Professional Documents
Culture Documents
A02 037
A02 037
Amines, Aromatic
Amines, Aliphatic; Aminophenols; Aniline; Benzidine and Benzidine Derivatives; Naphthalene Derivatives;
Phenylenediamines and Toluenediamines; Toluidines and Xylidines are separate keywords
Peter F. Vogt, Mobay Chemical Corp., Pittsburgh, Pennsylvania 15205, United States(Chaps 2 – 4)
John J. Gerulis, Mobay Chemical Corp., Pittsburgh, Pennsylvania 15205, United States(Chap. 5)
aniline consumption grew from 0.29 to 0.49 Mio The effect of the phenyl groups becomes even
t in th United States, in Western Europe from more dominant in diphenylamine (K B = 10−14 ),
0.30 to 0.59 Mio t, and in Japan from 0.07 to which can form salts only with strong acids that
0.16 Mio t [6]. are completely ionized in water, whereas triph-
Analgesics and sulfonamides are examples enylamine rarely forms salts and has no basic
of important pharmaceuticals derived from aro- properties.
matic amines. Many sulfa drugs start from ac- The physical properties of the most important
etanilide (antifebrin) [103-84-4], which itself aromatic amines are given under → Aniline.
has been used as an antipyretic and analgesic
agent.
Diarylamines readily donate their amine hy- 2.2. Chemical Properties
drogen atom to terminate various free-radical
reactions. For this reason they are widely used The chemical reactions of aromatic amines are
as antioxidants for various polymers and elas- similar to those of aliphatic amines. These reac-
tomers, and as stabilizers for nitrocellulose [7]. tions are influenced greatly by the basicity of
Nearly all commercial synthetic rubbers are pro- the amine nitrogen. Therefore, such electron-
tected with alkylated diphenylamines. Because withdrawing substituents as nitro and cyano re-
they darken on oxidation, diphenylamines can- duce the base strength of the amine nitrogen
not be used in light colored rubber and polymer when substituted in the ortho or para positions of
compositions. In this case N,N -di-β-naphthyl- the benzene ring(s). Aromatic amines undergo a
p-phenylenediamines are used instead. Some di- variety of chemical reactions. The ones of great-
arylamines retard the effect of intense gamma or est industrial significance are described in this
neutron radiation [8]. Diarylamines have been section.
used to stabilize sulfur trioxide, are used as cor-
rosion inhibitors in roofing asphalt, and are es-
sential in promoting cross-linking in poly(vinyl 2.2.1. Acetylation and Similar Reactions
chloride) [9] and in polyethylene [10]. Diaryl-
Primary and secondary aromatic amines re-
amines containing other functional groups, such
act with carboxylic acids, acid chlorides, an-
as amino or hydroxy, are used as dye interme-
hydrides, and esters to form a wide variety
diates [11], antiozonants, in color photography,
of commercially important amides. For exam-
and for hair dyeing and have been patented for
ple, p-acetanisidine, N-(4-methoxyphenyl)acet-
use in the image formation process in photo-
amide [51-66-1], is obtained in nearly theoret-
graphic films [12], [13].
ical yield, especially if the water formed is re-
moved (e.g., by distillation).
2. Physical and Chemical Properties
2.2.6. Halogenation
2.2.9. Sulfonation
2.2.7. Nitration
Reaction of aromatic amines with sulfuric acid,
Generally, nitration of aromatic amines with oleum, or sulfur trioxide leads to the introduction
nitric acid results in concomitant oxidation of of the sulfonic acid group mainly in the positions
the amino function. If it is protected, predom- ortho or para to the amino group. 2-Methoxy-
inantly the para- and ortho-nitro isomers are 5-methylaniline [120-71-8] is sulfonated with
formed. Nitration of p-acetanisidine [51-66-1] in fuming sulfuric acid to 4-amino-5-methoxy-2-
sulfuric acid yields 2-nitro-4-acetaminoanisole methylbenzenesulfonic acid [6471-78-9] (the
[50651-39-3] as the major product. This com- intermediate to make the dye FD & C Red 40
pound can be hydrolyzed subsequently to the [25956-17-6] [2]).
free amine.
2.2.10. Reduction Only the first two reaction types are of gen-
eral importance. Chemical rearrangements and
Hydrogenation of aromatic amines results in degradations seldom lead to clean reaction prod-
the corresponding cycloaliphatic amines. This ucts in high yield.
process is of greatest importance with amines
that do not contain other easily reducible func-
tional groups. Such catalysts as Raney nickel, 3.1. Reduction
cobalt – alumina, and more exotic ones are
used [46]. Hydrogenation of aniline using an All aromatic carbon – nitrogen compounds with
alumina–silicate catalyst [47] leads to 80 % nitrogen oxidation numbers − 2 can be re-
cyclohexyl-amine [108-91-8] and 15 % dicy- duced to aromatic amines (for a summary see
lohexylamine [101-83-7]; bis(4-amino-3-meth- [52]). Only the reduction of nitro compounds
ylphenyl)methane is reduced in 89 % yield has gained widespread industrial acceptance,
on an alumina catalyst [48]. Hydrogenation be-cause the starting materials can be prepared
of aniline over a Raney nickel catalyst gives with a high degree of specificity for a wide va-
95 % dicyclohexylamine [49]. Good results riety of compounds. Other aromatic nitrogen
have been obtained with rhodium catalysts. 4,4 - compounds cannot be produced economically
Methylenedianiline (MDA) [101-77-9] has been enough to be used as starting materials for aro-
hydrogenated on a 5 % rhodium – aluminum cat- matic amines.
alyst to give bis(4-aminocyclohexyl)methane in
good yield [48].
3.1.1. Chemical Reduction
2.2.11. Other Reactions In the chemical reduction of aromatic nitro
compounds to aromatic amines, the hydrogen
In a reversal of the Bucherer reaction, naphthy-
that becomes attached to the nitrogen normally
lamines can be hydrolyzed to the corresponding
comes from the solvent, in many cases water,
naphthol in yields approaching 100 %. Sulfonic
or from the added acid. The most important re-
acid groups on the ring accelerate the reaction
ductants are metals, such as iron, tin, and zinc;
[50], [51].
phosphorus, sulfides, sulfites, and sulfur dioxide
are used also. Because oxidation of the reduc-
ing agent may result in a useless waste product,
which has to be removed in an environmentally
safe way, chemical reduction has lost its impor-
tance in favor of catalytic reduction for the large-
scale production of products.
3. Production Reduction with Iron. The reduction with
Generally, three types of reactions are used for iron in dilute acid was described by Béchamp in
the production of aromatic amines: 1854 and the process still carries his name. Iron
is still the most important metal for the reduc-
1) Reductions: using such metals as Fe, Zn, Sn, tion of nitro compounds to aromatic amines, and
and Al or their salts; sulfur compounds; elec- generally, all nitro compounds can be reduced
trochemical methods; and catalytic hydro- to the corresponding aromatic amines with iron
genation in water and acid. Side products are expected
2) Nucleophilic substitutions: replacement of only if the molecule contains other substituents
such substituents as halogen, hydroxyl, that can be reduced easily (e.g., nitroso, azo, hy-
alkoxy, and sulfo groups drazine, sulfoxide, and other nitro groups) or
3) Rearrangements and degradations: includ- can be saponified [52]. Carbon – carbon multi-
ing the benzidine and Beckmann rearrange- ple bonds are not attacked. Bayer (Germany)
ments, and the Schmidt and Hofmann degra- and Mobay (United States) both use this iron
dations.
8 Amines, Aromatic
reduction for the production of iron oxides with hydrogensulfide in the presence of ammonia can
aniline as the resulting side product. For a further be used [57], [60].
discussion, → Aniline, Section 2.3, and [52–55]. The reduction of aromatic nitro, nitroso, or
Another example of industrial impor- azo compounds with sulfite or hydrogensulfite
tance is the reduction of 4,4 -dinitro-2,2 - to the corresponding aromatic amines is known
stilbenedisulfonic acid to 4,4 -diamino-2,2 - as the Piria reaction (Piria, 1851). In aqueous
stilbenedisulfonic acid [81-11-8], which is still or alcoholic medium, mainly N- and C-sulfonic
done exclusively using iron in neutral medium. acids result [61]. On treatment of these with
Also, many small-volume dye intermediates are mineral acid, a mixture of aromatic amines and
reduced with iron. aminobenzenesulfonic acids is formed.
The quinone oxime intermediate facilitates
Reduction with Other Metals. Aromatic substitution of hydrogensulfite onto the aro-
nitro groups also can be reduced with zinc, tin, matic ring in the reduction of ortho- and para-
and aluminum, or their salts in acidic, neutral, nitrosophenols or naphthols:
or alkaline medium [52].
These reducing agents are generally very
mild and do not interfere with, e.g.,-OH, -OR,
-COOH, -CO-Ar, halogen, or -CN groups. How-
ever, except for laboratory applications they are
not of any industrial significance. Instead, cat-
alytic hydrogenation is used because of waste
water regulations.
Reductions with Sulfide, Hydrogensulfite, If the hydroxyl group is in the para position,
and Sulfur Dioxide. Compounds with sev- the sulfo group will enter in the 2 – position. Sub-
eral nitro groups can be reduced to nitro stituents in the 3 – position (e.g., Cl or COOH)
amines if a stoichiometric amount of sulfide are replaced by H [62].
is used [56], [57]. In this case, sodium or Only after methods were found to reduce the
ammonium sulfide is the reagent of choice. amount of C-sulfonation did reduction with SO2
m-Nitroaniline [99-09-2] can be obtained in gain industrial importance. This reduction is best
87 % yield from 1,3-dinitrobenzene [56]: carried out in a closed system in strongly acidic
media (e.g., 15 – 40 % aqueous sulfuric acid) at
temperatures of 80 – 180 ◦ C with iodine, hydro-
gen iodide, or iodine salts as catalysts. Glass-
lined reactors are the best [63].
Sodium dithionite reduces the aromatic nitro
and nitroso group nearly quantitatively [64]:
a special case of the chemical reduction. An in- [69], [70]. Ideally 1 mol of hydrazine gives four
organic compound is used as the reducing agent; reduction equivalents depending on the pH and
the oxidized form is then reduced at the cathode catalyst, but in practice fewer are formed, and an
and can react again. excess of hydrazine must be used. Carbon – car-
bon double bonds and carbonyl groups are not
attacked [71]. Depending on the reaction condi-
tions, the intermediates of the reduction can be
isolated.
phase at 200 ◦ C releases 493.2 kJ/mol. Unless Deionized water can be added to remove the heat
this heat is dissipated properly, explosions can of reaction by continuous evaporation. The wa-
result, especially if thermal decomposition of ter also affects the activity of the catalyst; e.g.,
the nitro compound occurs or condensation re- the more water present in the batch hydrogena-
actions are initiated as with chloro – nitro com- tion of dinitrotoluene without solvent, the lower
pounds [52]. To reduce these hazards, the con- the activity of the Pd on carbon catalyst [91],
centration of nitro compound, the amount and [92]. If the amine shows good water solubil-
partial pressure of hydrogen, the temperature, ity, water can be used as the solvent. Water also
and the activity of the catalyst are controlled. can be used in cases where the nitro compound
Vapor-Phase Hydrogenation. Industrial use forms water-soluble salts with alkali, such as
of vapor-phase hydrogenation is limited by the with nitrocarbonic or sulfonic acids. Sometimes
boiling point and the thermal stability of the nitro 30 – 40 % solutions of the amine in water can be
compounds. Most aniline produced in the United produced directly in the hydrogenation reactor
States is made by vapor-phase hydrogenation without an additional concentration step [52],
of nitrobenzene over copper – silica catalyst in [93].
99 % yield, whereas Pd – alumina is used by Solvents. Methanol and 2-propanol are pre-
Bayer in Europe and Brazil. ferred; also dioxane, tetrahydrofuran, and N-
Liquid-Phase Hydrogenation. It is prefer- methylpyrrolidone have been used; e.g., o-
able to hydrogenate most aromatic nitro com- nitrophenol is hydrogenated in good yields
pounds in the liquid phase. In this case the pres- in methanol with Pt on carbon. The concen-
sure and temperature can be changed indepen- tration of the nitro compound can vary sub-
dently. The temperature is limited by the hydro- stantially. According to [94] a 33 wt% solu-
genation reaction of the aromatic ring which oc- tion of dinitrotoluene in methanol is fed into
curs above 170 – 200 ◦ C. Normally the reduction the hydrogenation reactor, whereas Olin rec-
is carried out at 100 – 170 ◦ C. Some compounds ommends a 15 – 35 wt% solution [95]. In the
(e.g., 1-bromo-4-nitrobenzene) must be hydro- hydrogenation with a water-immiscible sol-
genated at lower temperatures (20 – 70 ◦ C) to vent, such as toluene, the water must be re-
avoid cleavage of sensitive groups. Pressures of moved, as in solvent-free hydrogenation, in or-
1 – 15 MPa (10 – 150 bar) are used industrially. der to maintain the activity of the catalyst.
For the hydrogenation of sensitive nitro aromatic Very polar nitro compounds, e.g., bis(4-amino-
compounds lower pressures are advisable (0.1 – 3-nitrophenyl)sulfone, are hydrogenated in liq-
5 MPa, 1 – 50 bar) [82–84]. Generally the pres- uid ammonia [96].
sure only influences the speed of the reaction by Hydrogenation Catalysts. For vapor-phase
increasing the phase transfer and saturation of hydrogenation only metals or metal derivatives
the catalyst with hydrogen. The reaction time on supports are used in fixed beds or fluidized
depends on many parameters, such as hydro- beds, whereas metals with large surfaces (Raney
gen pressure, concentration, temperature, activ- nickel) or metals and metal derivatives on sup-
ity and concentration of the catalyst, and mixing. ports with large surfaces (carbon, alumina) are
Often an induction period is observed, which is used for the liquid-phase hydrogenation. In prac-
independent of the activity of the catalyst [85], tice only Raney nickel, Raney nickel – iron,
[86]. Generally the reaction time is from a few Raney cobalt, and Raney copper are used as
minutes to several hours. Considerably longer pure-metal catalysts because of their relatively
times are necessary if these parameters are not low cost. Precious-metal catalysts, such as Pt
optimized. and Pd, generally are used at concentrations
Because of the exothermic nature of the reac- of 0.5 – 5 wt% on support material with large
tion, many safety precautions must be observed, surfaces, such as charcoal, silica, aluminum
especially for the industrial hydrogenation of oxide, or alkaline-earth carbonates. The pow-
aromatic polynitro compounds in the liquid dered form of the catalyst is used in slurries and
phase without solvents [87–89]. The exothermic the pellet form in fixed beds [97]. Because the
reaction is controlled by the continuous addi- support material may activate or deactivate the
tion of small quantities of the nitro compound, catalyst [81], it is important to find the optimum
thus keeping its concentration below 2 % [90]. conditions that not only allow the catalyst to
Amines, Aromatic 11
be used repeatedly and to be regenerated but out loss of activity or selectivity while chlo-
also are economical for large-scale (> 500 t/a) rine cleavage was kept 0.1 %; yield of 2,5-
products [88], [98]. Decomposition and oxi- dichloroaniline [95-82-9] was 97 %. Also a 1 %
dation products generally deactivate catalysts Pt on carbon catalyst was treated with dimeth-
by blocking the active surfaces [81]. Even in ylsulfoxide in water before it was used in the hy-
small quantities, compounds containing sul- drogenation of chloronitro aromatic compounds
fur, arsenic, or antimony are catalyst poisons. in 98.4 % yield [104]. Additional treatment with
However, with increased oxidation state (e.g., hydrazine hydrate increased the activity of the
As3− → As5+ or S2− → S4+ ) these compounds catalyst with yields of 99.6 % for 2-chloroaniline
have less effect as catalyst poisons. With noble [95-51-2]. Modification of Pt on carbon with
metal catalysts, such ions as halide, sodium, and lead, bismuth, or silver salts for the hydro-
magnesium, cobalt metal, and CO2 reduce the genation of chloronitrobenzene at 100 ◦ C gave
activity. Nitro aromatic compounds containing chloroaniline in 99 % yield, whereas untreated
sulfur are better reduced with molybdenum or catalyst at 77 ◦ C resulted in 100 % hydroly-
tungsten sulfide [99], or with nickel catalysts sis [105]. 3-Bromonitrobenzene has been hydro-
that contain zinc or calcium carbonate [102]. In genated using Pt on barium or strontium carbon-
the hydrogenation with Pd on carbon, copper ate at 20 ◦ C, 0.1 MPa (1 bar) [106]. The catalytic
salts are catalyst poisons, whereas in the hy- activity of Raney nickel can be modified also.
drogenation of dinitrotoluene, both nitrophenol For the hydrogenation of 3-chloronitrobenzene
and nitrocresol are strong catalyst poisons and the addition of 0.1 – 20 % of thiocyanate to the
decomposition activators [46], [101]. catalyst has proved beneficial [84].
Hydrogenation of Halide-Substituted Nitro Equipment and Construction Materials. Hy-
Compounds. Whereas most aromatic nitro com- drogenation in the vapor phase is carried out
pounds are hydrogenated at 100 – 170 ◦ C, lower only continuously, but in the liquid phase it
temperatures are used with halogen-substituted can be done in batch or continuous operation
nitro compounds to avoid halide – hydrogen ex- de-pending on volume. Continuous liquid-phase
change. The catalysts have reduced activity, hydrogenation is used exclusively for a relatively
e.g., sulfide-poisoned metal catalysts. 1-Chloro few large-scale products, such as dinitrotoluene,
2 – nitrobenzene can be reduced at 80 ◦ C and nitrotoluene, and 1-nitronaphthalene [92]. The
1.0 – 5.0 MPa (10 – 50 bar) with a 5 wt% Pt on vast majority of aromatic amines have small
carbon catalyst, which is treated at 22 ◦ C with annual volumes (< 500 t) and are produced by
dilute sulfuric acid, then with H2 followed by batch hydrogenation with catalyst slurries. This
H2 S [102]. The catalyst can be recycled up allows fast changeover from one product to an-
to 30 times without any further purification. other, which is not possible when fixed-bed cat-
The reaction time is 30 min per batch and only alysts are used. The intensive mixing of the three
0.1 % chlorine is cleaved. Therefore, a product phases (hydrogen gas, nitro compound solution,
of high purity and stability can be obtained in and solid catalyst) is of great importance. The
nearly quantitative yield. Also 3-chloroaniline transport of the reactants toward the active cen-
[108-42-9], 4-chloroaniline [106-47-8], 2,5- ters of the catalyst, and of the products away
dichloroaniline [95-82-9], 3,4-dichloroaniline from them, must be rapid for good reaction.
[95-76-1], 2,6-dichloroaniline [608-31-1], 6- Although batch catalytic hydrogenations tra-
chloro-2-aminotoluene [87-60-5], and 4-chloro- ditionally are done in stirred, steel or stain-
2-aminotoluene [95-79-4] can be prepared in less steel autoclaves (Fig. 1), improvements
high yield and purity by this method. in performance are being realized increas-
A similar sulfide-poisoned catalyst has been ingly through loop reactor technology. Produc-
described [103], in which 5 % platinum on tion units employing the loop reactor princi-
carbon catalyst was treated with 1 % aque- ple (Fig. 2) have been available for the last two
ous sulfuric acid, hydrogen, and sodium sul- decades and have been applied successfully to
fide solution. 2,5-Dichloronitrobenzene was hy- the catalytic hydrogenation of aromatic nitro
drogenated with this catalyst at 90 – 100 ◦ C, compounds by Buss (Basel, Switzerland) [107–
1.0 – 3.0 MPa (10 – 30 bar), 40 min per batch. 110]. The major advantages reported over stirred
The catalyst was recycled at least 30 times with- autoclaves are increased heat and mass trans-
12 Amines, Aromatic
fers and improved reaction selectivity. In con- ment at the nozzle exit. The autoclave acts as a
tinuous hydrogenation, generally shorter batch holding vessel. A loop reactor allows for simple
cycle times and higher product yields result. In and reliable transfer from pilot plant to produc-
addition catalyst usage is often lower. tion, because the scaleup is based only on the
nozzle configuration and pump-around rate. In
the case of a stirred autoclave, scaleup is more
difficult because of the ratio between a small
pilot vessel and a large production vessel (e.g.,
1 : 1500 to 1 : 12500). Temperature and concen-
tration gradients as well as longer reaction times
in the production vessel often result in undesired
side reactions and a decreased product yield.
Loop reactors minimize these problems by limit-
ing the reaction to a highly agitated, well-defined
zone, with a considerably decreased cycle time.
The more basic the amine (unless it is ster- Reaction Conditions. The reaction is gener-
ically hindered), the faster the reaction with ally carried out in aqueous suspension or in so-
the haloaromatic compound. In the reaction lution at elevated temperature and pressure. Be-
of methylamine and ammonia with a solution cause the reaction of arylhalides with amines
or suspension of 2,4-dinitrochlorobenzene at is exothermic, it is especially important in the
higher temperature, good yields of N-methyl- batch process to watch the temperature while
2,4-dinitroaniline are obtained, rather than 2,4- heating to reaction conditions. This normally
dinitroaniline [120]. poses no problem in the continuous reaction. The
Reaction Conditions. 4-Nitroaniline hydrogen halide released during the reaction is
[100-01-6] is produced in an agitated tita- neutralized either by excess ammonia or by the
nium reactor in 99.3 % yield by reacting 4- addition of bases, such as sodium carbonate or
chloronitrobenzene [100-00-5] with a tenfold calcium oxide [113]. With excess amine the re-
excess of aqueous ammonia at 175 ◦ C and action generally proceeds with nearly quantita-
4.2 MPa (42 bar) for 10 h [121]. tive yield. With an insufficient excess of strongly
4-(4-Methylanilino)−3-nitrobenzenesulfon- basic amines in aqueous solution, side reac-
amide tions such as hydrolysis or the formation of di-
is prepared in 90.1 % yield by heat- arylamines, can occur. Cyano groups are hy-
ing 4-chloro-3-nitrobenzenesulfonamide and drolyzed to amides in aqueous solution, but this
p-toluidine [106-49-0] for 5 h at 130 ◦ C reaction can be avoided by using an inert sol-
[111]. 4-Nitrodiphenylamine [836-30-6] (pre- vent. Carboxylic acids are converted easily to the
cursor for antiozonants for rubber) is made corresponding amide by reaction in nonaqueous
by the condensation of 4-nitrochlorobenzene media.
with aniline in chlorobenzene. N-Alkylated p-
phenylenediamine derivatives, however, cannot
be produced in aqueous medium.
14 Amines, Aromatic
The carcinogenic potential of aromatic to the nucleic acid bases of DNA. The follow-
amines is of greatest concern. A number of ing reaction sequence has been proposed, where
them are known or are suspected of being car- ArNH2 is the aromatic amine [153].
cinogens. Indeed it has been reported that the
epidemiology of aromatic amine carcinogene-
sis is essentially the epidemiology of human
cancer of industrial origin [145]. The first sus-
picion of aromatic amine carcinogenesis was
raised in 1895 when cases of bladder cancer in
Swiss dye workers were reported [146]. Since This reaction sequence implies that structural
then a number of epidemiologic investigations factors in the aromatic amine favoring the cation
and animal studies have identified which aro- formation (e.g., electron-donating substituents
matic amines are carcinogenic [147–149]. Be- ortho and para to the amino group) enhance car-
cause most aromatic amines have not been ex- cinogenicity. Figure 4 is a sampling of some car-
amined thoroughly for carcinogenic potential, cinogenic amines [154].
researchers are attempting to develop theoreti- In addition to the effects cited in Table 1
cal models for determining which ones are car- [144], aromatic amines can cause a wide va-
cinogenic [150–152]. Structural requirements, riety of other symptoms, such as eye and skin
such as the type of aromatic ring system, the irritation. By drawing correlations from animal
position of the amine group on the ring, and the studies, exposure to some of these compounds
presence and position of other substituents, are may lead to liver and kidney damage.
believed to be important to carcinogenic poten-
tial. Chemical carcinogens exert their effect by
causing DNA damage, which leads to tumor for- 5.2. Exposure Limits
mation. The metabolic reaction products, rather
than the aromatic amines themselves, are be- Various countries have established their own ex-
lieved to damage the DNA. These reaction prod- posure limits for workers [156–160]. As an il-
ucts are electrophilic and are covalently bonded lustration, Table 2 lists those aromatic amines
Amines, Aromatic 17
Table 1. Effects of the chronic administration of primary amines on the blood, liver, and bladder of dogs
exposure is best prevented through the use of 4. United States International Trade Commission,
engineering controls. Whenever possible, pro- Publication 1548, “Import of Benzenoid
cesses containing aromatic amines should be Chemicals and Products 1983,” Graphics
enclosed. In a closed process exposure can oc- Branch, Washington, D.C., July 1984, pp. 10,
cur only when equipment fails or when process 23.
streams are sampled. If a process is not enclosed, 5. Japan Dyestuff Industry Assn., Japan Chem.
ventilation (both general diluted and local ex- 1982 (April 15) 8.
haust) should be used to prevent or reduce expo- 6. K. Weissermel, H.-J. Arpe, Industrielle
sure. Ventilation specifications for a number of Organische Chemie, Wiley-VCH, Weinheim
1998.
industrial processes are available [164]. When
7. W. L. Semon in Davis, Bake (ed.): The
ventilation controls are not sufficient to lower
Chemistry and Technology of Rubber,
exposure, respirators should be used until ef- Reinhold Publ. Co., New York 1937, p. 414.
fective controls are installed. When respirators 8. R. G. Bauman, J. W. Born, J. Appl. Polym. Sci.
are used, a complete respiratory protection pro- 1, (1959) 351.
gram should be instituted that includes regular 9. G. S. Petrov, V. F. Prosvirkina, Zh. Prikl. Khim.
training, maintenance, inspection, cleaning, and (Moscow) 30, (1956) 1660. Chem. Abstr. 52
evaluation. Where skin contact may occur, work- (1958) 5028 f.
ers should wear impervious clothing, including 10. G. Oster, US 3014799, 1961.
gloves and boots. Contaminated clothing should 11. H. E. Fierz-David, L. Blangey: Fundamental
be stored in closed containers until discarded or Processes of Dye Chemistry, 5th ed.,
cleaned. Safety showers should be available in Interscience, New York 1949, pp. 99, 140, 179,
the immediate area where exposure can occur so 306.
that the body can be washed quickly. 12. Horizon Inc., US 3082086, 1963 (R. H.
Sprague).
13. Horizon Inc., US 3056673, 1962 (E. Wainer).
5.4. Environmental Monitoring 14. Du Pont, US 3673143, 1971 (T. I. Bair, P. W.
Morgan).
15. R. E. Wilfong, J. Zimmerman, Rubber World
Routine monitoring of the airborne aromatic
166 (1972) 40, 47.
amine concentration should be performed
16. A. Galat, G. Elion, J. Am. Chem. Soc. 65
to evaluate worker exposure. Measurements (1943) 1566.
should be taken on a single 8-h sample or two 17. G. R. Petit, E. G. Thomas, J. Org. Chem. 24
4-h samples to determine the 8-h TWA expo- (1959) 895.
sure. In addition, short-term samples should be 18. C. S. Marvel, G. S. Hiers, Org. Synth. Coll. 1
taken to determine peak exposure when work- (1941) 327.
ers are doing specific tasks with a potential for 19. K. H. Slotta, H. Dressler, Ber. Dtsch. chem.
exposure. Air samples should be taken in the Ges. 63 (1930) 889, 894. Houben-Weyl 9,
worker’s breathing zone. Several methods are 871.
available for airborne aromatic amine monitor- 20. F. B. Dains, R. Q. Brewster, C. P. Olander, Org.
ing [165, 166] [167]. Synth. Coll. 1 (1941) 447.
21. Shell Development Co., US 2580284, 1951
(T. J. Deahl, F. H. Stross, M. D. Taylor).
6. References 22. Du Pont, US 3649693, 1975 (D. R. Coulson).
23. Biller, Michealis & Co., US 2991311, 1961
1. M. N. Desai, Trans. Saest 16 (1981) no. 2, (M. Thoma).
77 – 87. Chem. Abstr. 95 (1981) 105208 p. 24. A. K. Bhattacharyya, D. K. Naudi, Ind. Eng.
2. Colour Index, 3rd ed., Society of Dyers and Chem. Prod. Res. Dev. 14 (1975) no. 3, 162.
Colourists, Bradford, England, and American 25. R. Stroh, J. Ebersberger, H. Haberland, W.
Association of Textile Chemists and Colorists, Hahn, Angew. Chem. 69 (1957) 124.
North Carolina, United States, 1971. 26. Ethyl Corp., US 4219502, 1980 (K. G.
3. United States International Trade Commission, Ihrmann, M. Brandt).
Publication 1588, U.S. Government Printing 27. Ethyl Corp., US 4128582, 1978 (L. J.
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Amines, Aromatic 19
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