United States Patent (19) (11) 3,728,392

Levy et al. (45) Apr. 17, 1973

54 PREPARATION OF P- 3,429,924 2/969 Ellerbrook et al....................260/576
NITROSODPHENYLAMNE
8 Primary Examiner-Lewis Gotts
75 Inventors: Joseph Levy, Paramus, N.J.; Louis Assistant Examiner-C. F. Warren
Seif, Bronx, N.Y. Attorney-James R. Hoatson, Jr. and Bernard L.
73) Assignee: Universal Oil Products Company, Kramer
Des Plaines, Ill.
57 ABSTRACT
22 Filed: July 20, 1970 57
Preparation of a p-nitrosodiphenylamine by rearrange
(21) Appl. No.: 56,692 ment of an N-nitrosodiphenylamine at a temperature
of from about 20 to about 50°C. in the presence of
52 U.S. Cl...................................................260/576 hydrogen chloride and a two solvent system compris
51 int. Cl............................................... C07c87/54 ing a water immiscible alcohol and an aromatic sol
58) Field of Search....................................... 260/576 vent having boiling points of from about 80 to about
160°C.
56 References Cited
10 Claims, No Drawings
UNITED STATES PATENTS
2,782,235 2/1957 Lantz................................... 260/576
 3,728,392
1 2
PREPARATION OF P-NTROSODPHENY LAMINE p-phenylenediamine is prepared by the reductive al
BACKGROUND OF THE INVENTION
kylation of p-nitrosodiphenylamine with cyclohex
anone. Similarly, the secalkyl derivatives are obtained
The synthesis of p-nitrosodiphenylamine involves the by reductive alkylation with acetone, methylethyl
nitrosation of diphenylamine, followed by rearrange ketone, methylpropyl ketone, methylbutyl ketone,
ment of the N-nitroso derivative to the p-nitroso com methylamylketone, methylhexyl ketone, etc.
pound under the influence of acidic reagents. The While the process of the present invention is particu
preparation of the N-nitroso derivative is readily ef. larly useful for the rearrangement of N-nitrosodiphen
fected and appears to offer no problem. However, the O
ylamine, it is understood that the process also may be
rearrangement step has been the subject of considera used for the rearrangement of derivatives thereof or re
ble study as it presents many difficulties, both in con lated compounds including, for example, N-nitroso-N-
ducting the reaction and in isolating the product. In methylaniline, N-nitroso-N-benzylaniline, N-nitroso
general, an alcoholic solvent seems necessary for ob 2,2'-dimethyldiphenylamine, N-nitroso-2-methoxy-2'-
taining a satisfactory reaction and anhydrous hydrogen 15
methyldiphenylamine, N-nitroso-4-cyclohex
chloride appears to be the most effective acid for ac ylaminodiphenylamine, N-nitrosophenyl-beta
complishing the transformation. In one method naphthylamine, N-nitroso-di-alpha-naphthylamine, etc.
proposed in the prior art, the rearrangement is effected Thus, one or both of the aryl rings may contain a sub
by adding molten N-nitrosodiphenylamine with stitutent which is inert to the conditions of the reaction
vigorous stirring to n-butanol to form a slurry, followed 20 and may be selected from alkyl of from one to about
by the addition thereto of a solution of anhydrous five carbon atoms, alkoxy of from one to about five car
hydrogen chloride also in butanol, thereby carrying out bon atoms, alkylamino of from one to about five car.
the reaction via a fine suspension of the nitroso com bon atoms, cycloaklylamino or other cycloalkyl con
pound in the alcohol solvent. However, here again taining substituent in which the cycloalkyl ring contains
isolation of the product and recovery of the solvent 25 from five to six carbon atoms, aralkylamino and
proved troublesome, halogen.
DESCRIPTION OF THE INVENTION The alcohol solvent for use in the two solvent system
is immiscible with water and has a boiling point of from
It now has been found that the arrangement is readily about 100°C. to about 160°C. Particularly preferred
accomplished by effecting the reaction in a two solvent 30 solvents comprise n-butanol, isobutanol, n-pentanol,
system comprising a water immiscible alcohol and an and n-hexanol. By the term water immiscible, we mean
aromatic solvent having boiling points of about 80° to that the alcohol forms a separate phase in contact with
about 160°C. This improved process produces high water, but may be partially miscible. The aromatic sol
yields of p-nitrosodiphenylamine of high purity, vent has a boiling point of from about 80° to about.
Furthermore, improved isolation and separation of the 35 160°C., with toluene being particularly preferred.
product as well as recovery of the solvent are accom Other aromatic solvents include benzene, xylene,
plished. chlorobenzene, ethylbenzene, cumene, anisole, etc.
As another advantage to the present invention, the The proportions of alcohol and aromatic solvent may
intermediate N-nitrosodiphenylamine need not be iso be varied over rather wide ranges but generally will be
lated but can be extracted into the aromatic solvent or 40
within the limits of from about 20 to about 80 and
alcohol-aromatic mixture, as desired, from the reaction preferably from about 40 to about 60 parts by weight of
mixture in which it has been prepared. The extract then one solvent and correspondingly from about 80 to
may be dried azeotropically and used directly for the about 20 and preferably from about 60 to about 40
rearrangement. This avoids the more laborious filter 45 parts by weight of the other solvent. The total amount
ing, washing and drying operations previously utilized of solvent used also may vary over wide limits but will
in the isolation of this intermediate product prior to be sufficient to form suitable solutions of the reactants
rearrangement. and generally will range from about 1 to about 5 and
In one embodiment, the present invention relates to preferably from about 1.5 to about 3 parts by weight of
a process for the rearrangement of an N-nitrosodiphen SO total solvent per part by weight of the N
ylamine to the corresponding p-nitrosodiphenylamine nitrosodiphenylamine.
which comprises effecting said rearrangement at a tem The rearrangement is effected in any suitable
perature of from about 20° to about 50°C. in the manner. In a particularly preferred method, a solution
presence of hydrogen chloride and a two solvent of the N-nitrosodiphenylamine in the aromatic solvent
system comprising a water in miscible alcohol and an 55 is first prepared and this solution then is added to a
aromatic solvent having boiling points of from about
80' to about 160°C. solution of anhydrous hydrogen chloride in the alcohol
In a preferred embodiment, N-nitrosodiphenylamine solvent. The addition is effected gradually, preferably
is rearranged to p-nitrosodiphenylamine. The p with suitable cooling to control the exothermic reac
nitrosodiphenylamine possesses varied utility, includ 60
tion temperature. In general, the addition may be made
ing use as an intermediate in the preparation of N over a period of from about 0.25 to about 4 and
phenyl-N'-substituted-p-phenylenediamines. For ex preferably from about 0.5 to about 2 hours. The pro
ample, N-phenyl-N'-cyclohexyl-p-phenylenediamine portions of hydrogen chloride and N-nitrosodiphen
and N-phenyl-N'-Ca-C-secalkyl-p-phenylenediamines ylamine will be within the range of from about 1 to
are effective antiozonants for use in rubber products. 65 about 2 molecular proportions of hydrogen chloride
These substituted products are readily obtained by per 1 molecular proportion of N-nitrosodiphenylamine
reductive alkylation of p-nitrosodiphenylamine with a and preferably from about 1 to about 1.5 molecular
suitable ketone. For example, N-phenyl-N'-cyclohexyl proportions.
 3,728,392
3 4
A dark red, crystalline precipitate commences to having a melting point of 67-68°C., which corresponds
form after the addition is started and continues to the reported melting point. The yield in this run was
throughout the addition. The slurry then is stirred and approximately 100 percent.
maintained at a temperature of from about 20 to about In another method of isolating the product, the reac
50°C. and preferably from about 25° to about 35°C. 5 tion mixture was extracted at 70°C. with 200 g of
The time of stirring will be sufficient to effect substan toluene, and the toluene layer then was separated and
tially complete reaction and may range from about 1 to dried by azeotropically distilling out the water with
about 8 and preferably 2 to about 5 hours. Preferably toluene. The resulting solution was adjusted to the
the time of reaction should be as short as possible 10
desired weight with toluene for the subsequent rear
because excessive time may result in deterioration of rangement reaction.
the product because of contact with the excess EXAMPLE I
hydrogen chloride. Similarly, the temperature should
be as low as satisfactory because too high a tempera The rearrangement of N-nitrosodiphenylamine to p
ture may also cause decomposition, 15 nitrosodiphenylamine was effected as follows. The
The reaction is terminated in any suitable manner reaction was carried out in a 2 liter 4-neck flask
and conveniently by the addition of sufficient aqueous equipped with a stirrer, dropping funnel, thermometer,
alkaline solution such as aqueous sodium hydroxide, water condenser and gas bubbler. There were charged
aqueous potassium hydroxide, aqueous sodium car 230 g. of n-hexanol and anhydrous hydrogen chloride
bonate, aqueous potassium carbonate, aqueous am 20 was bubbled in with cooling, keeping the temperature
monia, etc. to neutralize the hydrogen chloride, follow at about 20-30°C. until 48 g. were absorbed. The reac
ing which the reaction mixture may be steam distilled tion mixture was cooled to about 25°C. and, while
to recover the solvents. Prior to the steam distillation, maintaining the temperature at 25-35°C. with cooling,
the pH of the mixture should be adjusted to within the 200 g. ( 1.01 mol) of N-nitrosodiphenylamine dissolved
range of 5.5 to 7 and preferably from about 6 to 7. It 25 in 200 g of toluene were added over a period of about
has been found that steam distillation at a pH above 1 hour.
about 7 results in tarry byproducts, whereas at a pH Separation of a dark red, crystalline precipitate com
below about 5.5, the product is converted into an in menced after about 15-20 minutes and continued
soluble material of undetermined composition. It is also throughout the addition. The slurry was then stirred for
advisable to conduct the steam distillation under 30 about 4 hours at about 35°C, after which the reaction
reduced pressure so that the temperature of the reac was terminated by the addition, with vigorous stirring,
tion mixture does not exceed about 70°C. in order to of a solution of 60 g. of sodium hydroxide in 240 g. of
avoid hydrolytic decomposition which results in the water keeping the temperature below about 50°C.
formation of tars. The 4-nitrosodiphenylamine 35
The alkaline mixture consisted of a heavy but stirra
separates in well defined crystals at the conclusion of ble slurry. The pH was then adjusted to about 6.5 with
the steam distillation, and the aqueous slurry so ob hydrochloric acid and the solvents recovered by steam
tained is readily filtered and washed to recover the distillation, in vacuo, at a pot temperature of about
product. 50-65C. and pressure ranging from about 150 mm.,
As hereinbefore set forth, the process of the present 40 initially, to 10 mm. at the conclusion of the distillation.
invention affords high yields of p-nitrosodiphenylamine The p-nitrosodiphenylamine separated as well
of a high purity. The use of the alcohol-aromatic sol defined crystals which were readily filtered, washed
vent system offers advantages in recovering the with water and dried. There were recovered 197 g.of
product as well as in recovering the solvents for reuse bluish black crystals having a melting point of 142-14
as compared to the cumbersome isolating procedures 45 4°C., (reported melting point; 143-144°C). The yield
of the prior art. in this run was 98.5 percent overall, based on the
The following examples are introduced to further il diphenylamine charged to the initial nitrosation step.
lustrate the novelty and utility of the present invention The product was soluble in acetone and 10 percent
but not with the intention of unduly limiting the same. aqueous sodium hydroxide. The purity as determined
EXAMPLE I
50 by U.V. analysis compared to a commercial sample was
96.5 percent.
The N-nitrosodiphenylamine for use in the rear The wet recovered solvent was fractionally distilled
rangement reaction was prepared by charging 340 g. to give a recovery of 95 percent of the toluene and 92.5
(2.05 mol) of diphenylamine, 91 g of water and 110 g. percent of the hexyl alcohol.
of sulfuric acid (93 percent) into a 5 liter 4-neck flask 55
EXAMPLE III
equipped with a stirrer, dropping funnel, thermometer,
water condenser and gas bubbler. The mixture was Another run was made in substantially the same
heated to 65°C. with good mixing. While maintaining manner as described in Example I except that benzene
the temperature at 65-70°C., 114 g (2.1 mol) of sodi 60
was used as the aromatic solvent and n-butyl alcohol as
um nitrite dissolved in 340 g. of water were added over the alcohol solvent. In this run a solution of 48 g. of
a period of about 1 hour. Stirring was continued for hydrogen chloride dissolved in 250 g. of n-butyl alcohol
about an additional 30 minutes. and 200 g. of N-nitrosodiphenylamine dissolved in 200
The reaction mixture was cooled to about 25°C. with g. of benzene were charged to the process. While com
stirring. Crystallization of the product occurred and the 65 parable yields of p-nitrosodiphenylamine were ob
crystals were collected by filtering and then water tained, the recovery of the solvents was somewhat
washed and dried. There were recovered 406 g. (2.05 more difficult because of the relatively low boiling
mol) of N-nitrosodiphenylamine as light brown crystals point of benzene. Accordingly, toluene and n-hexyl al
 3,728,392
5 6
cohol are the preferred solvent system as illustrated in chloride and a two solvent system consisting of a water
Example II for this rearrangement. immiscible alcohol and an aromatic solvent having
boiling points from 80° to 160°C.
EXAMPLE IV 2. The process of claim 1 in which N-nitrosodiphen
Still another run was made in substantially the same 5 ylamine is rearranged to p-nitrosodiphenylamine in a
manner as described in Example II except that a mix two solvent system of a water immiscible alcohol hav
ture of n-butyl alcohol and toluene was used for both ing a boiling point from about 100-160°C. and
solutions. A solution of 24 g. of anhydrous hydrogen toluene.
chloride in 75 g. of n-butyl alcohol and 100 g. of 3. The process of claim 2 in which said alcohol is n
toluene was charged to a reaction flask and then a solu O butyl alcohol.
tion of 100 g. of N-nitrosodiphenylamine in 75 g, of n 4. The process of claim 2 in which said alcohol is
butyl alcohol and 100 g. of toluene was gradually added isobutyl alcohol.
to the reaction flask. In this run about twice the total 5. The process of claim 2 in which said alcohol is n
volume of solvent was required because of the lower hexyl alcohol.
solubility of the N-nitroso compound in the solvent
15 6. The process of claim 1 in which a solution of the
N-nitrosodiphenylarylamine in the aromatic solvent is
mixture. However, with this system, recovery of the added gradually to a solution of the hydrogen chloride
mixture of solvents is accomplished without the necess in the alcohol solvent.
ity of fractionally distilling them apart because of their 7. The process of claim 6 in which a toluene solution
close boiling points. Isobutyl alcohol may also be used 20 of N-nitrosodiphenylamine is added to a hydrogen
in admixture with toluene in this procedure. chloride solution in n-hexyl alcohol.
EXAMPLE V 8. The process of claim 1 in which a solution of the
N-nitrosodiphenylamine in a mixture of the aromatic
In another run, which was made in substantially the and alcohol solvents is added gradually to a solution of
same manner as described in Example II, the toluene 25 hydrogen chloride in a mixture of the aromatic and al
solution of N-nitrosodiphenylamine used as the charge cohol solvents.
was obtained by extracting the reaction mixture of the 9. The process of claim 1 in which the reaction is ter
nitrosation step with toluene, separating the toluene minated by the addition of an aqueous alkaline solution
layer and drying by azeotropic distillation. In this run, selected
potassiumfrom aqueous aqueous
hydroxide, sodium hydroxide, aqueous
sodium carbonate,
the toluene solution was added to a solution of an 30
hydrous hydrogen chloride in butanol. This run gave an aqueous potassium carbonate and aqueous ammonia.
overall weight yield of 99.5 percent. 10. The process of claim 9 in which the pH of the
We claim as our invention: reaction mixture is adjusted to from about 5.5 to about
1. A process for the rearrangement of an N 7 and then subjected to steam distillation under
nitrosodiarylamine to the corresponding p-nitrosodia 35 vacuum to separate the p-nitrosodiphenylamine and to
rylamine by effecting said rearrangement at a tempera recover the solvents.
at k is k k
ture of from 20° to 50°C. in the presence of hydrogen

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