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 Benzyl alcohol, C7H8O, is a colorless liquid with
also the industrially most important aromatic a faint aromatic odor and a mildly irritating effect
alcohol. LIEBIG and W€
oHLER first prepared benzyl on the mucous membranes.
alcohol from bitter almond oil (benzaldehyde) Mr 108.14, bp 205.4
C at 101.3 kPa, mp
in 1832 [3]. The structure of benzyl alcohol 15.4
C, refractive index n20D 1:5400, density
was determined in 1853 by CANNIZZARO [4]. r 1.061 g/cm3 at 0
C, 1.045 g/cm3 at 20
C,
CANNIZZARO used the reaction named after him, 1.030 g/cm3 at 40
C, 1.015 g/cm3 at 60
C.
in which benzaldehyde is disproportionated into Specific heat 1972 J kg1 K1 at 20
C, 2135 J
1 1
benzoic acid and benzyl alcohol through the kg K at 50
C, heat of fusion 82.9 J/g, heat of
action of an alkali. 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 %.
Benzyl alcohol occurs in nature both free and Table 1 shows the vapor pressure in relation
in combined forms. In the latter case it exists as to temperature.
esters of acetic, benzoic, salicylic, and cinnamic Benzyl alcohol is miscible with many organic
acids, among others. It is known to occur in the solvents. At 20
C, 4.0 g of benzyl alcohol is
balsams of Peru and Tolu, in the flower oils of soluble in 100 g of water and 5.1 g of water is
hyacinths and wallflowers, in ylang-ylang oil, soluble in 100 g of benzyl alcohol. The composi-
and in other essential oils. It also occurs as a tions of several binary azeotropic mixtures are
glucoside in maize. 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 Benzyl Alcohol 359

break a closed vessel [14]. Thus, for safety In the discontinuous hydrolysis of benzyl
reasons, benzyl alcohol should not be heated to chloride the reaction time can be reduced by
temperatures above 100
C unless it is free from hydrolyzing the final residue of benzyl chloride
acidic matter and dissolved iron. with sodium hydroxide solution after the saponi-
fication with soda solution has been in progress
for three hours [15]. The total saponification time
4. Production required is then only four hours. Normally 8 –
12 % of dibenzyl ether is formed as an unavoid-
Benzyl alcohol can be produced in many ways. able byproduct of the alkaline hydrolysis of
At present there are only two processes of sub- benzyl chloride. Pure dibenzyl ether is recovered
stantial industrial importance. by distillation from the residue in the distillation
column. The use of alkali hydroxides instead of
1. The hydrolysis of benzyl chloride 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
2. The hydrogenation of benzaldehyde 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-
4.1. Hydrolysis of Benzyl Chloride ficient pressure to maintain the reactants in the
liquid phase. Thorough mixing of the reactants is
The hydrolysis of benzyl chloride is a reversible important; it can be achieved by the use of
reaction which leads to the almost quantitative suitable baffles in the flow reactor [16] or by
formation of benzyl alcohol only in the pres- maintaining an adequate flow rate [17]. The
ence of alkaline saponifying agents that com- residence time need then be no more than a few
bine with the hydrogen chloride as it is formed. minutes. The mixture emerging from the hydro-
It is therefore carried out by heating benzyl lysis zone is processed in the normal way. Only a
chloride with stoichiometric excesses of aque- small amount of dibenzyl ether is formed and this
ous solutions of oxides, hydroxides, or carbo- can be further reduced by using an inert solvent.
nates of the alkali or alkaline earth metals. As in In a new continuous process, benzyl chloride,
the following example, soda is the preferred flowing in one direction, and the alkaline saponi-
saponifying agent. fying agent, flowing in the other, are reacted as
To 610 parts of boiling 10 % soda solution counter-currents in an inert organic solvent (e.g.,
126.5 parts of benzyl chloride is added with toluene, xylene) in a flow reactor. In the extrac-
stirring. The reaction mixture is refluxed and tion zone, the alcohol dissolved in the aqueous
stirred until carbon dioxide no longer escapes; alkaline phase is extracted by an inert organic
this takes an average of five to six hours. An solvent flowing in the opposite direction. Water,
alkali-resistant steel reactor with brick walls is likewise as a countercurrent, washes the solution
used. The stirrer and heating coil are made of an of the crude benzyl alcohol in a washing zone.
alloy with a high nickel content. After the reac- The flow reactor, extracting zone, and washing
tion mixture has cooled, the upper layer, consist- zone are integrated in a special apparatus
ing of crude benzyl alcohol, is removed. The (Fig. 1). The wash water and extract are returned
sodium chloride solution below still contains to the hydrolysis zone. This process can be
some soda. Dissolved benzyl alcohol can be operated at low reaction temperatures (120 –
obtained from it by adding salt or by extracting 150
C) and with a small stoichiometric excess
with benzene or toluene. The crude benzyl alco- of saponifying agent (5 – 25 %); a small reactor
hol is carefully fractionated at a reduced pressure can be used [18].
in an efficient column. The yield is 85 parts of In a two-step process, benzyl chloride reacts
benzyl alcohol and 10 parts of dibenzyl ether. with sodium acetate to form benzyl acetate,
360 Benzyl Alcohol 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
Figure 1. Hydrolysis of benzyl chloride to form benzylal- the Cannizzaro reaction.
cohol in a continuous-flow reactor [18]

which is then saponified to form benzyl alcohol 4.3. Oxidation of Toluene

[19]. In a similar process, benzyl chloride reacts
with an alkali or alkaline earth formate in the The catalytic oxidation of toluene [32] gives only
presence of a catalyst to form benzyl formate. low yields of benzyl alcohol because the reaction
The benzyl alcohol is liberated by subsequent conditions support further oxidation to benzalde-
transesterification using an alcohol and a catalyst hyde and benzoic acid. Therefore intermediates
[20]. Neither of these processes has acquired are isolated in most benzyl alcohol production
much importance in the manufacture of benzyl processes that start with toluene. The liquid-phase
alcohol. However, they could have advantages in oxidation of toluene with oxygen-depleted air at
the hydrolysis of certain substituted benzyl chlor- 170 – 220
C and pressure sufficient to keep the
ides that react with soda solution to give dibenzyl reaction medium liquid is carried out in the
ethers and not the desired alcohol. presence of stabilizers for organic hydroperoxides
(e.g., sodium pyrophosphate or sodium fluoride).
It leads mainly to benzyl hydroperoxide [33] if not
4.2. Hydrogenation and Reduction of more than 10 % of the toluene is permitted to
Benzaldehyde react. The subsequent decomposition of the oxi-
dation product at 165
C in the presence of solu-
The industrial production of benzyl alcohol by ble cobalt salts yields benzyl alcohol. Benzalde-
the hydrogenation of benzaldehyde gained hyde and benzoic acid are formed in fairly large
importance because substantial quantities of quantities as byproducts. Benzyl hydroperoxide
Vol. 5 Benzyl Alcohol 361

can also be reduced to benzyl alcohol using alkali acid esters can be hydrogenated to form benzyl
metal sulfites [34]. alcohol under mild conditions and with high
The oxidation of toluene as a liquid phase in selectivity.
air is conducted in the presence of acids, acid Other processes for the production of benzyl
chlorides, or acid anhydrides; it forms the benzyl alcohol include the hydrogenation of benzoic
esters of these acids. These are then saponified to acid [40], the electrochemical reduction of ben-
form benzyl alcohol. For example, the oxidation zoic acid [41], the hydrolysis of benzylsulfonic
of toluene in the presence of acetic anhydride at acid [42], and the decarboxylation of benzyl
temperatures of 140 – 240
C and pressures of formate [43]. These processes have no impor-
1 – 3 MPa yields benzyl acetate [35]. The oxi- tance in the industrial production of benzyl alco-
dation is discontinued after 10 % of the toluene hol, but they may be used to produce derivatives
has reacted. After the saponification of the oxi- substituted on the aromatic nucleus. Benzyl al-
dation product, 350 g of benzyl alcohol, 55 g of cohol can also be obtained from the benzyl
benzaldehyde, and 67 g of benzoic acid are benzoate which is formed in the manufacture of
obtained from 500 g of reacted toluene. Phenolic benzoic acid [44].
impurities, e.g., cresols, are unavoidably present
in the benzyl alcohol obtained by the oxidation of
toluene. These impurities can be removed by 5. Quality Standards and Test
washing the benzyl alcohol vapor with a coun- Methods
tercurrent of alkali benzylate solution in a plate
column or a packed column [36]. Several grades of benzyl alcohol are commer-
cially available (Table 3). Technical grade is
obtained as the first and last fractions in the
4.4. Other Manufacturing Processes distilla tion of the crude alcohol, it has little
importance. Pure benzyl alcohol is the most
The hydrogenation of benzoic acid esters to form important grade in terms of volume and is re-
benzyl alcohol is of particular interest in cases quired for most applications. Double-distilled
where benzoic acid esters are formed in substan- benzyl alcohol is used mainly in the perfume
tial amounts. For example, methyl benzoate is and pharmaceutical industries and must therefore
formed in the production of dimethyl terephthal- be exceptionally pure and free of foreign odors.
ate by the Witten process. Catalysts containing At 25
C it forms a clear 4 % aqueous solution.
copper are preferred. Benzoic acid esters can be The photographic grade normally contains
hydrogenated to form benzyl alcohol with the aid 0.01 – 0.02 % of hydroquinone monomethyl
of a copper catalyst and a carrier consisting of ether to inhibit oxidation.
alkaline earth oxides or carbonates [37]. The Gas chromatography using packed or capil-
selectivity can be increased if the catalyst also lary columns is suitable for the quantitative
contains chromium. Temperatures of 100 – determination of benzyl alcohol. It is more accu-
300
C and pressures above 6 MPa are used. rate than the method involving acetylation of the
The hydrogenation of methyl benzoate in the hydroxyl group with pyridine and acetic anhy-
presence of a copper–chromium catalyst is a dride. Traces of chlorine compounds are un-
feature of a three-step process for the production avoidably present in the benzyl alcohol produced
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 Table 3. Specifications for certain grades of benzyl alcohol (wt %)
step. The hydrogenation of methyl benzoate to Grades
form benzyl alcohol is performed in the final step.
This process produces benzyl alcohol at an ex- Tech- Pure Double Photo-
ceptionally low cost. Compound nical distilled graphic
Ruthenium, rhodium, platinum, and palladi- Benzyl alcohol > 97.0 > 99.0 > 99.8 > 99.5
um, activated by alkali metal arenes, ketyls, or Benzaldehyde < 0.5 < 0.2 < 0.04 < 0.03
alkoxides, are catalysts for the hydrogenation of Chlorine < 0.2 < 0.02 < 0.01 < 0.005
Dibenzyl ether < 2.0 < 0.05 < 0.02 < 0.02
the esters [39]. Using these catalysts, benzoic
362 Benzyl Alcohol Vol. 5

by hydrolysis of benzyl chloride. Byproducts, Benzyl alcohol is a starting material for the
e.g., cresols, may be present in the benzyl alcohol preparation of numerous benzyl esters that are
obtained by the oxidation method or via benzal- used as odorants, flavors, stabilizers for volatile
dehyde. Chlorine is quantitatively determined by perfumes, and plasticizers. Benzyl alcohol is also
Wickbold combustion [45], and cresols can be used in the extractive distillation of m- and p-
detected by color reactions with aminoantipyrine xylenes and m- and p-cresols.
[36]. Benzaldehyde can be quantitatively deter-
mined using hydroxylamine hydrochloride.
The pharmacopoeias of the various countries 8. Derivatives
should be consulted regarding the testing of
benzyl alcohol which is to be used in the phar- The most important derivatives of benzyl alcohol
maceutical industry. are dibenzyl ether, benzyl acetate, benzyl benzo-
ate, and benzyl salicylate.

6. Storage, Transportation, and

8.1. Dibenzyl Ether
Safety Regulations
Dibenzyl ether [103-50-4], C14H14O, M r 198.27,
Benzyl alcohol is stored in stainless steel tanks. is a colorless liquid with a faint odor; mp 3.6
C,
Because benzyl alcohol oxidizes readily, it is bp 296 – 298
C at 101.3 kPa, bp 157 –158
C
advisable to cover the surface of the liquid with at 1.2 kPa, density r 1.043 g/cm3 at 20
C, re-
nitrogen. Benzyl alcohol can be transported in

fractive index n20 D 1:5622, flash point 135 C.
drums protected by stoving finishes and in tank The compound is very slightly soluble in water.
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 Production. Dibenzyl ether is formed when
labeling of benzyl alcohol must comply with the benzyl alcohol is heated with strong acids or
national and international regulations on danger- bases. It is produced almost exclusively by the
ous substances. alkaline hydrolysis of benzyl chloride. Heat
treatment decomposes dibenzyl ether into benz-
aldehyde and toluene.
7. Uses
Use. Dibenzyl ether is used as a plasticizer in
By virtue of its good solvent properties, benzyl the surface coatings industry, for special pur-
alcohol is an important solvent for surface-coat- poses in the rubber and textile industries, and as a
ing materials and resins. It dissolves cellulose solvent for musk and other odorants.
esters and ethers, alkyd resins, acrylic resins, and Excess dibenzyl ether can be converted into a
fats; it is also used as an ingredient in the inks for mixture of benzotrichloride and benzoyl chloride
ball-point pens. It is added in small amounts to under the conditions of side chain chlorination
surface-coating materials to improve their flow with chlorine [46]. Treatment of dibenzyl ether
and gloss. In the textile industry, it is used as an with hydrochloric acid in the presence of trialkyl-
auxiliary in the dyeing of wool, polyamides, and or tetraalkylammonium salts gives benzyl chlo-
polyesters. Because it has only a relatively faint ride [47].
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 8.2. Benzyl Acetate
development accelerator. In pharmacy it is used
as a local anesthetic and, because of its microbi- Benzyl acetate [140-11-4], C9H10O2, Mr 150.18,
cidal effect, as an ingredient of ointments and is a colorless liquid with an odor of pears and
other preparations. jasmine. It is a constituent of jasmine, gardenia,
Vol. 5 Benzyl Alcohol 363

and other flower oils; mp  51.5
C, bp 215
C plasticizer in the surface coatings and plastics
at 101.3 kPa, density r 1.056 g/cm3 at 20
C, industries.


refractive index n20
D 1:5020, flash point 102 C,
very slightly soluble in water.
8.4. Benzyl Salicylate

Benzyl salicylate [118-58-1], C14H12O3, Mr

228.25, is a colorless, viscous liquid with a
Production and Use. Benzyl acetate is pro- pleasant odor. It occurs naturally in several es-
duced by reacting benzyl chloride with an alkali sential oils; mp 24
C, bp 211
C at 2.67 kPa,
acetate or by esterifying benzyl alcohol with density r 1.175 g/cm3 at 25
C, refractive index
acetic anhydride. It is also formed in the oxida- n25
D 1:5787, slightly soluble in water.
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.

Production and Use. Benzyl salicylate can

8.3. Benzyl Benzoate be manufactured by reacting benzyl chloride
with an alkali salicylate or by the transesterifica-
Benzyl benzoate [120-51-4], C14H12O2, Mr tion of methyl salicylate with benzyl alcohol. It is
212.25, is a colorless, viscous liquid with a used as a perfume stabilizer and, because it
pleasant odor. It is the main constituent of Peru absorbs ultraviolet light, as an ingredient in
balsam, Tolu balsam, and certain flower oils; mp sunscreening preparations.
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.
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-
Production. Benzyl benzoate is produced duced in Western Europe in 1983. Approxi-ma-
from benzyl alcohol and sodium benzoate in the tely 3.4 kt of benzyl alcohol was produced in the
presence of triethylamine or by transesterifica- United States in 1979.
tion of methyl benzoate with benzyl alcohol in
the presence of an alkali benzyl oxide. In another
manufacturing process benzaldehyde is con- 10. Toxicology
densed to form benzyl benzoate in the presence
of sodium (Claisen-Tishchenko condensation). Benzyl alcohol is used in pharmaceuticals, soaps,
The presence of a small amount of an aliphatic detergents, and cosmetics as a fragrance, preser-
ether improves this reaction [48]. Benzyl benzo- vative, and antimicrobial, and is ‘‘generally re-
ate is a byproduct in the manufacture of benzoic garded as safe’’ (GRAS) for use in food by the U.
acid by the oxidation of toluene; it is present in S. Food and Drug Administration. It has indus-
the benzoic acid distillation residue. trial applications as a solvent and dye assistant,
but no environmental or workplace exposure
Use. Benzyl benzoate is used in perfume limits have been established.
manufacture, mainly to stabilize volatile odor- Benzyl alcohol is moderately toxic with acute
ants. It has vasodilating and spasmolytic effects oral LD50 values of 1.2 g/kg in rats and 1.6 g/kg
and is present in many asthma and whooping in mice [49]. The LD50 for inhalation exposure is
cough drugs. It is used as an insect repellent and approximately 1.0 g/kg (eight hours) in rats [50].
to treat scabies. Benzyl benzoate is used as a Benzyl alcohol can be absorbed through the skin
364 Benzyl Alcohol Vol. 5

in sufficient quantities to cause toxicity; the 8 A. McKillop, M. E. Ford, Synth. Commun. 2 (1972)
dermal LD50 in guinea pigs is < 5 mL/kg 307 – 313.
[51]. In vitro screening tests for chemical carci- 9 F. M. Menger, C. Lee, Tetrahedron Lett. 22 (1981)
1655 – 1656.
nogens in a repair-deficient bacterial strain
10 SCM Corp., DE 2556161, 1975 (W. J. Ehmann, W. E.
(P 3478 E. coli) were negative [52]. Benzyl Johnson, Jr.,
alcohol is not considered to be a carcinogen and 11 J. F. Norris, Am. Chem. J. 38 (1907) 631.
no data are available regarding teratogenic or 12 ICI, GB 310909, 1928 (B. W. Henderson).
reproductive effects. 13 A. Masuda, H. Mitani, K. Oku, Y. Yamazaki, Nippon
Benzyl alcohol is widely used as a preserva- Kagaku Kaishi 1982, 249 – 256; Chem. Abstr. 96 (1982)
tive in solutions of drugs for intravenous admin- 141989 y.
istration. The minimum lethal dose in dogs (i.v.) 14 E. Iselin, F. Barfuss, Chem. Ing. Tech. 44 (1972) 462.
15 National Oil Products Co., US 2221882, 1938 (L. T.
is between 88 and 113 mL/kg of a 0.9 vol %
Rosenberg).
solution of benzyl alcohol in water or in physio- 16 All-Union Scientific Research Institute of Synthetic and
logical saline solution [53]. Similar doses have Natural Perfumes, SU 225183, 1967 (V. V. Kashnikov, N.
been fatal for newborn humans receiving benzyl I. Gel’perin, S. A. Voitkevich, O. N. Zhuchkova, T. P.
alcohol in the course of intravenous drug treat- Khrenkova); Chem. Abstr. 70 (1969) 28614 x.
ment [54]. Benzyl alcohol is estimated to be more 17 Velsicol Chem. Corp., US 3557222, 1968 (H. W. Withers,
than twenty times more toxic than ethyl alcohol J. L. Rose).
(i.v.) [53]. 18 EKA, EP 64486, 1981 (R. K. Rantala, G. L. F. Hag).
19 Chemische Werke Witten, DE 1108677, 1959 (G. Re-
Benzyl alcohol is severely toxic and highly
nckhoff, H. L. H€ulsmann).
irritating to the eye. Contact with benzyl alcohol 20 Dynamit Nobel, DE 2825364, 1978 (G. Bernhardt, G.
causes mild to moderate skin irritation [55]. Daum).
Hypersensitivity reactions may occur in some 21 Kazakh Chemical-Technological Institute, SU 235 002,
individuals with both topical and parenteral ad- 1966 (F. B. Bizhanov, D. V. Sokol’skii, N. I. Popov, A. M.
ministration [56]. Khisametdinov, N. Ya. Malkina); Chem. Abstr. 70 (1969)
Signs of intoxication include vomiting and 114813 t.
diarrhea, collapse, central nervous system depres- 22 Hoechst, DE 2837022, 1978 (K. K€ummerle, H. Heise).
23 Mitsui Petrochem. Industries, JP-Kokai 77 27738, 1975
sion, excitability, muscle paralysis, convulsions, (K. Teranishi, T. Shimizu, K. Koga); Chem. Abstr. 87
dyspnea, and respiratory arrest [55]. Exposure (1977) 134502 v.
should be avoided by the use of adequate ventila- 24 Mitsui Petrochem. Industries, JP-Kokai 77 27737, 1975
tion systems, self-contained respiration equip- (K. Teranishi, T. Shimizu, K. Koga); Chem. Abstr. 87
ment, protective goggles, gloves, and clothing. (1977) 134501 u.
25 Sumitomo Chem. Co., JP-Kokai 82 26634, 1980; Chem.
Abstr. 96 (1982) 199279 h.
26 Mitsui Petrochem. Industries, JP-Kokai 76 86432, 1975
References (K. Teranishi, T. Ito); Chem. Abstr. 85 (1976)
192342 n.
General References 27 Universal Oil Products Co., US 3663626, 1969 (J. T.
1 Beilstein 6, 428; 6 (1), 217; 6 (2), 403; 6 (3), 1445; 6 (4) Arrigo, N. J. Christensen).
2222. 28 M & T Chemicals Inc., US 3708549, 1970 (G. H. Re-
2 M. Watanabe, K. Namikawa, CEER Chem. Econ. Eng. Rev. ifenberg, W. J. Considine).
2 (1970) 50 – 52. 29 Sagami Chem. Res. Center, JP-Kokai 76 39609, 1974 (T.
Fujisawa, K. Sugimoto, H. Ota); Chem. Abstr. 85 (1976)
Specific References 122719 s.
3 F. W€ ohler, Ann. Pharm. (Lemgo, Ger.) 3 (1832) 249, 30 Sumitomo Chem. Co., JP-Kokai 74 135933, 1973 (T.
254. Mizutani, Y. Ume, T. Matsuo); Chem. Abstr. 82 (1975)
4 S. Cannizzaro, Justus Liebigs Ann. Chem. 88 (1853) 129. 155745 p.
5 L. H. Horsley: ‘‘Azeotropic Data-III, ’’ Adv. Chem. Ser. 31 Politechnika Wroclawska, PL 114065, 1979 (J. Wis-
1973, no. 116, 374 – 376. niewski, A. Poranek, T. Winnicki); Chem. Abstr. 97
6 J. Gmehling, U. Onken, W. Arlt: ‘‘Vapor-Liquid Equilib- (1982) 214282 v.
rium Data Collection,’’ Dechema Chem. Data Ser., vol. I, 32 Universal Oil Products Co., US 3775472, 1970 (S. N.
part 1 a, 447 – 450, 1981, part 2 b, 434, 1978, part 2 d, Massie).
563 – 577, 1982. 33 Rhône-Poulenc, FR 1366078, 1963 (J. Bonnard, G.
7 M. Yamashita, Y. Takegami, Synthesis 1977, 803. Poilane).
Vol. 5 Benzyl Alcohol 365

34 Nippon Oils & Fats Co., JP-Kokai 78 21133, 1976 46 Bayer, DE 1909523, 1969 (W. B€ockmann).
(S. Suyama, H. Ishigaki); Chem. Abstr. 88 (1978) 47 Odessa State University, SU 872525, 1980 (G. L. Kama-
190371 j. lov, D. G. Chikhichin, L. Ya. Glinskaya, G. P. Fedorch-
35 Institute of Petrochemical Synthesis, DE 1912078, 1969 enko, F. P. Filek); Chem. Abstr. 96 (1982) 85217 f.
(A. N. Baskirov, M. M. Grozhan, V. V. Kamzolkin, Yu. A. 48 Dow Chem. Co., US 3387020, 1964 (C. E. Handlovits, J.
Lapitskii). B. Louch).
36 Rhône-Poulenc, DE 1668646, 1967 (J. Bonnart, P. Rey). 49 P. M. Jenner, E. C. Hagan, J. M. Taylor, E. L. Cook, O. G.
37 Nippon Mining Co., DE 1768262, 1967 (M. Watanabe, Fitzhugh, Food Cosmet. Toxicol. 2 (1964) 327 – 343.
K. Mamikawa, K. Yasuda, M. Takagi). 50 H. F. Smyth, Jr., C. P. Carpenter, C. S. Weil, AMA Arch.
38 K. Kato, K. Namikawa, M. Watanabe, Bull. Jpn. Pet. Ind. Hyg. Occup. Med. 4 (1951) 120.
Inst. 14 (1972) 206 – 216; Chem. Abstr. 78 (1973) 51 D. L. J. Opdyke, Food Cosmet. Toxicol. 11 (1973) 1011 –
60190 g. 1081.
39 Allied Chem. Corp., EP 36939, 1980 (R. A. Grey, G. P. 52 E. R. Fluck, L. A. Poirier, H. W. Ruelius, Chem. Biol.
Pez). Interact. 15 (1976) 219 – 231.
40 Sumitomo Chem. Co., EP 28422, 1979 (T. Takano, 53 E. T. Kimura, T. D. Darby, R. A. Krause, H. D. Brondyk,
G. Suzukamo, M. Ishino, K. Ikimi). Toxicol. Appl. Pharmacol. 18 (1971) 60 – 68.
41 Union Rheinische Braunkohlen Kraftstoff AG, DE 54 J. Gershanik, B. Boecler, H. Ensley, S. McCloskey, W.
2237612, 1972 (G. Schwarzlose). George, N. Engl. J. Med. 307 (1982) 1384 – 1388.
42 Universal Oil Products Co., US 3641165, 1967 55 V. K. Rowe, S. B. McCollister in G. D. Clayton, F. E.
(L. Schmerling, R. A. Dombro). Clayton (eds.): Patty’s Industrial Hygiene and Toxicolo-
43 Dynamit Nobel, DE 2825362, 1978 (G. Bernhardt). gy, vol. 2 C, John Wiley & Sons, New York 1982,
44 Stamicarbon B. V., EP 19341, 1979 (C. Jongsma, L. H. B. pp. 4636 – 4703.
Frijns, P. A. M. Raven-Donners). 56 J. A. Grant, O. A. Bilodeau, B. G. Guernsey, F. H.
45 F. Ehrenberger, S. Gorbach: Methoden der organischen Gardner, N. Engl. J. Med. 307 (1982) 108.
Elementar- und Spurenanalyse, Verlag Chemie, Wein-
heim, Germany 1973, p. 238 ff.