Benzyl Alcohol 1

Benzyl Alcohol
Friedrich Brühne, Bayer AG, Krefeld-Uerdingen, Federal Republic of Germany (Chaps. 1 – 9)

Elaine Wright, General Motors Research Laboratories, Warren, Michigan 48090, United States (Chap. 10)

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

2. Physical Properties . . . . . . . . . . . . 1 Regulations . . . . . . . . . . . . ..... 6
3. Chemical Properties . . . . . . . . . . . 2 7. Uses . . . . . . . . . . . . . . . . . ..... 6
4. Production . . . . . . . . . . . . . . . . . . 3 8. Derivatives . . . . . . . . . . . . . ..... 6
8.1. Dibenzyl Ether . . . . . . . . . . ..... 6
4.1. Hydrolysis of Benzyl Chloride . . . . . 3
8.2. Benzyl Acetate . . . . . . . . . . ..... 7
4.2. Hydrogenation and Reduction of Ben- 8.3. Benzyl Benzoate . . . . . . . . . ..... 7
zaldehyde . . . . . . . . . . . . . . . . . . . 4 8.4. Benzyl Salicylate . . . . . . . . . ..... 7
4.3. Oxidation of Toluene . . . . . . . . . . . 4 9. Economic Aspects . . . . . . . . ..... 7
4.4. Other Manufacturing Processes . . . . 5 10. Toxicology . . . . . . . . . . . . . ..... 7
5. Quality Standards and Test Methods 5 11. References . . . . . . . . . . . . . ..... 8

1. Introduction M r 108.14, bp 205.4 ◦ C at 101.3 kPa, mp

−15.4 ◦ C, refractive index n20
D 1.5400, density
Benzyl alcohol [100-51-6] is the simplest and
1.061 g/cm3 at 0 ◦ C, 1.045 g/cm3 at 20 ◦ C,
also the industrially most important aromatic al- 1.030 g/cm3 at 40 ◦ C, 1.015 g/cm3 at 60 ◦ C.
cohol. Liebig and Wöhler first prepared ben- Specific heat 1972 J kg−1 K−1 at 20 ◦ C,
zyl alcohol from bitter almond oil (benzalde- 2135 J kg−1 K−1 at 50 ◦ C, heat of fu-
hyde) in 1832 [3]. The structure of benzyl al- sion 82.9 J/g, heat of evaporation 467.0 J/g at
cohol was determined in 1853 by Cannizzaro 205.4 ◦ C, standard combustion enthalpy 34.58
[4]. Cannizzaro used the reaction named after kJ/g.
him, in which benzaldehyde is disproportionated Flash point 101 ◦ C, autoignition tempera-
into benzoic acid and benzyl alcohol through the ture 435 ◦ C, lower explosive limit (at 170 ◦ C
action of an alkali. 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 occurs in nature both free and Table 1. Vapor pressure of benzyl alcohol vs. temperature
in combined forms. In the latter case it exists as
Temperature, ◦ C Vapor pressure, kPa
esters of acetic, benzoic, salicylic, and cinnamic
acids, among others. It is known to occur in the 60 0.18
balsams of Peru and Tolu, in the flower oils of 80 0.66
100 2.02
hyacinths and wallflowers, in ylang-ylang oil, 120 5.28
and in other essential oils. It also occurs as a 140 12.20
160 25.47
glucoside in maize. 180 48.88
200 87.43

2. Physical Properties Benzyl alcohol is miscible with many organic

solvents. At 20 ◦ C, 4.0 g of benzyl alcohol is
Benzyl alcohol, C7 H8 O, is a colorless liquid soluble in 100 g of water and 5.1 g of water is
with a faint aromatic odor and a mildly irritating soluble in 100 g of benzyl alcohol. The compo-
effect on the mucous membranes. sitions of several binary azeotropic mixtures are

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

10.1002/14356007.a04 001
2 Benzyl Alcohol

given in Table 2. For further azeotropes, see [5]. furfural as a hydrogen acceptor [10]. Benzalde-
Liquid – vapor equilibrium data for binary mix- hyde is also formed slowly if benzyl alcohol is
tures of benzyl alcohol with water or organic exposed to air. Benzyl alcohol can be dehydro-
solvents are given in [6]. genated in the gas phase using catalysts contain-
ing copper or noble metals. The main product of
Table 2. Azeotropes of benzyl alcohol
the dehydrogenation is benzaldehyde.
Component bp (101.3 kPa), Benzyl alcohol, Depending on the reaction conditions, the
◦
C wt % hydrogenation of benzyl alcohol gives toluene,
Water 99.9 9.0 benzene, methylcyclohexane, cyclohexane, and
Hexachloroethane 182.0 12.0 hydroxymethylcyclohexane.
Ethylene glycol 193.4 46.5
Nitrobenzene 204.2 62.0
The reactions between benzyl alcohol and hy-
Dimethylaniline 193.9 6.5 drogen halides give the corresponding benzyl
Diethylaniline 204.2 72.0 halides [11]. Under the conditions for chlori-
Naphthalene 204.1 60.0
p-Cresol 206.8 62.0 nating the side chains of aromatic compounds,
p-Bromotoluene 184.5 8.0 benzyl alcohol forms benzoyl chloride [12].
With ammonia or amines, benzyl alco-
Dynamic viscosity η 5.584×10−3 Pa · s at hol can be converted into N-alkyl-, N,N-
20 C, surface tension σ 39.96×10−3 N/m at
◦ dialkyl-, N,N,N-trialkylamines. In the presence
20 ◦ C. Dipole moment µ (measured in liquid of Friedel-Crafts catalysts, aromatic hydrocar-
benzene) 5.571×10−30 C · m (1.67 D), relative bons can be alkylated on the aromatic nucleus.
dielectric constant εr 11.92 at 30 ◦ C, 9.81 at Thus benzyl alcohol and benzene form diphenyl-
60 ◦ C. methane, whereas benzyl alcohol and phenol
give a mixture of 2- and 4-benzylphenols.
With organic and inorganic acids, acid
3. Chemical Properties halides, or acid anhydrides, benzyl alcohol re-
acts in the normal way to give the correspond-
The chemical properties of benzyl alcohol are ing esters. The acid-catalyzed reactions of ben-
determined mainly by the hydroxyl group. This zyl alcohol with aldehydes give acetals. The ad-
group shows the typical reactions of aliphatic al- dition of carbon monoxide to benzyl alcohol in
cohols (→ Alcohols, Aliphatic). The reactivity the presence of carbonyl catalysts, e.g., rhodium
of the hydroxyl group is increased by the prox- trichloride with benzyl iodide, leads to phenyl-
imity of the aromatic nucleus. Benzyl alcohol is acetic acid [13].
less acidic than the isomeric cresols and there- The treatment of benzyl alcohol with Friedel-
fore not completely soluble in aqueous alkalis. Crafts catalysts (e.g., anhydrous aluminum chlo-
If benzyl alcohol is heated in the presence of ride, zinc chloride, concentrated sulfuric acid, or
dehydrating compounds (e.g., aluminum oxide), perchloric acid) results in the elimination of wa-
dibenzyl ether, toluene, and benzaldehyde are ter and the formation of resinous products hav-
formed. Dibenzyl ether is also formed when ben- ing the composition H(C7 H6 )n OH and corre-
zyl alcohol is heated with strong acids or bases. sponding to the polybenzyl made from benzyl
Mixed ethers can be prepared simply through chloride. At temperatures above 150 ◦ C, as little
the action of alkyl halides on benzyl alcohol in as 1 % hydrogen bromide and 0.04 % iron (II)
the presence of bis(acetylacetonato)nickel as a can cause the exothermic polycondensation of
catalyst [7]. benzyl alcohol to proceed very rapidly. In this
Oxidation results in benzaldehyde or benzoic reaction the temperature rises to 240 ◦ C, and
acid, depending on the nature of the oxidizing the sudden pressure increase may be sufficient
agent and the reaction conditions. Thus nitric to break a closed vessel [14]. Thus, for safety
acid as an oxidizing agent gives benzaldehyde reasons, benzyl alcohol should not be heated to
[8], whereas solid sodium permanganate mono- temperatures above 100 ◦ C unless it is free from
hydrate gives benzoic acid [9]. Under the condi- acidic matter and dissolved iron.
tions of the Oppenauer oxidation, benzyl alcohol
is oxidized to benzaldehyde in the presence of

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 presence
of alkaline saponifying agents that combine with
the hydrogen chloride as it is formed. It is there-
fore carried out by heating benzyl chloride with
stoichiometric excesses of aqueous solutions of
oxides, hydroxides, or carbonates of the alkali
or alkaline earth metals. As in the following ex-
ample, 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 re-
action mixture has cooled, the upper layer, con-
sisting of crude benzyl alcohol, is removed. The
sodium chloride solution below still contains
some soda. Dissolved benzyl alcohol can be ob-
tained from it by adding salt or by extracting with
benzene or toluene. The crude benzyl alcohol 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.
In the discontinuous hydrolysis of benzyl
chloride the reaction time can be reduced by
hydrolyzing the final residue of benzyl chlo-
ride with sodium hydroxide solution after the
saponification with soda solution has been in
progress for three hours [15]. The total saponi-
fication time required is then only four hours.
Normally 8 – 12 % of dibenzyl ether is formed
Benzyl Alcohol 3
as an unavoidable byproduct of the alkaline hy-
drolysis of benzyl chloride. Pure dibenzyl ether
is recovered by distillation from the residue in
the distillation column. The use of alkali hydrox-
ides instead of carbonates reduces the reaction
time but favors the formation of dibenzyl ether,
which may then exceed 20 % in the crude ben-
zyl 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 so-
lution of saponifying agent react in a flow re-
actor at an elevated temperature (150 – 350 ◦ C)
and sufficient pressure to maintain the reactants
in the liquid phase. Thorough mixing of the re-
actants 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
hydrolysis 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. Wa-
ter, likewise as a countercurrent, washes the so-
lution of the crude benzyl alcohol in a wash-
ing zone. The flow reactor, extracting zone, and
washing zone are integrated in a special appa-
ratus (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 re-
acts with sodium acetate to form benzyl acetate,
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
4 Benzyl Alcohol
transesterification using an alcohol and a cata-
lyst [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
chlorides that react with soda solution to give
dibenzyl ethers and not the desired alcohol.
Figure 1. Hydrolysis of benzyl chloride to form benzyl
alcohol in a continuous-flow reactor [18]
4.2. Hydrogenation and Reduction of
Benzaldehyde
The industrial production of benzyl alcohol by
the hydrogenation of benzaldehyde gained im-
portance because substantial quantities of ben-
zaldehyde were available as a byproduct of
the production of phenol (Dow process) and ε-
caprolactam (Snia Viscosa process) by the oxi-
dation of toluene (→ Benzaldehyde).
Depending on the reaction conditions, ben-
zaldehyde can be hydrogenated to form benzyl
alcohol, toluene, hydroxymethylcyclohexane,
methylcyclohexane, and other products. How-
ever, very high yields of benzyl alcohol are ob-
tainable if suitable reaction conditions and cata-
lysts are chosen. Raney nickel doped with transi-
tion 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 process [27],
benzaldehyde is hydrogenated to form benzyl
alcohol with a high degree of efficiency and a
high selectivity in the presence of a platinum–
aluminum oxide–lithium oxide catalyst. Stan-
nane [28], sodium hydride [29], zinc [30], and
microorganisms [31] can also be used to reduce
benzaldehyde to benzyl alcohol, but these pro-
cesses have no industrial importance. Benzyl al-
cohol 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
benzaldehyde and benzoic acid. Therefore in-
termediates 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 suf-
ficient to keep the reaction medium liquid is
carried out in the presence of stabilizers for or-
ganic hydroperoxides (e.g., sodium pyrophos-
phate or sodium fluoride). It leads mainly to ben-
zyl hydroperoxide [33] if not more than 10 %
of the toluene is permitted to react. The subse-
quent decomposition of the oxidation product at
165 ◦ C in the presence of soluble cobalt salts
yields benzyl alcohol. Benzaldehyde and ben-
zoic acid are formed in fairly large quantities
as byproducts. Benzyl hydroperoxide 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 ob-
tained 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 terephtha-
late 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 se-
lectivity can be increased if the catalyst also con-
tains 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 fea-
ture 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 sec-
ond step. The hydrogenation of methyl benzoate
to form benzyl alcohol is performed in the final
step. This process produces benzyl alcohol at an
exceptionally low cost.
Ruthenium, rhodium, platinum, and palla-
dium, activated by alkali metal arenes, ketyls,
or alkoxides, are catalysts for the hydrogenation
of the esters [39]. Using these catalysts, benzoic
acid esters can be hydrogenated to form benzyl
Benzyl Alcohol 5
alcohol under mild conditions and with high se-
lectivity.
Other processes for the production of ben-
zyl 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 for-
mate [43]. These processes have no importance
in the industrial production of benzyl alcohol,
but they may be used to produce derivatives sub-
stituted on the aromatic nucleus. Benzyl alcohol
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 ob-
tained as the first and last fractions in the dis-
tilla tion of the crude alcohol, it has little impor-
tance. Pure benzyl alcohol is the most important
grade in terms of volume and is required 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 hydro-
quinone monomethyl ether to inhibit oxidation.
Gas chromatography using packed or cap-
illary columns is suitable for the quantitative
determination of benzyl alcohol. It is more
accurate than the method involving acetyla-
tion of the hydroxyl group with pyridine and
acetic anhydride. Traces of chlorine compounds
are unavoidably present in the benzyl alco-
hol produced by hydrolysis of benzyl chloride.
Byproducts, e.g., cresols, may be present in
the benzyl alcohol obtained by the oxidation
method or via benzaldehyde. Chlorine is quan-
titatively determined by Wickbold combustion
[45], and cresols can be detected by color reac-
tions with aminoantipyrine [36]. Benzaldehyde
can be quantitatively determined using hydrox-
ylamine hydrochloride.
The pharmacopoeias of the various countries
should be consulted regarding the testing of ben-
zyl alcohol which is to be used in the pharma-
ceutical industry.
6 Benzyl Alcohol
Table 3. Specifications for certain grades of benzyl alcohol (wt %)
Compound Grades
Tech- Pure
nical
Benzyl alcohol > 97.0 > 99.0
Benzaldehyde < 0.5 < 0.2
Chlorine < 0.2 < 0.02
Dibenzyl ether < 2.0 < 0.05
6. Storage, Transportation, and
Safety Regulations
Benzyl alcohol is stored in stainless steel tanks.
Because benzyl alcohol oxidizes readily, it is ad-
visable 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, ben-
zyl alcohol is an important solvent for surface-
coating materials and resins. It dissolves cel-
lulose esters and ethers, alkyd resins, acrylic
resins, and fats; it is also used as an ingredi-
ent 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 in-
dustry, 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 accel-
erator. In pharmacy it is used as a local anesthetic
and, because of its microbicidal effect, as an in-
gredient of ointments and other preparations.
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.
Double Photo-
distilled graphic
> 99.8 > 99.5
< 0.04 < 0.03
< 0.01 < 0.005
< 0.02 < 0.02
8. Derivatives
The most important derivatives of benzyl alco-
hol are dibenzyl ether, benzyl acetate, benzyl
benzoate, and benzyl salicylate.
8.1. Dibenzyl Ether
Dibenzyl ether [103-50-4], C14 H14 O, 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
1.043 g/cm3
at 20 ◦ C, refractive 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 ben-
zaldehyde 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 chlo-
ride under the conditions of side chain chlorina-
tion with chlorine [46]. Treatment of dibenzyl
ether with hydrochloric acid in the presence of
trialkyl- or tetraalkylammonium salts gives ben-
zyl chloride [47].

8.2. Benzyl Acetate
Benzyl acetate [140-11-4], C9 H10 O2 , M r
150.18, is a colorless liquid with an odor of pears
and jasmine. It is a constituent of jasmine, gar-
denia, and other flower oils; mp − 51.5 ◦ C, bp
215 ◦ C at 101.3 kPa, density
1.056 g/cm3 at
20 ◦ C, refractive index n20D 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 al-
kali 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], C14 H12 O2 , M r
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
1.112 g/cm3 at 25 ◦ C, refractive index 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 transester-
ification of methyl benzoate with benzyl alco-
hol in the presence of an alkali benzyl oxide. In
another manufacturing process benzaldehyde is
condensed to form benzyl benzoate in the pres-
ence of sodium (Claisen-Tishchenko condensa-
tion). The presence of a small amount of an
aliphatic ether improves this reaction [48]. Ben-
zyl benzoate is a byproduct in the manufacture
of benzoic acid by the oxidation of toluene; it is
present in the benzoic acid distillation residue.
Benzyl Alcohol 7
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
plasticizer in the surface coatings and plastics
industries.
8.4. Benzyl Salicylate
Benzyl salicylate [118-58-1], C14 H12 O3 , M r
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
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 transesterifi-
cation 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.
9. Economic Aspects
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-
mately 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,
preservative, and antimicrobial, and is “gener-
ally regarded as safe” (GRAS) for use in food
by the U.S. Food and Drug Administration. It
has industrial applications as a solvent and dye
8 Benzyl Alcohol
assistant, but no environmental or workplace ex-
posure 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
in sufficient quantities to cause toxicity; the der-
mal LD50 in guinea pigs is < 5 mL/kg [51]. In
vitro screening tests for chemical carcinogens
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 preser-
vative in solutions of drugs for intravenous ad-
ministration. 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 ben-
zyl alcohol in the course of intravenous drug
treatment [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 alco-
hol 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 de-
pression, excitability, muscle paralysis, convul-
sions, dyspnea, and respiratory arrest [55]. Ex-
posure should be avoided by the use of ad-
equate ventilation systems, self-contained res-
piration equipment, protective goggles, gloves,
and clothing.
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