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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)
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
Benzyl Alcohol 3
transesterification using an alcohol and a cata- Depending on the reaction conditions, ben-
lyst [20]. Neither of these processes has acquired zaldehyde can be hydrogenated to form benzyl
much importance in the manufacture of benzyl alcohol, toluene, hydroxymethylcyclohexane,
alcohol. However, they could have advantages methylcyclohexane, and other products. How-
in the hydrolysis of certain substituted benzyl ever, very high yields of benzyl alcohol are ob-
chlorides that react with soda solution to give tainable if suitable reaction conditions and cata-
dibenzyl ethers and not the desired alcohol. 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.
The oxidation of toluene as a liquid phase alcohol under mild conditions and with high se-
in air is conducted in the presence of acids, acid lectivity.
chlorides, or acid anhydrides; it forms the benzyl Other processes for the production of ben-
esters of these acids. These are then saponified to zyl alcohol include the hydrogenation of benzoic
form benzyl alcohol. For example, the oxidation acid [40], the electrochemical reduction of ben-
of toluene in the presence of acetic anhydride at zoic acid [41], the hydrolysis of benzylsulfonic
temperatures of 140 – 240 ◦ C and pressures of acid [42], and the decarboxylation of benzyl for-
1 – 3 MPa yields benzyl acetate [35]. The oxi- mate [43]. These processes have no importance
dation is discontinued after 10 % of the toluene in the industrial production of benzyl alcohol,
has reacted. After the saponification of the oxi- but they may be used to produce derivatives sub-
dation product, 350 g of benzyl alcohol, 55 g of stituted on the aromatic nucleus. Benzyl alcohol
benzaldehyde, and 67 g of benzoic acid are ob- can also be obtained from the benzyl benzoate
tained from 500 g of reacted toluene. Phenolic which is formed in the manufacture of benzoic
impurities, e.g., cresols, are unavoidably present acid [44].
in the benzyl alcohol obtained by the oxidation
of toluene. These impurities can be removed by
washing the benzyl alcohol vapor with a coun- 5. Quality Standards and Test
tercurrent of alkali benzylate solution in a plate
column or a packed column [36].
Methods
Several grades of benzyl alcohol are commer-
cially available (Table 3). Technical grade is ob-
4.4. Other Manufacturing Processes tained as the first and last fractions in the dis-
tilla tion of the crude alcohol, it has little impor-
The hydrogenation of benzoic acid esters to form tance. Pure benzyl alcohol is the most important
benzyl alcohol is of particular interest in cases grade in terms of volume and is required for most
where benzoic acid esters are formed in substan- applications. Double-distilled benzyl alcohol is
tial amounts. For example, methyl benzoate is used mainly in the perfume and pharmaceutical
formed in the production of dimethyl terephtha- industries and must therefore be exceptionally
late by the Witten process. Catalysts containing pure and free of foreign odors. At 25 ◦ C it forms
copper are preferred. Benzoic acid esters can be a clear 4 % aqueous solution. The photographic
hydrogenated to form benzyl alcohol with the grade normally contains 0.01 – 0.02 % of hydro-
aid of a copper catalyst and a carrier consisting of quinone monomethyl ether to inhibit oxidation.
alkaline earth oxides or carbonates [37]. The se- Gas chromatography using packed or cap-
lectivity can be increased if the catalyst also con- illary columns is suitable for the quantitative
tains chromium. Temperatures of 100 – 300 ◦ C determination of benzyl alcohol. It is more
and pressures above 6 MPa are used. accurate than the method involving acetyla-
The hydrogenation of methyl benzoate in the tion of the hydroxyl group with pyridine and
presence of a copper–chromium catalyst is a fea- acetic anhydride. Traces of chlorine compounds
ture of a three-step process for the production of are unavoidably present in the benzyl alco-
benzyl alcohol from toluene [38]. The first step hol produced by hydrolysis of benzyl chloride.
is the oxidation of toluene to form benzoic acid. Byproducts, e.g., cresols, may be present in
The acid is esterified with methanol in the sec- the benzyl alcohol obtained by the oxidation
ond step. The hydrogenation of methyl benzoate method or via benzaldehyde. Chlorine is quan-
to form benzyl alcohol is performed in the final titatively determined by Wickbold combustion
step. This process produces benzyl alcohol at an [45], and cresols can be detected by color reac-
exceptionally low cost. tions with aminoantipyrine [36]. Benzaldehyde
Ruthenium, rhodium, platinum, and palla- can be quantitatively determined using hydrox-
dium, activated by alkali metal arenes, ketyls, ylamine hydrochloride.
or alkoxides, are catalysts for the hydrogenation The pharmacopoeias of the various countries
of the esters [39]. Using these catalysts, benzoic should be consulted regarding the testing of ben-
acid esters can be hydrogenated to form benzyl 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
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
7. Uses
By virtue of its good solvent properties, ben-
zyl alcohol is an important solvent for surface- Production. Dibenzyl ether is formed when
coating materials and resins. It dissolves cel- benzyl alcohol is heated with strong acids or
lulose esters and ethers, alkyd resins, acrylic bases. It is produced almost exclusively by the
resins, and fats; it is also used as an ingredi- alkaline hydrolysis of benzyl chloride. Heat
ent in the inks for ball-point pens. It is added treatment decomposes dibenzyl ether into ben-
in small amounts to surface-coating materials to zaldehyde and toluene.
improve their flow and gloss. In the textile in-
dustry, it is used as an auxiliary in the dyeing Use. Dibenzyl ether is used as a plasticizer
of wool, polyamides, and polyesters. Because it in the surface coatings industry, for special pur-
has only a relatively faint odor, it is used as a poses in the rubber and textile industries, and as
solvent and diluting agent in the manufacture of a solvent for musk and other odorants.
perfumes and flavors. In color photography it is Excess dibenzyl ether can be converted into
increasingly important as a development accel- a mixture of benzotrichloride and benzoyl chlo-
erator. In pharmacy it is used as a local anesthetic ride under the conditions of side chain chlorina-
and, because of its microbicidal effect, as an in- tion with chlorine [46]. Treatment of dibenzyl
gredient of ointments and other preparations. ether with hydrochloric acid in the presence of
Benzyl alcohol is a starting material for the trialkyl- or tetraalkylammonium salts gives ben-
preparation of numerous benzyl esters that are zyl chloride [47].
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.
Benzyl Alcohol 7
assistant, but no environmental or workplace ex- 4. S. Cannizzaro, Justus Liebigs Ann. Chem. 88
posure limits have been established. (1853) 129.
Benzyl alcohol is moderately toxic with acute 5. L. H. Horsley: “Azeotropic Data-III,” Adv.
oral LD50 values of 1.2 g/kg in rats and 1.6 g/kg Chem. Ser. 1973, no. 116, 374 – 376.
in mice [49]. The LD50 for inhalation exposure is 6. J. Gmehling, U. Onken, W. Arlt:
approximately 1.0 g/kg (eight hours) in rats [50]. “Vapor-Liquid Equilibrium Data Collection,”
Benzyl alcohol can be absorbed through the skin Dechema Chem. Data Ser., vol. I, part 1 a,
in sufficient quantities to cause toxicity; the der- 447 – 450, 1981, part 2 b, 434, 1978, part 2 d,
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vitro screening tests for chemical carcinogens
803.
in a repair-deficient bacterial strain (P 3478 E.
8. A. McKillop, M. E. Ford, Synth. Commun. 2
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considered to be a carcinogen and no data are 9. F. M. Menger, C. Lee, Tetrahedron Lett. 22
available regarding teratogenic or reproductive (1981) 1655 – 1656.
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