Benzylamine 1

Benzylamine
Lutz Heuer, Lanxess Deutschland GmbH, Federal Republic of Germany

1. Physical Properties . . . . . . . . . . . . . . 1 5. Uses . . . . . . . . . . . . . . . . . . . . . . . . 2

2. Chemical Properties . . . . . . . . . . . . . 1 6. Storage and Transportation . . . . . . . . 2
3. Production . . . . . . . . . . . . . . . . . . . 2 7. Ecology and Toxicology . . . . . . . . . . . 3
4. Quality Specifications and Analysis . . . 2 8. References . . . . . . . . . . . . . . . . . . . 3

Benzylamine (α-aminotoluene) [100-46-9] is Benzylamine is miscible with water, alcohol,

an important industrially used amine, which is
readily available by hydrogenation of benzoni-
trile or amination of benzaldehyde or benzyl
chloride. It also occurs in nature and can be iso-
lated from the leaves of Reseda media in small
amounts. Benzylamine is a colorless liquid of
ammonia-like odor, which is miscible with wa-
ter in all proportion. It is used in the chemical in-
dustry as a starting material for other products or
as a corrosion inhibitor. Benzylamine is listed in
EINECS 202-854-1, TSCA, and MITI/MO and
traded world-wide. It can be transported in steel
drums and in high-density polyethylene (HDPE)
containers.Benzylamine is harmful in contact
with skin and if swallowed. It causes burns, es-
pecially when skin is exposed to benzylamine
for prolonged periods. Because of the fast reac-
tion of benzylamine and carbon dioxide, slightly
leaking flanges or other seals are easily identi-
fied by the white solid formed.Benzylamine is
produced by Lanxess and other companies and
is available in drums, IBC’s (intermediate bulk
containers), and in bulk.
and diethyl ether in all proportions; bp 184.5 ◦ C
at 101.3 kPa, bp 90 ◦ C at 1.6 kPa, solidifica-
tion point < −30 ◦ C, vapor pressure ca. 60 Pa at
20 ◦ C, ca. 130 Pa at 30 ◦ C, and 520 Pa at 50 ◦ C.
Examples of azeotropic mixtures are given in
Table 1.
Heat of vaporization 49 kJ/mol, heat of
combustion 4058.7 kJ/mol at 101.3 kPa and
20 ◦ C, refractive index n20 D 1.5401, density
d20
4 0.9813, d 86.6
4 0.9272, dielectric constant 4.6
at 20.6 ◦ C, electrolytic dissociation constant
in water 2.35 × 10−5 at 20 ◦ C, viscosity 1.78
mPa · s at 21.2 ◦ C, 0.295 mPa · s at 178.2 ◦ C,
surface tension 38.82 × 10−5 N/cm at 21.1 ◦ C,
31.70 × 10−5 N/cm at 88 ◦ C, autoignition tem-
perature 390 ◦ C, flash point 65 ◦ C, explosion
limit 0.9 % (lower) to 14 % (upper); dipole mo-
ment (20 ◦ C) 1.18 D (neat), 1.25 D in toluene,
1.29 D in hexane, 1.30 D in cyclohexane,
and 1.33 D in benzene [7]; dynamic viscosity
0.01596 g cm−1 s−1 at 25 ◦ C [8]; absorption
maximum λmax in water 255.9 nm (ε 249 L
mol−1 cm−1 ) [9], magnetic susceptibility −
75.3 × 10−6 cm3 /mol [10].

1. Physical Properties
Benzylamine [100-46-9], EINECS 202-854-1,
TSCA and MITI/MO listed, α-aminotoluene,
phenylmethylamine, moringine, C7 H9 N, M r
107.16, is a colorless liquid with a weak amine-
like odor.
2. Chemical Properties
Benzylamine is a stronger base than its tolui-
dine isomers and reacts strongly alkaline even
if diluted with some water (pH 11.6 in water
at 100 g/L) [11]. It forms addition compounds
with, e.g., phenol (1 : 3, mp 15.3 ◦ C), p-cresol
(1 : 1, mp − 6 ◦ C), and formic acid (1 : 1, mp
81 ◦ C). Examples of the salts of benzylamine
−
are the hydrochloride, C6 H5 CH2 NH+ 3 Cl , mp
260 C (decomp.), and the picrate, mp 194 ◦ C.
◦

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a04 009.pub2
2 Benzylamine
Table 1. Azeotropic mixtures containing benzylamine
Other component, A bp of A, ◦ C
Aniline 184.35
Phenol 182.2
m-Cresol 202.2
Benzylamine absorbs carbon dioxide from the
air to form the solid carbamic acid salt. If
benzylamine is boiled with glacial acetic acid,
N-acetylbenzylamine is formed. Benzylamine
reacts with isocyanates to give substituted
ureas, C6 H5 CH2 NHCONHR. Benzylamine is
nitrated on the aromatic nucleus (8 % ortho-,
49 % meta-, 43 % para-nitrobenzylamine) by ni-
tric acid. Catalytic hydrogenation gives hexa-
hydrobenzylamine, C6 H11 CH2 NH2 .
3. Production
Benzylamine is produced by the reaction of ben-
zyl chloride with ammonia [12] in aqueous solu-
tion. The catalytic hydrogenation of benzonitrile
[13 – 15] and the reaction of benzaldehyde with
ammonia in the presence of hydrogen and cat-
alysts [16, 17] are alternatives. Both processes
use some organic solvent in the reaction mixture.
In the benzaldehyde process, 8 kg of Raney
nickel that has been kept under water (corre-
sponding to about 4 kg of 100 % Ni), 10 g of
glacial acetic acid, and 110 kg of ammonia are
added to a mixture of 250 kg of methanol and
500 kg of benzaldehyde. The resulting batch
is hydrogenated in a 1200-L steel autoclave at
100 ◦ C and 15 MPa. The process takes 3 – 5 h.
The hydrogen consumed in the reaction is made
up at intervals of about 10 min. The contents of
the reaction vessel are maintained at the same
temperature and pressure for 30 min after hy-
drogen consumption ends. The catalyst is then
separated from the reaction products on a pres-
sure filter [16]. The filtrate contains 470 kg of
benzylamine, about 1 kg of benzyl alcohol, less
than 1 kg of dibenzylamine, and about 2 kg of
Schiff base (N-benzalbenzylamine), in addition
to methanol, reaction water, and ammonia. The
yield is 93 %. Vacuum distillation yields benzy-
lamine of the required technical purity.
Benzylamine has been isolated as a natural
compound in the leaves and flowers of Reseda
media [18].
bp of azeotropic mixture, ◦ C Component A in the azeotropic
mixture, wt %
186.2 42
196.8 45
207.2 56
4. Quality Specifications and
Analysis
Commercial benzylamine has an assay of 99 %
or more and contains less than 1.0 % water. De-
pending on the production process, some mi-
nor impurities are specified. Color number is
typically less than 20 Hazen (APHA; DIN-ISO
6271), and the density at 20 ◦ C 0.98 g/cm3 . For
use in the pharmaceuticals industry, some cus-
tomers require the absence of organic solvents
such as benzene, xylene, and chlorinated sol-
vents.
Benzylamine can be analyzed by gas chro-
matography on commercial columns such as
Chrompack CP-SIL 8 for amines or Chrompack
WACHS 51 for amines. The results should be
corrected for water content.
5. Uses
Benzylamine is used in synthetic textiles, in
paints, and as corrosion inhibitor [19]. It is also
used as an intermediate in the production of
pharmaceutical active substances [21] and com-
pounds for plant and material protection. In this
cases benzylamine is often used as “protected
nitrogen” [24].
6. Storage and Transportation
For storage and transportation of benzylamine,
most types of steel may be used (unalloyed steel,
V2A, V4A types; e.g. 1.4301, 1.4306, 1.4571,
1.4401 [DIN 6601]). If chloride or bromide is
present, some steel types should be avoided
[DIN 6601]. One-tonne containers made from
HDPE (Lupolen 4261 A) are also suitable (e.g.
Schütz Container, intermediate bulk containers),

as are drums lined with this material. Benzy-
lamine is slowly oxidized on contact with air
and forms benzalbenzylamine. It also reacts with
carbon dioxide to form its solid carbamic acid
salt. It therefore should be stored in a tight closed
container for not more than one year. For longer
storage, a nitrogen blanket is recommended. In
Germany the conditions for storage are classified
as 8L (VCI-Lagerklasse) [25]. The handling of
benzylamine is shown in a video sequence.
Benzylamine (EC No. 612-047-00-x) is in-
cluded in the list of substances contained in EC
Guideline 67/548, Appendix I and is therefore
to be considered a dangerous industrial material.
Containers must be marked as follows (EEC La-
bel No. 202-854-1):
C Corrosive; Benzylamine
R 21/22 Harmful in contact with skin and if swallowed.
R 34 Causes burns.
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 36/37/39 Wear suitable protective clothing, gloves, and
eye/face protection.
S 45 In case of an accident or if you feel unwell,
seek medical advice immediately (show the
label where possible).
The following symbols and indications are
required on labels and/or transport papers [25]:
Sea (GGVSee/IMDG Code) Class 8, UN no. 2735, MFAG
320, EmS 8-05, Packing
Group (PG) III, Marine
Pollutant (MPO): No
Rail/road, Germany (GGVE/GGVS)Class 8, Item 53C
Rail/road, international (RID/ADR) Class 8, Item 53C
Hazard symbol Hazard 080, Compound 2735
Inland vessels (ADNR) Class 8, Item 53C
Air (ICAO/IATA-DGR) Class 8, UN no. 2735, PG III
Benzylamine is not allowed to be sent by mail
within Germany but can be sent by express mail
within Germany if 12 L per package is not ex-
ceeded. Declarations are as follows:
Land UN no. 2735,amines, liquid, corrosive, n.o.s.
(Benzylamine), Class 8, Item 53c, ADR (RID)
Sea UN no. 2735, amines, liquid, corrosive, n.o.s.
(Benzylamine)
Air UN 2735, amines, liquid, corrosive, n.o.s. (Benzylamine)
Benzylamine 3
7. Ecology and Toxicology
Results of laboratory investigations into the eco-
logical behavior of benzylamine are summarized
in Table 2 [25].
Table 2. Biodegradability of benzylamine
Method [26] Degree of Result
elimination
OECD screening test > 95 % readily
biodegradable
Sturm test 90 % readily
biodegradable
Zahn – Wellens test 95 % well eliminated
Benzylamine is readily biodegradable. It
is harmful in aquatic environment [German
class for hazards in aquatic environment:
1 (weak effect) (WGK 1)]. Acute toxicity:
Pseudomonas fluorescens (bacteria) 500 mg
(EC0 ); Scenedesmus quadricauda (algae) 6 mg
(96-h EC10 ); Daphnia magna 60 mg (48-h
EC50 ); Leuciscus idus (fish) 20 mg (48-h EC0 );
Pimephals promelas (fish) 102 mg (96-h EC50 )
[25].
Benzylamine causes burns to skin and eyes
and may cause sensitization. Rinse immediately
with plenty of water. Wash skin also with soap.
When used regularly a 5 % aqueous solution of
acetic acid should be available for neutraliza-
tion of contaminated skin. If swallowed dilute by
drinking water, rinse mouth. If risk of inhalation
is given, use ABEK filters in breathing masks
(DIN 3181).
Benzylamine is Ames test negative (no mu-
tagenic effect). Acute oral toxicity: LD50 1130
mg/kg (rat). Acute percutaneous toxicity: LD50
1340 mg/kg (rat) [25]. Toxicity class 3 (Switzer-
land). All rats inhaling benzylamine for 3 h sur-
vived a two-week period (full body exposure).
After full body exposure for 5 h, 17 % died.
8. References
General References
1. Beilstein 12, 1013; 12 (1), 445; 12 (2), 540; 12
(3), 2194; 12 (4), 2155.
2. Houben-Weyl, 11/1, Stuttgart 1957.
3. Merck Index, 12th ed., 1160.
4. Merck FT-IR, 1532.
5. Fieser, 10 26.
6. Kühn-Birett, B050.
4 Benzylamine
Specific References
7. Beilstein 12 (3), 2194; 12 (4), 2155.
8. A. G. Mussell, F. B. Thole, A. E. Dunstan, J.
Chem. Soc. 101 (1912) 1014.
9. P. R. Haddad, R. C. Foley, Anal. Chem. 61
(1989) 1435 – 1441.
10. French, Trans. Faraday Soc. 1954, 1320 –
1321.
11. Merck, Data Sheet for Benzylamine for
Synthesis, 801812, Catalogue 1999.
12. A. T. Mason, J. Chem. Soc. 63 (1893) 1311.
California Research Corp., US 2987548, 1961.
13. W. H. Carothers, G. A. Jones, J. Am. Chem.
Soc. 47 (1925) 3051
14. BASF, FR 2165515, 1939.
15. M. Grunfeld, US 2449036, 1941.
16. C. F. Winans, J. Am. Chem. Soc. 61 (1939)
3566.
17. BASF, FR 146354, 1966.
18. O. Olsen, H. Soerensen, Phytochemistry, 19
(1980) 1783 – 1788.
19. B. Wanderott, Z. Metallkd. 56 (1965) no. 1, 63
– 64.
20. Chem. Abstr. 47 (1950) 7149 h.
21. H. Ippen: Index Pharmacorum, Thieme
Verlag, Stuttgart 1968.
22. Deutsche Einheitsverfahren zur Wasser-,
Abwasser- und Schlamm-Untersuchung, 3rd.
ed., Verlag Chemie, Weinheim 1960 – 1971.
23. Bayer AG, Toxicological Institute, Elberfeld
1977.
24. T. W. Green (Ed.): Protective Groups in
Organic Synthesis, Wiley, New York,
1981, p. 272.
25. Lanxess Safety Data Sheet Benzylamine
012193 (Sept. 26, 2005).
26. P. Gerike, W. K. Fischer, Ecotoxicol. Saf. 3
(1979) 159 – 173.