.
C6 H5 CCl3 + H2 O → C6 H5 COCl + 2 HCl
This series of reactions consumes a large quan-
tity of chlorine. An alternative process uses ben-
zoic acid.

C6 H5 CCl3 + C6 H5 COOH −→ 2 C6 H5 COCl + HCl
Phosphorous chlorides or iron chlorides are
used as catalysts at the solvolytic stage of both
processes. Benzoyl chloride can also be made
by the reaction of benzoic acid with phosgene,
thionyl chloride, or phosphorous pentachloride
[15]; chlorination of benzaldehyde, benzyl alco-
hol, or benzyl benzoate [16]; and direct reaction
of benzene with phosgene or the combination of
carbon monoxide and chlorine [17].
The benzoyl chloride prepared by the con-
ventional processes may contain trace amounts
of chlorobenzoyl chloride, but the product ob-
tained by the reaction of molten phthalic anhy-
dride with hydrogen chloride at 200 ◦ C is free
of such impurities.
Uses. Benzoyl chloride is used in making
organic peroxides. Benzoyl peroxide [94-36-0]
and tert-butyl peroxybenzoate [614-45-9] are
widely used as polymerization initiators and as
curing agents in the polymer industries. Other
uses include intermediates for rubber additives,
UV absorbers, dyes, insecticides, and pharma-
ceuticals.
Specifications. Assay 99.5 % min., sp
above − 0.5 ◦ C, benzal chloride 0.01 % max.,
trichlorobenzal chloride 0.01 % max., color
(APHA) 10 max.
8.4. Benzonitrile
Physical Properties. Benzonitrile [100-47-0],
C7 H5 N, M r 103.12, mp −13.8 ◦ C, bp 191.1 ◦ C,
vapor pressure 1.37 kPa at 70 ◦ C, 2.27 kPa at
79 ◦ C, 4.53 kPa at 94 ◦ C, colorless liquid, al-
mond oil odor, n15 20
D 1.53056, d 4 1.0052, sol-
ubility in water 1 wt % at 100 ◦ C, miscible
with common organic solvents, heat capacity cp
1.840 J g−1 K−1 , heat of vaporization 46 kJ/mol,
heat of formation −155 kJ/mol, heat of combus-
tion 3063 kJ/mol, flash point 70 ◦ C.
Chemical Properties. Benzonitrile is stable
in air and light. In the presence of a strong
base or acid, benzonitrile is hydrolyzed to ben-
zoic acid and ammonia (via benzamide). Ben-
zylamine [100-46-9] and dibenzylamine can be
prepared from benzonitrile by hydrogenation.
Benzoic Acid and Derivatives 7
Benzonitrile is a powerful solvent. At room
temperature it dissolves poly(vinyl chloride),
poly(vinyl acetate) resins, polystyrene, poly-
methacrylate, and nitrocellulose. It does not dis-
solve polyethylene, polyamide, poly(vinyl alco-
hol), or fluoropolymers.
Production. Benzonitrile is produced by
the high-temperature vapor-phase oxidation of
toluene in the presence of ammonia. The tra-
ditional catalysts are vanadium and molyb-
denum, but they suffers from low selectivity
and serious decomposition of ammonia [18]. A
tungsten – manganese complex catalyst shows
better performance [19]. With the latter catalyst,
the reaction is carried out in a fixed-bed reactor
at 450 ◦ C. The concentration of toluene in the
feed stream is 1.5 vol %. The ratio of ammonia
to toluene is 4 : 1 with a contact time of 2.4 s. The
reaction converts 97 % of the toluene and 30 %
of the ammonia. The selectivity is 87.4 %. The
crude product, which contains ammonia, hydro-
gen cyanide, toluene, and high-boilers, is puri-
fied by distillation.
Benzonitrile has also been produced from
benzoic acid and ammonia in the vapor phase
at 400 – 410 ◦ C over alumina [20] or in the liq-
uid phase at 225 – 245 ◦ C [21]. Other methods
include liquid-phase ammoxidation of toluene in
the presence of a cobalt or manganese bromide
catalyst [22], dehydrogenative condensation of
benzyl alcohol or benzaldehyde with ammonia,
the high-temperature reaction of toluene with
nitrous oxide, and cyanation of benzene with
cyanogen chloride or dicyanogen.
Uses. The major derivative of benzonitrile
is benzoguanamine [91-76-9], which is made
by the reaction of benzonitrile with dicyanodi-
amide in the presence of a strong base [23]. Ben-
zoguanamine reacts with formaldehyde and/or
alcohols to afford a heat-resistant thermosetting
resin.
8.5. Alkyl and Acyl Analogues
Methylbenzoic acids, C8 H8 O2 , M r 136.15.
The physical properties of the methylbenzoic
acids are presented in Table 6.
8 Benzoic Acid and Derivatives

The chemical properties of the methylben-

495 ± 5

570 ± 5
Ignition
point,

zoic acids are similar to those of benzoic acid.

◦
C

They are better preservatives than benzoic acid,

but their higher toxicity limits their application.
148 ± 3

181 ± 1

Their alkali metal salts have better anticorrosion

point,
Flash

146
C

effects than benzoates.

◦
formation,

−416.5
−426.1
−429.2

2-Methylbenzoic acid [118-90-1], o-toluic

Heat of

kJ/mol

acid, can be produced by the oxidation of o-

xylene. It is an intermediate for agrochemicals,
combustion,

such as the fungicide mepronil and the herbicide

londax.
Heat of

kJ/mol

3887
3886
3880

3-Methylbenzoic acid [99-04-7], m-toluic

acid, is predominantly used for the production
Heat of
fusion,

J g−1 K−1 kJ/mol

of an insect repellant, N,N’-diethyl-m-toluamide

20.2
15.7
22.7

[134-62-3]. Other uses are as an intermediate for

poly(vinyl chloride) stabilizers and agrochemi-
capacity,

cals.
1.285
1.219
1.204
Heat

4-Methylbenzoic acid [99-94-5], p-toluic

xylene, 14 ◦ C,

acid, is an intermediate in the production of

sponding
in corre-

terephthalic acid by oxidation of p-xylene. The

wt %

methyl group of 4-methylbenzoic acid, unlike

6.64
7.89
1.45

that of toluene or p-xylene, is resistant to oxida-

in chloro-

tion by molecular oxygen with a conventional

benzene,
31.8 ◦ C,
mol %

12.73
14.07
1.76

cobalt catalyst. The addition of bromide over-

comes this difficulty. 4-Methylbenzoic acid can
be prepared from p-xylene by vapor-phase oxi-
100 ◦ C,

wt %

dation or nitric acid oxidation. 4-Methylbenzoic

1.16

acid is used for producing intermediates for an-

Solubility
in water

tibiotic pharmaceuticals, and organic pigments.

25 ◦ C,

0.118
0.098
0.034
wt %

4-tert-Butylbenzoic acid [98-73-7],

C11 H14 O2 , M r 178.23, crystals, mp 168.5 –
169 ◦ C, dissociation constant 6.99 × 10−7 at
1.0543 at 112 ◦ C
◦
1.062 at 115 C

25 ◦ C.
1.23 at 20 ◦ C

4-tert-Butylbenzoic acid is obtained by the

Density,
Table 6. Physical properties of the methylbenzoic acids

g/cm3

liquid-phase air oxidation of 4-tert-butyltoluene

(prepared from toluene and isobutylene) [24]. It
is a modifier for alkyd resins and a polymeriza-
263
274
259
C
bp,

tion regulator for polyesters. It is also used as

an additive in cutting oils and as a corrosion in-
110
180
105
mp,

hibitor. It is hydrogenated to afford the fragrance

◦

4-tert-butylbenzaldehyde [939-97-9].
3-Methylbenzoic acid
4-Methylbenzoic acid
2-Methylbenzoic acid

2-Benzoylbenzoic acid [85-52-9], benzophenone-

o-carboxylic acid, C14 H10 O3 , M r 226.23, mp
127 ◦ C.
The Friedel – Crafts acylation of benzene
with phthalic anhydride is generally used to pro-
duce 2-benzoylbenzoic acid. 2-Benzoylbenzoic
 Benzoic Acid and Derivatives 9
Table 7. Physical properties of the monochlorobenzoic acids

2-Chlorobenzoic acid 3-Chlorobenzoic acid 4-Chlorobenzoic acid

◦
mp, C 141 154 241.5
bp, ◦ C 279 275 276
Density, g/cm3 1.544 at 20 ◦ C 1.517 at 25 ◦ C 1.571 at 24 ◦ C
Solubility, wt %
in water at 25 ◦ C 0.21 0.045 0.0077
at 100 ◦ C 4.02 0.5 0.11
in benzene at 14 – 16 ◦ C 0.92 0.66 0.017
Heat capacity, J g−1 K−1 1.042 1.042 1.073
Heat of fusion, kJ/mol 25.68 23.85 32.25
Heat of combustion, kJ/mol 3084 3069 3066
Dissociation constant at 25 ◦ C, Ka 1.2×10−3 1.5×10−4 1.05×10−4
Flash point, ◦ C 173 ± 6 150 238 ± 1

Table 8. Physical properties of the aminobenzoic acids

2-Aminobenzoic acid 3-Aminobenzoic acid 4-Aminobenzoic acid

◦
mp, C 146.1 177.9 188.0
Crystal structure rhombic monocline monoclinic
Density
at 20 ◦ C, g/cm3 1.367 1.5105
Solubility, wt %
0.59 at 25 ◦ C,
in water 0.35 at 14 ◦ C 0.59 at 15 ◦ C 1.1 at 100 ◦ C
in 90 % ethanol 10.7 at 9.6 ◦ C 2.2 at 9.6 ◦ C 11.3 at 9.6 ◦ C
in benzene 0.18 at 11.4 ◦ C 0.06 at 11 ◦ C
Dissociation constant at 25 ◦ C
Kacid 1.07×10−5 1.67×10−5 1.2×10−5
Kbase 1.1×10−12 7.9×10−12 1.7×10−12

Table 9. Physical properties of the mononitrobenzoic acids

2-Nitrobenzoic acid 3-Nitrobenzoic acid 4-Nitrobenzoic acid

mp, ◦ C 148 142 240

Density, g/cm3 1.575 1.494 1.610
Solubility, g per 100 mL of solvent at 10 ◦ C
in water 0.75 (at 25 ◦ C) 0.24 (at 15 ◦ C) 0.02 (at 15 ◦ C)
in methanol 42.72 47.34 9.6
in benzene 0.294 0.795 0.017 (at 12.5 ◦ C)
Heat capacity, J g−1 K−1 1.149 1.035 1.077
Heat of fusion, kJ/mol 28.02 29.33 37.02
Heat of combustion, kJ/mol 3078 3053 3881
Dissociation constant, Ka 6.1×10−3 at 18 ◦ C 3.48×10−4 at 25 ◦ C 3.93×10−4 at 25 ◦ C
Decarboxylation temperature, ◦ C 180 238 > 240

acid is principally used for the production of
photosensitizers.
8.6. Chlorobenzoic Acids
The physical properties of the monochloroben-
zoic acids are listed in Table 7.
2-Chlorobenzoic acid [118-91-2], C7 H5 ClO2 , [2136-89-2]. 2-Chlorobenzoic acid is used
M r 156.57.
2-Chlorobenzoic acid is the strongest acid
among the three isomers. Its chlorine atom is
easily exchangeable. It is decarboxylated in
aqueous solution at 300 ◦ C. With sodium sulfite
it gives 2-sulfobenzoic acid. 2-Aminobenzoic
acid is formed with ammonia. 2-Chlorobenzoic
acid is produced by oxidation of 2-chlorotoluene
[95-49-8] with molecular oxygen [25] or by
the hydrolysis of α,α,α,2-tetrachlorotoluene
10 Benzoic Acid and Derivatives
for the manufacture of sweeteners, anti-
inflammatory pharmaceuticals, and fungicides.
3-Chlorobenzoic acid [535-80-8], C7 H5 ClO2 .
The reactivity of the chlorine atom of 3-
chlorobenzoic acid is sluggish compared with
the other isomers. Decarboxylation at higher
temperatures is insignificant, and it resists ox-
idation. 3-Chlorobenzoic acid is made by the
oxidation of 3-chlorotoluene [108-41-8] or
by the hydrolysis of 3-chlorobenzoyl chloride
[618-46-2], which is derived from benzoyl chlo-
ride. 3-Chlorobenzoic acid is used for making
diphenyl ether type herbicides.
4-Chlorobenzoic acid [74-11-3], C7 H5 ClO2 is
produced by the oxidation of 4-chlorotoluene
[106-43-4].
2,4-Dichlorobenzoic acid [50-84-0],
◦ 2-Aminobenzoic acid is called vitamin L1 ;
C7 H4 Cl2 O2 , M r 191.01, mp 164 C, needles,
slightly soluble in water.
2,4-Dichlorobenzoic acid is an important
pharmaceutical chemical used in diuretics, an-
tirheumatics, and antimalarials. It is produced by is an intermediate for indigo synthesis. Mordant
the oxidation of 2,4-dichlorotoluene [95-73-8],
which is obtained by the direct chlorination of
toluene.
2,5-Dichlorobenzoic acid [50-79-3],
C7 H4 Cl2 O2 , mp 154.4 ◦ C, bp 301 ◦ C.
2,5-Dichlorobenzoic acid is made from ben-
zoyl chloride by chlorination and hydrolysis. It
is used as a starting material in the production
of herbicides.
8.7. Aminobenzoic Acids
Aminobenzoic acids, C7 H7 NO2 , M r 137.14.
The physical properties of aminobenzoic
acids are presented in Table 8.
2-Aminobenzoic acid [118-92-3],
thranilic acid, was first obtained from indigo
by alkali fusion. The methyl derivative is found
in essential oils. It is an off-white crystalline
powder of sweetish taste, sublimable, and freely
soluble in hot water. It has an amphoteric char-
acter as a weak acid and a weak base. Therefore,
it is soluble in strong acids and bases. It is easily
decarboxylated to form aniline.
2-Aminobenzoic acid is usually made from
phthalic anhydride via sodium phthalamate.
Oxidative decarboxylation (the Hofmann re-
action) is carried out by the addition of sodium
hypochlorite solution at 60 – 100 ◦ C followed by
acidification.
The product is purified with activated car-
bon and bisulfite. The overall yield is 88 %.
Other synthetic routes include the amination of
2-chlorobenzoic acid and the reduction of 2-
nitrobenzoic acid.
it enhances the milk production of cows. The
major use of 2-aminobenzoic acid is as an inter-
mediate for dyes. As its occurrence suggests, it
Brown 40 and Vat Violet 13 are other derivatives.
4-Hydroxy-1-methyl-carbostyril [1677-46-9] is
an important derivative used in making dyes and
pigments. Its methyl and ethyl esters are used as
fragrances for toiletries. In the pharmaceutical
industry, it is used as an intermediate for tran-
quilizers and antiphlogistics.
3-Aminobenzoic acid [99-05-8] is prepared
by the reduction of 3-nitrobenzoic acid and used
in dye syntheses. Its derivative N,N-dimethyl-3-
aminobenzoic acid [99-64-9] is also used in the
production of dyes.
4-Aminobenzoic acid [150-13-0] is widely
found in nature as a factor in vitamin B
complex. Baker’s yeast contains 5 or 6 mg/kg
of 4-aminobenzoic acid, and brewer’s yeast
an- 10 – 100 mg/kg. It enhances the growth of var-
ious microorganisms, and it is essential to the
anaerobic metabolism of some bacteria. It is
known as bacterial vitamin H and is antagonistic
to sulfonamide drugs. It darkens slightly on ex-
posure to air or light. It is slightly soluble in cold
water. The pH of a 0.5 wt % aqueous solution is
3.5. It is soluble in ethyl acetate and acetic acid
but practically insoluble in petroleum ether.
 Benzoic Acid and Derivatives 11

Table 10. Acute toxicity data for benzoic acid and its derivatives (RTECS)

Compound Species Route Acute toxicity

Benzoic acid rat oral LD50 1700 mg/kg

[65-85-0] mouse oral LD50 1940 mg/kg
rat inhalation LC50 > 26 mg/m3
rat i.p. LD50 1600 mg/kg
mouse i.p. LD50 1460 mg/kg
human skin TDL0 6 mg/kg
rabbit s.c. LDL0 2 g/kg
rabbit irritation (skin) mild
rabbit irritation (eye) severe
Sodium benzoate rat oral LD50 4070 mg/kg
[532-32-1] mouse oral LD50 1600 mg/kg
dog oral LD50 2 g/kg
mouse i.v. LD50 1440 mg/kg
rat s.c. LD50 2 g/kg
mouse i.m. LD50 2306 mg/kg
Methyl benzoate rat oral LD50 1177 mg/kg
[93-58-3] mouse oral LD50 3330 mg/kg
rabbit irritation (skin) mild
rabbit irritation (eye) mild
n-Butyl benzoate rat oral LD50 735 mg/kg
[136-60-7] rabbit skin LD50 4 g/kg
rabbit irritation (skin) severe
rabbit irritation (eye) mild
Diethylene glycol dibenzoate rat oral LD50 2830 mg/kg
[120-55-8] rabbit skin LD50 20 g/kg
rabbit irritation (skin) mild
rabbit irritation (eye) mild
Phenyl benzoate mouse oral LD50 1225 mg/kg
[93-99-2]
Benzyl benzoate rat oral LD50 1700 µL/kg
[120-51-4] mouse oral LD50 1400 µL/kg
dog oral LD50 > 22.44 g/kg
mouse i.p. LD50 > 500 mg/kg
rabbit skin LD50 4 g/kg
Benzoyl chloride rat oral LD50 1900 mg/kg
[98-88-4] rat inhalation LC50 1870 mg/m3
Benzonitrile rat oral LDL0 720 mg/kg
[100-47-0] mouse oral LD50 971 mg/kg
rat inhalation LCL0 950 ppm
mouse inhalation LC50 1800 mg/m3
mouse i.p. LD50 400 mg/kg
rabbit s.c. LDL0 200 mg/kg
rabbit skin LD50 1250 mg/kg
rabbit irritation (skin) moderate
Benzaldehyde rat oral LD50 1300 mg/kg
[100-52-7] mouse oral LD50 28 mg/kg
rat inhalation LC50 > 500 mg/m3
rat s.c. LDL0 5 g/kg
mouse i.p. LD50 9 mg/kg
rabbit irritation (skin) moderate
2-Methylbenzoic acid mouse i.p. LD50 422 mg/kg
[118-90-1]
3-Methylbenzoic acid rat oral LD50 > 5 g/kg
[99-04-7] mouse oral LD50 1630 mg/kg

The conventional method of producing 4-
aminobenzoic acid is the reduction of 4-
nitrobenzoic acid. The Hofmann degradation re-
action of terephthalic acid is another source of 4-
aminobenzoic acid. Dimethyl terephthalate re-
acts with one equivalent of potassium hydroxide
in methanol. The resultant salt is then amidated
with liquid ammonia in dimethylformamide at
130 – 140 ◦ C to give potassium terephthalamate.
This then reacts with sodium hypochlorite solu-
tion at 50 – 92 ◦ C. The overall yield is approxi-
mately 70 % [26].
12 Benzoic Acid and Derivatives
Table 10. (Continued)

Compound Species Route Acute toxicity

mouse i.p. LD50 562 mg/kg

4-Methylbenzoic acid mouse oral LD50 2340 mg/kg
[99-94-5] rat i.p. LD50 874 mg/kg
mouse i.p. LD50 916 mg/kg
4-tert-butylbenzoic acid rat oral LD50 700 mg/kg
[98-73-7] rat inhalation LC50 > 1900 mg/m3
2-Chlorobenzoic acid rat oral LD50 > 500 mg/m3
[118-91-2] rat i.p. LD50 2350 mg/kg
rabbit irritation (skin) mild
rabbit irritation (eye) moderate
3-Chlorobenzoic acid rat i.p. LD50 750 mg/kg
[535-80-8]
4-Chlorobenzoic acid rat oral LD50 1170 mg/kg
[74-11-3] mouse oral LD50 1170 mg/kg
rat i.p. LD50 1 g/kg
2,4-Dichlorbenzoic acid mouse oral LD50 830 mg/kg
[50-84-0] mouse s.c. LD50 1200 mg/kg
2,5-Dichlorobenzoic acid mouse i.p. LD50 237 mg/kg
[50-79-3] mouse s.c. LD50 1200 mg/kg
2-Aminobenzoic acid rat oral LD50 5410 mg/kg
[118-92-3] mouse oral LD50 1400 mg/kg
mouse i.v. LD50 > 500 mg/kg
mouse i.p. LD50 2500 mg/kg
3-Aminobenzoic acid mouse oral LD50 6300 mg/kg
[99-05-8] mouse i.p. LD50 500 mg/kg
4-Aminobenzoic acid rat oral LD50 > 6 g/kg
[150-13-0] mouse oral LD50 2850 mg/kg
dog oral LD50 1 g/kg
rabbit i.v. LD50 2 g/kg
rat i.p. LD50 > 3450 mg/kg
3-Nitrobenzoic acid mouse i.v. LD50 640 mg/kg
[121-92-6] mouse i.p. LD50 610 mg/kg
4-Nitrobenzoic acid rat oral LD50 1960 mg/kg
[62-23-7] mouse i.v. LD50 770 mg/kg
mouse i.p. LD50 880 mg/kg
rabbit irritation (eye) moderate
Hexahydrobenzoic acid rat oral LD50 3265 mg/kg
[98-89-5]

Folic acid [59-30-3], another derivative of 4-

aminobenzoic acid, is a hematopoietic vitamin.

8.8. Nitrobenzoic Acids

The physical properties of the mononitrobenzoic
acids are given in Table 9.

2-Nitrobenzoic acid [27178-83-2], C7 H5 NO4 ,

A two-stage Hofmann reaction has been de-
veloped. The yield is 93 % [27].
4-Aminobenzoic acid is used principally
in the pharmaceuticals industry. Other uses
are as a cross-linking agent for polyurethane
resins, dyes, and feedstock additives. Ethyl
4-aminobenzoate [94-09-7], anesthesin, mp
90 – 91 ◦ C is a local anesthetic of low toxicity,
irritation, and persistency. It is used especially
by dentists.
M r 167.12, can be prepared by the oxidation of
2-nitrotoluene [88-72-2] with nitric acid.
3-Nitrobenzoic acid [121-92-6] is prepared
by nitrating benzoic acid at low temperature.
Approximately 20 % of the 2-nitro isomer and
1.5 % of the 4-nitro isomer are co-produced.
The 3-Nitrobenzoic acid can be purified by re-
crystallization of the sodium salt. The oxidation
of 3-nitrobenzaldehyde [99-61-6], prepared by

the controlled oxidation of benzaldehyde, gives
a higher yield. 3-Nitrobenzoic acid is an inter-
mediate in the preparation of 3-aminobenzoic
acid and azo dyes. Its derivative 4-chloro-3-
nitrobenzoic acid [96-99-1] is an intermediate
in the production of dyes.
4-Nitrobenzoic acid [62-23-7] is produced
commercially by the oxidation of 4-nitrotoluene
[99-99-0] with molecular oxygen. Oxidation
with 15 % nitric acid at 175 ◦ C produces the
acid in 88.5 % yield. An interesting method in-
volves the nitration and subsequent oxidation of
polystyrene [28]. This method uses the steric
hindrance of the polymer chain to improve the
para to ortho ratio of the product.
4-Nitrobenzoic acid is an intermediate for
4-aminobenzoic acid. 4-Nitrobenzoyl chloride
[122-04-3], mp 75 ◦ C, is a starting material for
procaine hydrochloride and folic acid.
8.9. 3-Sulfobenzoic Acid
3-Sulfobenzoic acid [121-53-9], mp 141 ◦ C, mp
of dihydrate 98 ◦ C, hygroscopic, soluble in wa-
ter and ethanol. It is produced by the direct sul-
fonation of benzoic acid with oleum in ca. 85 %
yield. 3-Sulfobenzoic acid is chiefly used for the
production of 3-hydroxybenzoic acid [99-06-9]
by alkali fusion.
8.10. Hexahydrobenzoic Acid
Hexahydrobenzoic acid [98-89-5], cyclo-
hexanecarboxylic acid, C7 H12 O2 , M r 128.17,
mp 30 – 31 ◦ C, bp 232 – 234 ◦ C, bp 150.7 ◦ C
at 6.53 kPa, bp 120 – 121 ◦ C at 1.87 kPa, d 20 4
1.0274, slightly soluble in water, soluble in eth-
anol and petroleum ether.
Hexahydrobenzoic acid reacts with nitrosyl-
sulfuric acid to produce caprolactam. This is the
basic reaction of the toluene-based caprolactam
process (→ Caprolactam). Hexahydrobenzoic
acid can be oxidized by molecular oxygen at
220 ◦ C in the presence of a copper catalyst [29].
The main products are cyclohexene and cyclo-
hexanone. It can be dehydrocarbonylated in the
vapor phase over a heteropoly acid catalyst to
yield cyclohexene [30]. Hexahydrobenzoic acid
Benzoic Acid and Derivatives 13
is produced in quantitative yield by the hydro-
genation of benzoic acid over noble metal cata-
lysts at 150 – 170 ◦ C, at elevated pressure.
9. Toxicology
Acute toxicity data for benzoic acid and its
derivatives are given in Table 10.
Benzoic acid is not accumulated in the hu-
man body. After administration it reacts with
glycine to form hippuric acid, which is excreted
in the urine. The FAO/WHO guideline for the
upper limit of daily intake of benzoic acid is
5 – 10 mg/kg. The reproductive toxicity test for
rats showed no abnormality.
Benzoic acid has an irritating effect on hu-
man mucous membranes. When dust formation
is anticipated, protections should be arranged.
Benzoyl chloride is significantly toxic,
like other acid chlorides. It irritates mu-
cous membranes strongly (for further data on
toxicology, see → Chlorinated Hydrocarbons,
Chap. 10.2.6.).
Benzonitrile is less toxic than aliphatic ni-
triles. It is, nevertheless, absorbed through the
skin and may cause convulsions of tissue and
paralysis of nerves.
The esters of 4-aminobenzoic acid have a lo-
cal anesthetic effect. After absorption they stim-
ulate the central nervous system. At the work-
place, some of these derivatives may have an
allergenic and skin hypersensitizing effect.
4-Nitrobenzoic acid has a significant bacteri-
cidal action against Staphylococci and Strepto-
cocci. It is reported to be slightly mutagenic.
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8. BIOS 1786; BIOS (Misc.) 112.
14 Benzoic Acid and Derivatives
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10. Mitsubishi Chem. Ind., JP-Kokai 56-39045,
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27. Akzo, DE 2313580, 1973.
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29. J. A. Bigot, P. L. Kerkhoffs, Recl. Trav. Chim.
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Benzoin → Ketones
Benzophenone → Ketones
30. Mitsubishi Chem. Ind., JP 55-37532, 1980;
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37. European Parliament Council, Official Journal,
no. L061 (1995) 0001 – 0040.
38. Iowa
State University, material safety data sheets, see
http://avogadro.chem.iastate.edu/msds/msds.html
39. Safety Information on the Internet, see
http://siri.org/index.html
40. C. Barron:

Benzoic acid

in SRI
International Chemical Economics Handbook,
1995, 618, 8000A.
41. 21 CFR 184. 1733 (Report no. 88, US Dept. of
Agriculture).
42. Chemical Market Reporter Sept. 29, 1997.