Jan. 1, 1963 H. J. KEHE E.

A 3,071,619
PREPARATION OF SECONDARY ARYL AMINES
Filed June 9, 1959
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45 53
43 54 INVENTORS
FG. 2 HENRY U. KEHE
RoGER. T. JoHNSON
COOLING AND WILLIAM J.DRISCOLL
SET LNG CHAMBER BY Epit R. BLOOR

REacToR Y44 55
%-47.1 ATTY.
 3,071,619
United States Patent Office Patented Jan. 1, 1963

2
resistant gas-tight gasket 14 disposed between flanges 15,
3,071,69 16 of the reactor.
PREPARATION OF SECONDARY ARYL AMNES The reaction temperature is controlled by a thermo
Henry J. Keae, Akron, and Roger T. Johnson, William J. couple, disposed in thermowell 17, the thermocouple is
Drisco, and Robert R. Bloor, Lorain, Ohio, assignors connected by wires to a temperature indicator 18, which,
to The B. F. Goodrich Company, New York, N.Y., a in turn, is connected to an electrical system, such as a
corporation of New York rheostat, for control of the flow of current through the
Fied June 9, 1959, Ser. No. 89,108 heating elements.
8 Caias. (C. 260-576)
At the bottom of the reactor is a drain line 19, having
This invention relates to a method for preparing sec O a valve 20. This line connects with receiver 21, having
ondary aryl amines from primary aryl amines and more a valve 22.
particularly pertains to a method for preparing secondary Tube 23, having a rupture disc 24, communicates with
aryl amines of the benzene series by reacting primary the interior of the reactor.
amines of the series in liquid phase at elevated tempera A mixture of primary aryl amine and catalyst is fed
tures in the presence of a catalyst containing boron and 5 into the reaction chamber through tube 25, which is
fluorine atoms. connected to a source of supply (not shown) of the
Secondary aryl amines of the benzene series are useful reactants. The temperature of the reaction mixture is
as raw materials for making antioxidants, as stabilizers raised to 275-450° C. and the pressure is permitted to
for explosives and as dye intermediates. Thus, for ex build up in the reactor to keep the reaction mixture
ample, when diphenylamine is melted with elemental sul 20 in a liquid state. Preferably, the mixture is agitated by
fur it is converted to thiodiphenylamine (phenothiazine), a stirrer (not shown) during the reaction. Vapors from
which is the parent substance of thiazine dyes. Acridine the reaction pass through line 26, which has attached to
can be prepared by reacting diphenylamine with formic it a condenser 27. This can be either an air or liquid
acid in the presence of zinc chloride. cooled condenser. Ordinarily an air condenser is ade
All catalysts heretofore used for preparing secondary 25 quate to cool the primary amine vapors, but, if desired,
aryl amines are highly corrosive to equipment made of the condenser can be cooled with a warm liquid, such as
ferrous metal, including stainless steel. These catalysts hot water. A pressure gauge 28 connected to line 26
includes such compounds as HCl, NHCl, NHBr, FeCls, is useful for regulating the pressure conditions in the
ZnCl2 and AiCl3. In addition, the above catalysts effect reactor to insure that the reaction mixture remains liquid.
considerable side reaction as evidenced by comparatively 30 During the course of the reaction ammonia is split out
large amounts of tar formation and the catalyst, once and vaporized. The ammonia vapor pressure can be util
used, cannot be recovered readily from the reaction mix ized to maintain the reaction mixture in a liquid state.
ture, so that on separation of the secondary amines the It is desirable, but not essential, to remove the ammonia
catalyst exerted additional deleterious effects. from the reaction system. For this purpose bleeding of
Contrary to expectations NH4F exerts substantially no 35 ammonia without loss of amine can be effected by operat
catalytic action on the reaction and alkali metal fluo ing valve 29 on line 30, which is connected to line 26.
borates are also inactive. A liquid trap 31 may be connected to line 30. After
We have found, surprisingly, that NHBF4 and BF holding the reaction mixture for the requisite time at the
or BF containing compounds or complexes which are desired temperature and pressure the hot mixture is per
convertible to NHBF4 at elevated temperatures of about 40 mitted to flow into the receiver. On cooling the mixture
125 to about 450° C. in the presence of ammonia or to about 275 C. the catalyst is substantially crystallized
primary amines will catalyze the conversion of aromatic therefrom. About 80-90% of the initial catalyst is in
primary amines of the benzene series to secondary aro soluble in the diarylamine and the remaining 10-20%
matic amines, when the reaction is carried out in liquid is either soluble or is lost in the process. The crude
phase at about 175-450° C. The catalyst in the finished 45 reaction mixture can then be filtered, the crystalline cata
reaction mixture is in crystalline form and represents lyst recovered and re-used in another batch of reactants,
about 80 to slightly more than 90% of that originally and the diarylamine can be purified, if so desired, by dis
employed, so that the crude reaction mixture need only tilling off the unreacted primary amine, dissolving the sec
be filtered and the catalyst can be reused as is, or slightly ondary amine in a suitable solvent and crystallizing the
less than 10 to 20% additional fresh catalyst can be
50 So purified diarylamine.
added and very good yields of secondary aryl amines are The apparatus of FIG. 1 can also be employed for con
obtained. tinuous operation if the feed and withdrawal of product
Referring to the drawings, FIG. 1 is a vertical section is each regulated so as to maintain the reactants under
of an apparatus that can be employed for diarylamines by pressure for sufficient time to convert the primary aryl
55 amine to a secondary diarylamine.
the batch process. A modified form of apparatus for continuous operation
FIG. 2 represents a vertical section of an apparatus is shown in FIG. 2. The primary aromatic amine and
which can be employed for a continuous process of pre catalyst mixture is fed into reactor 40 through tube 42.
paring the diarylamines. The tube extends close to the bottom of the reactor. The
Referring now to FIG. 1, the apparatus consists of a 60 reactor has a jacket 43 with an inlet 44 and outlet 45 for
stainless steel reactor 10 mounted on supports 1. The entry and exit, respectively, of a hot circulating fluid,
reactor has a plurality of electrical heating elements, 12 which may be liquid or gaseous, to maintain the tempera
surrounding its outer wall, and insulation 13 to minimize ture of the reaction mixture in the proper range. Vapors
heat loss to the atmosphere. The chamber has a heat from the reaction pass through tube 46 into air condenser
 3,071,619
3 4.
47. A pressure gauge 48 is attached to the top of the air separate aniline and diphenylamine out of the ammonia
condenser and a laterally extending line 49, with a valve vapor. After completion of the reaction the mixture
50 is also connected to the condenser. This waive serves was passed into another pressure vessel and cooled rap
to maintain the pressure at the proper level and also to idly. A mixture of aniline and diphenylamine was dis
vent ammonia which is formed during the reaction. The 5 tilled at 3-5 mm. Hg. Unreacted aniline was stripped
return tube 51 from the condenser extends almost to the from the mixture and the diphenylamine was recovered by
bottom of the reactor and has a convolute turn which distillation at 100-120° C. and 0.5-1 mm. pressure. The
serves as a liquid Seal. At the reaction temperature the small amount of residue was a tar. In all these runs
catalyst is essentially in solution so that stirring is not nec NHBF was the catalyst. The table below contains the
essary, but the mixture can be stirred if desired to insure O results of the several runs.
maximum contact between catalyst and primary amine.
With this construction, the unreacted primary amine ini
tially entering the reaction zone and the condensed vapors Ratio, Percent Percent,
both enter the heated zone near the bottom of the reac Run Aniline Cata- aminel Temp., Time, conver yield
tor, so that time and contact with catalyst is at a maxi lyst catalyst C hrs. sion of diphenyl
15 aniline amine
mum. As the amount of reactants builds up in this reac
tor it will completely fill it and overflow through tube 52 930 13.1 80: 350 3 43.1 97.1
into a cooling chamber 53. This cooling chamber has a 930
930
26.2
3.1
40:1
80:
350
330
3.
3
33.5
29.4
97.0
94.0
jacket 54 together with an inlet 55, and outlet 56 for cir 930 13.1 80:l 370 3 46.0 94.6
culating a cooling medium, if such is desirable. It is also 930
930
6.6
3.
60:
80:1
350
350
3
6
24.8
50.3
96.7
93.9
desirable to stir the product in the cooling and settling 930 13.1 80:1 360 2 33.8 96.7
chamber so that as this chamber fills up the cooled prod
uct will be taken off through tube 57 which has a valve
58 for controlling the outlet rate. In place of the con The insoluble residue from run 7 was filtered from
struction shown, it is also possible to have the bottom of 25 the reaction mixture and charged back to another batch
the cooling chamber in the form of an inverted cone hav of 930 parts aniline, and 2.6 parts of fresh NHBF4.
ing an outlet valve. In such event it would be unneces This weight of NHBF, amounts to 20% of the 80: 1
sary to stir the cooled product since the catatlyst in crys ratio used in the above example. This procedure of
talline form can be drained from the bottom of the cool recovering catalyst, adding 20% fresh catalyst and charg
ing chamber, filtered and returned to the reactor. The 30 ing to a new batch was repeated ten times. In the tenth
fitrate can be subjected to distillation to separate the un charge so made the aniline converted to diphenylamine
reacted primary amine which is returned to the reactor. was 42.6% and the yield was 94.4%. This latter reac
The amount of catalyst employed can vary quite widely. tion was run at 360° C. for 3.5 hours.
* Good results have been obtained with molar ration of In another series, using BF3 initially and as make up
. . aniline to catalyst from about 160:1 to about 10:1, but 35 catalyst at 80% recovered catalyst and 20% fresh cat
for economic reasons it is most desirable to use ratios of alyst forty-eight batches of diphenylamine were made
about 40-80 moles of aniline for each mole of catalyst. without encountering and difficulty. The aniline catalyst
Representative primary amines which can be reacted ratio was 40 to 1 and temperatures of 300-400° C.
include aniline and mono- or polyloweralkyl substituted were employed. These batches were run both with and
anilines, representative members of which are ortho-tolu 40
idine, meta-toluidine, para-toluidine, 2-ethyl aniline, 3 without venting of NH3.
A mixture of 12.8 moles of aniline and 1 mole of
ethyl aniline, 4-ethyl aniline, 2,3-dimethyl aniline, 2,4-di
methyl aniline, 2,5-dimethyl aniline and 2,6-dimethyl ani BF35 C.
was reacted for 36 hours at a temperature of 183
at atmospheric pressure. Ammonia was vented
line, 3,4-dimethyl aniline, and 3,5-dimethyl aniline. from the
Halogenated amines, such as mono-, di- and trichloro 45 The highestreaction mixture as the reaction proceeded.
percentage of aniline converted was 5 and
anilines, ring halogenated mono-, di- and trichlorotolui the yield of diphenylamine based on the aniline reacted
dines, ring halogenated xylidines and ring halogenated
ethyl benzene can also be used. Mixtures of primary batch57.of aniline
was 20% additional catalyst was added to a fresh
in the same ratio as above. The re
amines can also be reacted to form secondary arylamines.
The venting of ammonia is not absolutely essential for 50 action was then run for 36 hours at a temperature of
184-88-C. with venting of ammonia and at atominous
obtaining good results, but removal of the ammonia aids pressure. The yields of diphenylamine were substan
in shifting the reaction towards the desired direction, be tially the same as that described above.
cause it is known that ammonia slows down the forma
tion of the secondary amines. EXAMPLE II
The catalyst can be added as BFs, as a complex of BF, 55 Good yields are obtained when the reaction mixture
such as an etherate, ammonia BF complex, or amine is run at a higher temperature even though the aniline
BFs complex or it can be added in any form which is con catalyst ratio is somewhat lower. Thus, a reaction mix
vertible to NHBF4 under reaction conditions. It can ture made from about 28.6 mole of aniline per mole
also be added as ammonium fluoborate. In fact, any of BF3 was run at 275-290° C. for 5 hours at a pres
boron trifluoride containing compound which is conver 60 Sure of 130 to 140 pounds per square inch. Ammonia
tible to amomnium fluoborate under the reaction condi was periodically vented from the system. The yield of
tions herein described is satisfactory for catalytic pur the diphenylamine based on the reactant aniline was
poses. It is preferred, however, to add the catalyst as 84.2% and the percent conversion to diphenylamine
ammonium fluoborate. was 12.5%.
In the following examples the parts are given by weight 65 EXAMPLE II
unless otherwise specified.
EXAMPLE I When the proportions of reactants used in Example
II are employed and the temperature is raised through
A series of runs were made using aniline and NHBF, about 325-350° C. at a pressure of 260-75 pounds per
for the production of diphenylamine. The time, temper 70 Square inch with venting of ammonia the percent con
ature and catalyst ratios were varied. In making these Version to diphenylamine is 48.4% and the yield is
runs the aniline and catalyst were charged to an autoclave. 88.5%.
The mixture was heated and the autoclave was vented EXAMPLE IV
manually each /2 to 1 hour to remove excess ammonia. To the catalyst recovered from the run in Example
The vent gases were passed through a reflux condenser to 75 III was added 20% additional BF in mole ratio of
 8,071,619
5
one mole of catalyst per 28.6 moles of aniline. The was added per run. The results obtained are shown in
reaction was run for 5 hours at a temperature of 325 Table B below.
50° C. and a pressure of about 275 to 300 pounds per Table B
square inch with venting of ammonia. The percent con
version in this run was 28.1. The diphenylamine yield 5
was close to 100%. Conversion, Yield, Weight
EXAMPLE V No. Or runs percent percent cat. res.,
gns.
A mixture containing a molar ratio of 28.6 moles of
aniline per mole of BF was run for one hour at a 37.9
46.4
95.5 --------------
94.9 20.4
temperature of 400 to 410° C. at a pressure of 400 to 49.5 95.0 25.4
450 pounds per square inch with venting of ammonua. 48.7 95.7 23.2
The percent conversion was 43.2 and the diphenylamine 41.2 94.8 127.0
yield was 84.0%. 44.1
43.9
96.1
96.8
38.0
37.0
EXAMPLE VI 26.9 98.5 --------------
39. 97.4 20.2
A BFs. NH3. complex in a mole ratio of 1 per 28.6 44.4 96.4 26.9
moles of aniline was heated to 400-410° C. at a pres 43.5 95.9 32. I.
sure of 600-700 pounds per square inch for one hour. 44.9 95.6 32.3
Under these conditions the BF3.NH complex is con 45.1 95.6 24.4
45.1 95.2 29.9
verted to ammonium fluoborate. Ammonia was vented 47.3 95.6 34.2
periodically during this period. Percent conversion to 42.9
44.9
94.7 --------------
94.6 3.7
diphenylamine was 18.0 and the diphenylamine yield 46.0 94.2 3.9
was 76.6. In an identical reaction with the exception
that the pressure was reduced to 550 pounds per square 1 Switched to 335 C.
inch the diphenylamine conversion was 28 and the yield 25 a Started using 55% recycle NH, K X
was 87.4.
EXAMPLE VII
A mixture of aniline and BF in a molar ratio of It is apparent that continued reuse of the catalyst with
40:1 was reacted for one hour at 400° C. at a pressure only very small amounts of make up does not affect its
of 740 pounds per square inch. During this reaction 30 activity.
ammonia was not vented. The percent conversion to di EXAMPLE X
phenylamine was 22.0 and the percent yield on the A mixture of aniline and BF at a mole ratio of 160 to 1.
ammonia reacted was 90.5. was prepared. This was heated to 400° C. and held at
EXAMPLE VIII 35 this temperature for 1 hour. Ammonia was not vented
during this reaction period. Percent conversion to di
A mixture of aniline and BF in a mole ratio of 80 phenylamine was 24.6% and the yield on the aniline re
to 1 was reacted for 2 hours at a temperature of 400 acting was 96.5.
20 C. at a pressure of 350-500 pounds per square EXAMPLE XII
inch. Ammonia was vented during this run. Percent 40 In a continuous process a mixture containing a 40 to 1.
conversion to diphenylamine was 22.3 and the percent
yield based on the aniline reacted was 74.5%. mole ratio of aniline-BF was passed through a reactor
EXAMPLE X
over a period of one hour at a temperature of 400° C.
at a pressure of 600 to 750 pounds per square inch. Am
Aniline was blended with a B.F.NH complex in a monia was not vented in this run. The percent conversion
mole ratio of 40 to 1. This was heated to 400 to 415 45 to diphenylamine is 18.0. In another run using the same
C. and the reaction was run for one hour at 600 to 700 proportion of reactants and catalyst for the same time,
pounds per square inch with venting of ammonia. The but lowering the pressure to 400-500 C. and venting of
percent conversion to ammonia was 38.3 and the yield ammonia the percent conversion of aniline to diphenyl
based on the aniline reacted was 89.2. amine was about 20.5. In each case the catalyst could
EXAMPLE X 50 be removed from the reaction mixture by filtration and re
turned to the reactor without loss of catalytic activity.
A series of batch runs was made at 350° C., except EXAMPLE XII
as otherwise indicated, with an aniline to catalyst ratio
of 40 to 1. Ammonium fluoborate was the catalyst. A mixture of para-toluidine and ammonium fluoborate
The reaction period was 3 hours. The ammonia was 55 in a mole ratio of 40 to 1 was reacted for 3 hours at 330°
vented during the reaction period. After each run the C. After running this reaction for 2 hours the system
reaction mixture was filtered, the catalyst was recovered, was vented and found to contain ammonia. No addi
20% new catalyst was added and the run repeated under tional venting was carried on during the remainder of the
substantially the same conditions. The table below run. The percent conversion of para-toluidine was 17.6
shows the results obtained in these tests. 60 and the percent yield of di(methylphenyl)amine based on
the toluidine reactant was 67.8.
Table A EXAMPLE XIV
A mixture of Xylidines containing 2,3-, 2,4-, 2,5-, 2,6-
Conversion, Yield, Weight 65 dimethyl 3,4- and 3,5-aniline and sufficient ammonium
No. of runs percent percent cat. res.,
gms. fluoborate to provide a mole ratio of amine to catalyst of
from 40 to 1 was prepared and reacted at a temperature
45.9 95.8 -------------- of 335 C. for 3 hours. The system was vented after 2
48.2 95.6 23 hours and the vapors were found to contain ammonia.
47.9
49.7
95.2
94.5
22.5
27.5 70 After completion of the reaction the mixture was distilled
48.0 95.8 29.9 at 94 to 98 C. at 6 millimeters. At this temperature the
diaryl amines seemed to breakdown. However, there
remained a small amount of a yellow liquid which was a
In another series of tests the reaction conditions were mixture of diaryl amines that could not be separated with
substantially identical except that only 10% new catalyst 75 aS
 3,071,619
7 8
EXAMPLE XV possible the construction of reaction equipment, readily
Four runs were made at 350° C. over a 3 hour period available materials, does not require exceptional linings
using aniline as the amine in a 40 to 1 aniline catalyst Such as those necessary when the conversion of primary
ratio. In one group of two runs NHBF was the catalyst. amines to Secondary amines are effected by the highly
This was recovered at the end of the operation and 20% corrosive catalysts.
fresh catalyst was added to another batch of aniline and We claim:
the same reaction conditions as those above were fol 1. Method of preparing diphenylamine comprising
lowed. This same procedure of recovering catalyst was heating aniline in the presence of boron fluoride as a
also used with two runs using BF3 as a catalyst under con catalyst under superatmospheric pressure.
ditions described above, with 20% addition of fresh cata 10 2. A method for preparing diaryl amines of the ben
lyst in the second run. Zene Series comprising heating a primary amine from the
The results of these tests are shown below: class consisting of aniline and lower alkyl ring substituted
aniline in the presence of a catalyst consisting of a BF
Percent Percent containing compound which is convertible to NHBF
Catalyst Run conversion yield di
phenylamine
5 under the reaction conditions specified, at a temperature
of from about 175 to about 450° C., the moleratio of
NHabF4---------------------- 45.9 95.8
the catalyst to amine being from about 1 to 10 to about
NE 2 48.2 95.6 1 to 160.
3. A method of preparing diphenylamine comprising
BF3-----------
III. 2
47.0
48. 4
93.2
93.7 heating aniline in liquid phase in the presence of a BF
complex which is convertible to NHBF under the re
When other complexes of BF3, including etherates, but action conditions specified at a temperature of from about
not limited thereto, are used as a catalyst in the reaction 175 to about 450° C. the mole ratio catalyst to amine
systems, the conversion of primary aryl amines to sec being from about 1 to 20 to about 1 to 120.
25 4. The method of claim 3 in which the catalyst is
ondary aryl amines is effected, and substantially the same BF.
order of yields are obtained.
Also, other primary amines can be substituted in place 5. The method of claim 3 in which the catalyst is
of those described in the specific examples to prepare sec BF3 and aniline is the amine.
ondary aryl amine by the process of this invention. 30
6. The method of claim 3 in which the catalyst is
The corrosion rates for BF were also studied. 304 BF etherate.
and 316 type stainless steels and carbon steel were sub 7. The method of claim 3 in which the catalyst is
jected to NHBF4 containing reaction mixture, liquid and ammonium fluoborate.
vapor, at temperatures up to 350° C. for a period of 8. A method for preparing diphenylamine comprising
slightly more than 172 hours during several batch runs. 35
heating aniline in liquid phase in the presence of an
304 stainless steel in the liquid NHBF4 showed a corro monium fluoborate at a temperature of from about 300
sion rate of .0011 inch per year. In the vapor phase the to 350° C., the mole ratio of catalyst to amine being
corrosion rate was .0125 inch per year. With 316 stain from about 1 to 40 to 1 to 80.
less steel the liquid corrosion rate was .0010 inch per year
and the vapor phase corrosion rate was .0069 inch per 40 References Cited in the file of this patent
year. Carbon steel showed a corrosion rate of .0001 UNITED STATES PATENTS
inch per year when subjected to liquid NHBF and .0043
inch per year when subjected to the vapor phase. These 2,225,368 Craig ----------------- Dec. 17, 1940
corrosion rates are considerably lower than those of am 2,391,139 Dickey et al. ----------- Dec. 18, 1945
monia chloride, ammonia bromide, aluminum chloride, 45 2,656,389 Johannesen ------------ Oct. 20, 1953
Zinc chloride or ferric chloride. Therefore, it makes 2,834,799 Sowa ----------------- May 13, 1958
 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,071,619 January l, l963
Henry J. Kehe et al.
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.

Column la line 28, for "includes" read -- include --

Column 3 line 34 for "ration" read -- ratios --; column 4,
line 37 for "and" read -- any --; line 5O, for "i84-88-C."
read -- 184-88° C. --; column 6 line 67 for "trom" read
-- from --
Signed and sealed this 23rd day of July 1963.

(SEAL)
Attest:

ERNEST W. SWIDER DAVID L. LADD

Attesting Officer Commissioner of Patents