Article No : a04_001

Benzyl Alcohol
€
FRIEDRICH BRUHNE, Bayer AG, Krefeld-Uerdingen, Federal Republic of Germany
ELAINE WRIGHT, General Motors Research Laboratories, Warren, Michigan,
United States, 48090

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . 357 6. Storage, Transportation, and Safety

2. Physical Properties . . . . . . . . . . . . . . . . . . . 357 Regulations . . . . . . . . . . . . . . . . . . . ..... . 362
3. Chemical Properties . . . . . . . . . . . . . . . . . . 358 7. Uses . . . . . . . . . . . . . . . . . . . . . . . . . ..... . 362
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . . 359 8. Derivatives . . . . . . . . . . . . . . . . . . . . ..... . 362
4.1. Hydrolysis of Benzyl Chloride . . . . . . . . . . . 359 8.1. Dibenzyl Ether. . . . . . . . . . . . . . . . . ..... . 362
4.2. Hydrogenation and Reduction of 8.2. Benzyl Acetate . . . . . . . . . . . . . . . . . ..... . 362
Benzaldehyde . . . . . . . . . . . . . . . . . . . . . . . . 360 8.3. Benzyl Benzoate. . . . . . . . . . . . . . . . ..... . 363
4.3. Oxidation of Toluene . . . . . . . . . . . . . . . . . . 360 8.4. Benzyl Salicylate . . . . . . . . . . . . . . . ..... . 363
4.4. Other Manufacturing Processes. . . . . . . . . . 361 9. Economic Aspects . . . . . . . . . . . . . . ..... . 363
5. Quality Standards and Test Methods . . . . . 361 10. Toxicology . . . . . . . . . . . . . . . . . . . . ..... . 363
References . . . . . . . . . . . . . . . . . . . . ..... . 364

1. Introduction 2. Physical Properties

Benzyl alcohol [100-51-6] is the simplest and
also the industrially most important aromatic
alcohol. LIEBIG and W€
oHLER first prepared benzyl
alcohol from bitter almond oil (benzaldehyde)
in 1832 [3]. The structure of benzyl alcohol
was determined in 1853 by CANNIZZARO [4].
CANNIZZARO used the reaction named after him,
in which benzaldehyde is disproportionated into
benzoic acid and benzyl alcohol through the
action of an alkali.
Benzyl alcohol occurs in nature both free and
in combined forms. In the latter case it exists as
esters of acetic, benzoic, salicylic, and cinnamic
acids, among others. It is known to occur in the
balsams of Peru and Tolu, in the flower oils of
hyacinths and wallflowers, in ylang-ylang oil,
and in other essential oils. It also occurs as a
glucoside in maize.
Benzyl alcohol, C7H8O, is a colorless liquid with
a faint aromatic odor and a mildly irritating effect
on the mucous membranes.
Mr 108.14, bp 205.4
C at 101.3 kPa, mp
15.4
C, refractive index n20D 1:5400, density
r 1.061 g/cm3 at 0
C, 1.045 g/cm3 at 20
C,
1.030 g/cm3 at 40
C, 1.015 g/cm3 at 60
C.
Specific heat 1972 J kg1 K1 at 20
C, 2135 J
1 1
kg K at 50
C, heat of fusion 82.9 J/g, heat of
evaporation 467.0 J/g at 205.4
C, standard com-
bustion enthalpy 34.58 kJ/g.
Flash point 101
C, autoignition temperature
435
C, lower explosive limit (at 170
C and
101.3 kPa) 1.3 vol %, upper explosive limit
13.0 vol %.
Table 1 shows the vapor pressure in relation
to temperature.
Benzyl alcohol is miscible with many organic
solvents. At 20
C, 4.0 g of benzyl alcohol is
soluble in 100 g of water and 5.1 g of water is
soluble in 100 g of benzyl alcohol. The composi-
tions of several binary azeotropic mixtures are
given in Table 2. For further azeotropes, see

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a04_001
358 Benzyl Alcohol Vol. 5

Table 1. Vapor pressure of benzyl alcohol vs. temperature Oxidation results in benzaldehyde or benzoic


Temperature, C Vapor pressure, kPa
acid, depending on the nature of the oxidizing
agent and the reaction conditions. Thus nitric
60 0.18 acid as an oxidizing agent gives benzaldehyde
80 0.66
100 2.02 [8], whereas solid sodium permanganate mono-
120 5.28 hydrate gives benzoic acid [9]. Under the con-
140 12.20 ditions of the Oppenauer oxidation, benzyl alco-
160 25.47 hol is oxidized to benzaldehyde in the presence of
180 48.88
200 87.43 furfural as a hydrogen acceptor [10]. Benzalde-
hyde is also formed slowly if benzyl alcohol is
exposed to air. Benzyl alcohol can be dehydro-
[5]. Liquid – vapor equilibrium data for binary
genated in the gas phase using catalysts contain-
mixtures of benzyl alcohol with water or organic
ing copper or noble metals. The main product of
solvents are given in [6].
the dehydrogenation is benzaldehyde.
Dynamic viscosity h 5.584103 Pa  s at
Depending on the reaction conditions, the
20
C, surface tension s 39.96103 N/m at
hydrogenation of benzyl alcohol gives toluene,
20
C. Dipole moment m (measured in liquid
benzene, methylcyclohexane, cyclohexane, and
benzene) 5.5711030 C  m (1.67 D), relative
hydroxymethylcyclohexane.
dielectric constant r 11.92 at 30
C, 9.81 at 60
C.
The reactions between benzyl alcohol and
hydrogen halides give the corresponding benzyl
halides [11]. Under the conditions for chlorinat-
3. Chemical Properties ing the side chains of aromatic compounds,
benzyl alcohol forms benzoyl chloride [12].
The chemical properties of benzyl alcohol are
With ammonia or amines, benzyl alcohol can
determined mainly by the hydroxyl group. This
be converted into N-alkyl-, N,N-dialkyl-, N,N,N-
group shows the typical reactions of aliphatic
trialkylamines. In the presence of Friedel-Crafts
alcohols (! Alcohols, Aliphatic). The reactivity
catalysts, aromatic hydrocarbons can be alky-
of the hydroxyl group is increased by the prox-
lated on the aromatic nucleus. Thus benzyl alco-
imity of the aromatic nucleus. Benzyl alcohol is
hol and benzene form diphenylmethane, whereas
less acidic than the isomeric cresols and therefore
benzyl alcohol and phenol give a mixture of 2-
not completely soluble in aqueous alkalis.
and 4-benzylphenols.
If benzyl alcohol is heated in the presence of
With organic and inorganic acids, acid halides,
dehydrating compounds (e.g., aluminum oxide),
or acid anhydrides, benzyl alcohol reacts in the
dibenzyl ether, toluene, and benzaldehyde are
normal way to give the corresponding esters. The
formed. Dibenzyl ether is also formed when
acid-catalyzed reactions of benzyl alcohol with
benzyl alcohol is heated with strong acids or
aldehydes give acetals. The addition of carbon
bases. Mixed ethers can be prepared simply
monoxide to benzyl alcohol in the presence of
through the action of alkyl halides on benzyl
carbonyl catalysts, e.g., rhodium trichloride with
alcohol in the presence of bis(acetylacetonato)
benzyl iodide, leads to phenylacetic acid [13].
nickel as a catalyst [7].
The treatment of benzyl alcohol with Friedel-
Table 2. Azeotropes of benzyl alcohol
Crafts catalysts (e.g., anhydrous aluminum chlo-
ride, zinc chloride, concentrated sulfuric acid, or
bp (101.3 kPa), Benzyl alcohol, perchloric acid) results in the elimination of


Component C wt % water and the formation of resinous products
Water 99.9 9.0 having the composition H(C7H6)n OH and cor-
Hexachloroethane 182.0 12.0 responding to the polybenzyl made from benzyl
Ethylene glycol 193.4 46.5 chloride. At temperatures above 150
C, as little
Nitrobenzene 204.2 62.0
Dimethylaniline 193.9 6.5 as 1 % hydrogen bromide and 0.04 % iron (II)
Diethylaniline 204.2 72.0 can cause the exothermic polycondensation of
Naphthalene 204.1 60.0 benzyl alcohol to proceed very rapidly. In this
p-Cresol 206.8 62.0 reaction the temperature rises to 240
C, and the
p-Bromotoluene 184.5 8.0
sudden pressure increase may be sufficient to
Vol. 5
break a closed vessel [14]. Thus, for safety
reasons, benzyl alcohol should not be heated to
temperatures above 100
C unless it is free from
acidic matter and dissolved iron.
4. Production
Benzyl alcohol can be produced in many ways.
At present there are only two processes of sub-
stantial industrial importance.
1. The hydrolysis of benzyl chloride
2. The hydrogenation of benzaldehyde
4.1. Hydrolysis of Benzyl Chloride
The hydrolysis of benzyl chloride is a reversible
reaction which leads to the almost quantitative
formation of benzyl alcohol only in the pres-
ence of alkaline saponifying agents that com-
bine with the hydrogen chloride as it is formed.
It is therefore carried out by heating benzyl
chloride with stoichiometric excesses of aque-
ous solutions of oxides, hydroxides, or carbo-
nates of the alkali or alkaline earth metals. As in
the following example, soda is the preferred
saponifying agent.
To 610 parts of boiling 10 % soda solution
126.5 parts of benzyl chloride is added with
stirring. The reaction mixture is refluxed and
stirred until carbon dioxide no longer escapes;
this takes an average of five to six hours. An
alkali-resistant steel reactor with brick walls is
used. The stirrer and heating coil are made of an
alloy with a high nickel content. After the reac-
tion mixture has cooled, the upper layer, consist-
ing of crude benzyl alcohol, is removed. The
sodium chloride solution below still contains
some soda. Dissolved benzyl alcohol can be
obtained from it by adding salt or by extracting
with benzene or toluene. The crude benzyl alco-
hol is carefully fractionated at a reduced pressure
in an efficient column. The yield is 85 parts of
benzyl alcohol and 10 parts of dibenzyl ether.
Benzyl Alcohol 359
In the discontinuous hydrolysis of benzyl
chloride the reaction time can be reduced by
hydrolyzing the final residue of benzyl chloride
with sodium hydroxide solution after the saponi-
fication with soda solution has been in progress
for three hours [15]. The total saponification time
required is then only four hours. Normally 8 –
12 % of dibenzyl ether is formed as an unavoid-
able byproduct of the alkaline hydrolysis of
benzyl chloride. Pure dibenzyl ether is recovered
by distillation from the residue in the distillation
column. The use of alkali hydroxides instead of
carbonates reduces the reaction time but favors
the formation of dibenzyl ether, which may then
exceed 20 % in the crude benzyl alcohol. The
percentage of dibenzyl ether can be reduced if the
hydrolysis is performed in the presence of an
inert solvent, such as benzene, toluene, or xylene.
Benzyl alcohol can be produced continuously
if benzyl chloride and the aqueous alkaline solu-
tion of saponifying agent react in a flow reactor at
an elevated temperature (150 – 350
C) and suf-
ficient pressure to maintain the reactants in the
liquid phase. Thorough mixing of the reactants is
important; it can be achieved by the use of
suitable baffles in the flow reactor [16] or by
maintaining an adequate flow rate [17]. The
residence time need then be no more than a few
minutes. The mixture emerging from the hydro-
lysis zone is processed in the normal way. Only a
small amount of dibenzyl ether is formed and this
can be further reduced by using an inert solvent.
In a new continuous process, benzyl chloride,
flowing in one direction, and the alkaline saponi-
fying agent, flowing in the other, are reacted as
counter-currents in an inert organic solvent (e.g.,
toluene, xylene) in a flow reactor. In the extrac-
tion zone, the alcohol dissolved in the aqueous
alkaline phase is extracted by an inert organic
solvent flowing in the opposite direction. Water,
likewise as a countercurrent, washes the solution
of the crude benzyl alcohol in a washing zone.
The flow reactor, extracting zone, and washing
zone are integrated in a special apparatus
(Fig. 1). The wash water and extract are returned
to the hydrolysis zone. This process can be
operated at low reaction temperatures (120 –
150
C) and with a small stoichiometric excess
of saponifying agent (5 – 25 %); a small reactor
can be used [18].
In a two-step process, benzyl chloride reacts
with sodium acetate to form benzyl acetate,
360 Benzyl Alcohol
Figure 1. Hydrolysis of benzyl chloride to form benzylal-
cohol in a continuous-flow reactor [18]
which is then saponified to form benzyl alcohol
[19]. In a similar process, benzyl chloride reacts
with an alkali or alkaline earth formate in the
presence of a catalyst to form benzyl formate.
The benzyl alcohol is liberated by subsequent
transesterification using an alcohol and a catalyst
[20]. Neither of these processes has acquired
much importance in the manufacture of benzyl
alcohol. However, they could have advantages in
the hydrolysis of certain substituted benzyl chlor-
ides that react with soda solution to give dibenzyl
ethers and not the desired alcohol.
4.2. Hydrogenation and Reduction of
Benzaldehyde
The industrial production of benzyl alcohol by
the hydrogenation of benzaldehyde gained
importance because substantial quantities of
Vol. 5
benzaldehyde were available as a byproduct of
the production of phenol (Dow process) and
-caprolactam (Snia Viscosa process) by the oxi-
dation of toluene (! Benzaldehyde).
Depending on the reaction conditions, benz-
aldehyde can be hydrogenated to form benzyl
alcohol, toluene, hydroxymethylcyclohexane,
methylcyclohexane, and other products. Howev-
er, very high yields of benzyl alcohol are obtain-
able if suitable reaction conditions and catalysts
are chosen. Raney nickel doped with transition
metals [21], nickel or platinum metals with
phosphines or phosphine oxides [22], palladium
combined with an organic nitrogen [23] or alkali
base [24], water [25], or another transition metal
[26] can serve as the catalyst. If benzaldehyde is
hydrogenated at temperatures of 70 – 200
C
and a hydrogen pressure of 1 – 4 MPa, high
yields of benzyl alcohol are obtained in short
reaction times. In a well-known continuous pro-
cess [27], benzaldehyde is hydrogenated to form
benzyl alcohol with a high degree of efficiency
and a high selectivity in the presence of a plati-
num–aluminum oxide–lithium oxide catalyst.
Stannane [28], sodium hydride [29], zinc [30],
and microorganisms [31] can also be used to
reduce benzaldehyde to benzyl alcohol, but these
processes have no industrial importance. Benzyl
alcohol is no longer produced industrially using
the Cannizzaro reaction.
4.3. Oxidation of Toluene
The catalytic oxidation of toluene [32] gives only
low yields of benzyl alcohol because the reaction
conditions support further oxidation to benzalde-
hyde and benzoic acid. Therefore intermediates
are isolated in most benzyl alcohol production
processes that start with toluene. The liquid-phase
oxidation of toluene with oxygen-depleted air at
170 – 220
C and pressure sufficient to keep the
reaction medium liquid is carried out in the
presence of stabilizers for organic hydroperoxides
(e.g., sodium pyrophosphate or sodium fluoride).
It leads mainly to benzyl hydroperoxide [33] if not
more than 10 % of the toluene is permitted to
react. The subsequent decomposition of the oxi-
dation product at 165
C in the presence of solu-
ble cobalt salts yields benzyl alcohol. Benzalde-
hyde and benzoic acid are formed in fairly large
quantities as byproducts. Benzyl hydroperoxide
Vol. 5
can also be reduced to benzyl alcohol using alkali
metal sulfites [34].
The oxidation of toluene as a liquid phase in
air is conducted in the presence of acids, acid
chlorides, or acid anhydrides; it forms the benzyl
esters of these acids. These are then saponified to
form benzyl alcohol. For example, the oxidation
of toluene in the presence of acetic anhydride at
temperatures of 140 – 240
C and pressures of
1 – 3 MPa yields benzyl acetate [35]. The oxi-
dation is discontinued after 10 % of the toluene
has reacted. After the saponification of the oxi-
dation product, 350 g of benzyl alcohol, 55 g of
benzaldehyde, and 67 g of benzoic acid are
obtained from 500 g of reacted toluene. Phenolic
impurities, e.g., cresols, are unavoidably present
in the benzyl alcohol obtained by the oxidation of
toluene. These impurities can be removed by
washing the benzyl alcohol vapor with a coun-
tercurrent of alkali benzylate solution in a plate
column or a packed column [36].
4.4. Other Manufacturing Processes
The hydrogenation of benzoic acid esters to form
benzyl alcohol is of particular interest in cases
where benzoic acid esters are formed in substan-
tial amounts. For example, methyl benzoate is
formed in the production of dimethyl terephthal-
ate by the Witten process. Catalysts containing
copper are preferred. Benzoic acid esters can be
hydrogenated to form benzyl alcohol with the aid
of a copper catalyst and a carrier consisting of
alkaline earth oxides or carbonates [37]. The
selectivity can be increased if the catalyst also
contains chromium. Temperatures of 100 –
300
C and pressures above 6 MPa are used.
The hydrogenation of methyl benzoate in the
presence of a copper–chromium catalyst is a
feature of a three-step process for the production
of benzyl alcohol from toluene [38]. The first step
is the oxidation of toluene to form benzoic acid.
The acid is esterified with methanol in the second
step. The hydrogenation of methyl benzoate to
form benzyl alcohol is performed in the final step.
This process produces benzyl alcohol at an ex-
ceptionally low cost.
Ruthenium, rhodium, platinum, and palladi-
um, activated by alkali metal arenes, ketyls, or
alkoxides, are catalysts for the hydrogenation of
the esters [39]. Using these catalysts, benzoic
Benzyl Alcohol 361
acid esters can be hydrogenated to form benzyl
alcohol under mild conditions and with high
selectivity.
Other processes for the production of benzyl
alcohol include the hydrogenation of benzoic
acid [40], the electrochemical reduction of ben-
zoic acid [41], the hydrolysis of benzylsulfonic
acid [42], and the decarboxylation of benzyl
formate [43]. These processes have no impor-
tance in the industrial production of benzyl alco-
hol, but they may be used to produce derivatives
substituted on the aromatic nucleus. Benzyl al-
cohol can also be obtained from the benzyl
benzoate which is formed in the manufacture of
benzoic acid [44].
5. Quality Standards and Test
Methods
Several grades of benzyl alcohol are commer-
cially available (Table 3). Technical grade is
obtained as the first and last fractions in the
distilla tion of the crude alcohol, it has little
importance. Pure benzyl alcohol is the most
important grade in terms of volume and is re-
quired for most applications. Double-distilled
benzyl alcohol is used mainly in the perfume
and pharmaceutical industries and must therefore
be exceptionally pure and free of foreign odors.
At 25
C it forms a clear 4 % aqueous solution.
The photographic grade normally contains
0.01 – 0.02 % of hydroquinone monomethyl
ether to inhibit oxidation.
Gas chromatography using packed or capil-
lary columns is suitable for the quantitative
determination of benzyl alcohol. It is more accu-
rate than the method involving acetylation of the
hydroxyl group with pyridine and acetic anhy-
dride. Traces of chlorine compounds are un-
avoidably present in the benzyl alcohol produced
Table 3. Specifications for certain grades of benzyl alcohol (wt %)
Grades
Tech- Pure Double Photo-
Compound nical distilled graphic
Benzyl alcohol > 97.0 > 99.0 > 99.8 > 99.5
Benzaldehyde < 0.5 < 0.2 < 0.04 < 0.03
Chlorine < 0.2 < 0.02 < 0.01 < 0.005
Dibenzyl ether < 2.0 < 0.05 < 0.02 < 0.02
362 Benzyl Alcohol
by hydrolysis of benzyl chloride. Byproducts,
e.g., cresols, may be present in the benzyl alcohol
obtained by the oxidation method or via benzal-
dehyde. Chlorine is quantitatively determined by
Wickbold combustion [45], and cresols can be
detected by color reactions with aminoantipyrine
[36]. Benzaldehyde can be quantitatively deter-
mined using hydroxylamine hydrochloride.
The pharmacopoeias of the various countries
should be consulted regarding the testing of
benzyl alcohol which is to be used in the phar-
maceutical industry.
6. Storage, Transportation, and
Safety Regulations
Benzyl alcohol is stored in stainless steel tanks.
Because benzyl alcohol oxidizes readily, it is
advisable to cover the surface of the liquid with
nitrogen. Benzyl alcohol can be transported in
drums protected by stoving finishes and in tank
wagons of aluminum or stainless steel.
Benzyl alcohol belongs to Temperature Class
T 2 (autoignition temperature 435
C). The
transportation of benzyl alcohol by rail, road, or
water is not subject to special regulations. The
labeling of benzyl alcohol must comply with the
national and international regulations on danger-
ous substances.
7. Uses
By virtue of its good solvent properties, benzyl
alcohol is an important solvent for surface-coat-
ing materials and resins. It dissolves cellulose
esters and ethers, alkyd resins, acrylic resins, and
fats; it is also used as an ingredient in the inks for
ball-point pens. It is added in small amounts to
surface-coating materials to improve their flow
and gloss. In the textile industry, it is used as an
auxiliary in the dyeing of wool, polyamides, and
polyesters. Because it has only a relatively faint
odor, it is used as a solvent and diluting agent in
the manufacture of perfumes and flavors. In color
photography it is increasingly important as a
development accelerator. In pharmacy it is used
as a local anesthetic and, because of its microbi-
cidal effect, as an ingredient of ointments and
other preparations.
Vol. 5
Benzyl alcohol is a starting material for the
preparation of numerous benzyl esters that are
used as odorants, flavors, stabilizers for volatile
perfumes, and plasticizers. Benzyl alcohol is also
used in the extractive distillation of m- and p-
xylenes and m- and p-cresols.
8. Derivatives
The most important derivatives of benzyl alcohol
are dibenzyl ether, benzyl acetate, benzyl benzo-
ate, and benzyl salicylate.
8.1. Dibenzyl Ether
Dibenzyl ether [103-50-4], C14H14O, M r 198.27,
is a colorless liquid with a faint odor; mp 3.6
C,
bp 296 – 298
C at 101.3 kPa, bp 157 –158
C
at 1.2 kPa, density r 1.043 g/cm3 at 20
C, re-


fractive index n20 D 1:5622, flash point 135 C.
The compound is very slightly soluble in water.
Production. Dibenzyl ether is formed when
benzyl alcohol is heated with strong acids or
bases. It is produced almost exclusively by the
alkaline hydrolysis of benzyl chloride. Heat
treatment decomposes dibenzyl ether into benz-
aldehyde and toluene.
Use. Dibenzyl ether is used as a plasticizer in
the surface coatings industry, for special pur-
poses in the rubber and textile industries, and as a
solvent for musk and other odorants.
Excess dibenzyl ether can be converted into a
mixture of benzotrichloride and benzoyl chloride
under the conditions of side chain chlorination
with chlorine [46]. Treatment of dibenzyl ether
with hydrochloric acid in the presence of trialkyl-
or tetraalkylammonium salts gives benzyl chlo-
ride [47].
8.2. Benzyl Acetate
Benzyl acetate [140-11-4], C9H10O2, Mr 150.18,
is a colorless liquid with an odor of pears and
jasmine. It is a constituent of jasmine, gardenia,
Vol. 5
and other flower oils; mp  51.5
C, bp 215
C
at 101.3 kPa, density r 1.056 g/cm3 at 20
C,


refractive index n20
D 1:5020, flash point 102 C,
very slightly soluble in water.
Production and Use. Benzyl acetate is pro-
duced by reacting benzyl chloride with an alkali
acetate or by esterifying benzyl alcohol with
acetic anhydride. It is also formed in the oxida-
tion of toluene in the presence of acetic acid or
acetic anhydride. Benzyl acetate is one of the
most used odorants. It is also used as a flavor and,
to a small extent, as a high-boiling solvent.
8.3. Benzyl Benzoate
Benzyl benzoate [120-51-4], C14H12O2, Mr
212.25, is a colorless, viscous liquid with a
pleasant odor. It is the main constituent of Peru
balsam, Tolu balsam, and certain flower oils; mp
19 – 21
C, bp 323 – 324
C at 101.3 kPa, den-
sity r 1.112 g/cm3 at 25
C, refractive index

9. Economic Aspects
n24
D 1:5672, flash point 148 C, insoluble in water
and glycerol.
Production. Benzyl benzoate is produced
from benzyl alcohol and sodium benzoate in the
presence of triethylamine or by transesterifica-
tion of methyl benzoate with benzyl alcohol in
the presence of an alkali benzyl oxide. In another
manufacturing process benzaldehyde is con-
densed to form benzyl benzoate in the presence
of sodium (Claisen-Tishchenko condensation).
The presence of a small amount of an aliphatic
ether improves this reaction [48]. Benzyl benzo-
ate is a byproduct in the manufacture of benzoic
acid by the oxidation of toluene; it is present in
the benzoic acid distillation residue.
Use. Benzyl benzoate is used in perfume
manufacture, mainly to stabilize volatile odor-
ants. It has vasodilating and spasmolytic effects
and is present in many asthma and whooping
cough drugs. It is used as an insect repellent and
to treat scabies. Benzyl benzoate is used as a
Benzyl Alcohol 363
plasticizer in the surface coatings and plastics
industries.
8.4. Benzyl Salicylate
Benzyl salicylate [118-58-1], C14H12O3, Mr
228.25, is a colorless, viscous liquid with a
pleasant odor. It occurs naturally in several es-
sential oils; mp 24
C, bp 211
C at 2.67 kPa,
density r 1.175 g/cm3 at 25
C, refractive index
n25
D 1:5787, slightly soluble in water.
Production and Use. Benzyl salicylate can
be manufactured by reacting benzyl chloride
with an alkali salicylate or by the transesterifica-
tion of methyl salicylate with benzyl alcohol. It is
used as a perfume stabilizer and, because it
absorbs ultraviolet light, as an ingredient in
sunscreening preparations.
The benzyl alcohol production capacities of
Western Europe and the United States in 1983
were approximately 10 kt and 6 kt, respectively.
About 7 kt of benzyl alcohol was actually pro-
duced in Western Europe in 1983. Approxi-ma-
tely 3.4 kt of benzyl alcohol was produced in the
United States in 1979.
10. Toxicology
Benzyl alcohol is used in pharmaceuticals, soaps,
detergents, and cosmetics as a fragrance, preser-
vative, and antimicrobial, and is ‘‘generally re-
garded as safe’’ (GRAS) for use in food by the U.
S. Food and Drug Administration. It has indus-
trial applications as a solvent and dye assistant,
but no environmental or workplace exposure
limits have been established.
Benzyl alcohol is moderately toxic with acute
oral LD50 values of 1.2 g/kg in rats and 1.6 g/kg
in mice [49]. The LD50 for inhalation exposure is
approximately 1.0 g/kg (eight hours) in rats [50].
Benzyl alcohol can be absorbed through the skin
364 Benzyl Alcohol
in sufficient quantities to cause toxicity; the
dermal LD50 in guinea pigs is < 5 mL/kg
[51]. In vitro screening tests for chemical carci-
nogens in a repair-deficient bacterial strain
(P 3478 E. coli) were negative [52]. Benzyl
alcohol is not considered to be a carcinogen and
no data are available regarding teratogenic or
reproductive effects.
Benzyl alcohol is widely used as a preserva-
tive in solutions of drugs for intravenous admin-
istration. The minimum lethal dose in dogs (i.v.)
is between 88 and 113 mL/kg of a 0.9 vol %
solution of benzyl alcohol in water or in physio-
logical saline solution [53]. Similar doses have
been fatal for newborn humans receiving benzyl
alcohol in the course of intravenous drug treat-
ment [54]. Benzyl alcohol is estimated to be more
than twenty times more toxic than ethyl alcohol
(i.v.) [53].
Benzyl alcohol is severely toxic and highly
irritating to the eye. Contact with benzyl alcohol
causes mild to moderate skin irritation [55].
Hypersensitivity reactions may occur in some
individuals with both topical and parenteral ad-
ministration [56].
Signs of intoxication include vomiting and
diarrhea, collapse, central nervous system depres-
sion, excitability, muscle paralysis, convulsions,
dyspnea, and respiratory arrest [55]. Exposure
should be avoided by the use of adequate ventila-
tion systems, self-contained respiration equip-
ment, protective goggles, gloves, and clothing.
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