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Патент USA US3052677

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States Patent
3,552,657
M6
Patented Sept. 4, 1962
1
3,052,667
MERCAPTDAZO AND MERCAPTOAZOXY ARO
MATIC COMPOUNDS AND METHOD FOR THE
PREPARATION THEREOF
William E. Hanford and John W. Copenhaver, Short Hills,
and Horace R. Davis, Cedar Grove, N.J., assignors to
The M. W. Kellogg Company, Jersey City, N.J., a cor
poration of Delaware
No Drawing. Filed Nov. 12, 1954, Ser. No. 468,554
11 Claims. (Cl. 260-143)
0
T
I
N=N—
SR
Vor
O
T
10
N=N—
This invention relates to a method of preparing para
substituted aromatic bimolecular reduction products, some
of which are new and novel compositions of matter.
More particularly, this invention is concerned with a
SR
VI
in which R may be aryl, i.e., phenyl, diphenyl, or naph
novel method of preparing para-alkylmercapto and para 15 thyl, haloaryl, alkaryl in which the total number of car
arylmercapto mono and disubstituted azo and azoxy
bon atoms in the alkyl portion does not exceed 10, and
aromatic compounds by the reaction in an alkaline
the alkyl portion may be 1 or more alkyl radicals in
medium of the corresponding nitro and nitroso aromatic
which the total number of carbon atoms does not exceed
compounds with a mercaptan.
10, alkyl having from 1 to 20 carbon atoms, branched
The novel compounds according to this invention are
chain alkyl having from 4 to 7 carbon atoms, and benzyl
represented by the structural formulae:
radicals.
Y
Y
25
VII
30
Y‘
2
Y
VIII
35 in which R may be aryl, i.e., phenyl, diphenyl, or naph
thyl, haloaryl, alkaryl in which the total number of car
bon atoms in the alkyl portion does not exceed 10, i.e.,
the alkyl portion may be a single alkyl radical or a plural
ity thereof in which the total number of carbon atoms
40 does not exceed 10, alkyl having from 4 to 20 carbon
atoms, branched chain alkyl having from 4 to 7 carbon
in which R may be aryl, i.e., phenyl, diphenyl, or
atoms, and benzyl radicals; and Y may be halogen, alkoxy
naphthyl, haloaryl, alkaryl in which the total number of
having not in excess of 20 carbon atoms, alkyl having
carbon atoms in the alkyl portion does not exceed 10,
i.e., the alkyl portion may be a single alkyl radical or 45 not in excess of 20 carbon atoms, amino, alkylamino hav
ing not in excess of 20 carbon atoms in the alkyl por
a plurality thereof in which the total number of carbon
tion, i.e., the alkylamino substituent may be monoalkyl
atoms does not exceed 10, alkyl having from 4 to 20‘ car
amino or dialkylamino, and hydrogen. Also, when Y
bon atoms, branched chain alkyl having from 4 to 7
is other than hydrogen, R may be a methyl, ethyl, or
carbon atoms, and benzyl radicals; and Y may be halo—
gen, alkoxy having not in excess of 20 carbon atoms, 50 propyl radical.
‘alkyl having not in excess of 20 carbon atoms, amino,
, alkylarnino having not in excess of 20 carbon atoms in
the alkyl portion, i.e., the alkylamino substituent may be
‘ monoalkylamino or dialkylamino, and hydrogen.
Also,
when Y is other than hydrogen, R may be a methyl, 55
ethyl, or propyl radical.
60
IV
3,052,667
3
4
in which R may be aryl, i.e., phenyl, diphenyl, or naph
thyl, haloaryl, alkaryl in which the total number of car
bon atoms in the alkyl portion does not exceed 10, and
the alkyl portion may be 1 or more alkyl radicals in
aromatic ring which has been further substituted with an
other aromatic ring or rings in such a manner as to form
polycyclic aromatic compounds in which the position
meta to the nitro or nitroso group is involved in the sub
stitution, but in which the para-position is not, as in
which the total number of carbon atoms does not exceed
alpha-nitronaphthalene or alpha—nitrosonaphthalene; (3)
10, alkyl having from 1 to 20 carbon atoms, branched
aromatic nitro or nitroso compounds consisting of a nitro
chain alkyl having from 4 to 7 carbon atoms, and benzyl
or nitroso group substituted on an aromatic ring which
radicals.
been further substituted in the position meta to the
Other compounds which may also be prepared accord 10 has
nitro or nitroso group, as in m-nitrotoluene, m-nitroani
ing to the present invention are represented by the struc
line, rn-nitro-N,N-dimethylaniline, m-nitroanisole, m
tural formulae:
chloronitrobenzene or m-bromonitrobenzene. For the
purpose of this invention the term “nitro and nitroso
aromatic compounds” will designate compounds conform
15 ing to the aforegoing description.
The compounds contained in this invention, due to
their azo and azoxy con?gurations, are useful as insecti
cides, dyestuffs, dye intermediates and also as chemical
intermediates. Their appearance is usually that of a
20 crystalline solid ranging in color from yellow to orange
red. Conforming to the general properties attributed to
other classes of substituted azo and azoxy compounds,
they are as a rule insoluble in water, unattacked by alkali
and dilute acids, stable to heat, and crystallize well. They
in which R may be aryl, i.e., phenyl, diphenyl, or naph 25 produce ‘a dark violet color with concentrated acids, an
effect characteristic of substituted azo and azoxy sul?des
thyl, haloaryl, alkaryl in which the total number of car
and not reproducible with azo and azoxybenzene.
bon atoms in the alkyl portion does not exceed 10, and
The ratio of mercaptan to the nitro or nitroso aromatic
the alkyl portion may be 1 or a plurality of alkyl groups
compound is above 2:1 and preferably between 2:1 and
8:1 depending upon the individual mercaptan used. In
ceed 10, alkyl having from 4 to 20 carbon atoms,
creased molar ratios of aliphatic mercaptans to nitro or
branched chain alkyl having from 4 to 7 carbon atoms,
nitroso compounds decrease the amount of yield, while
and benzyl radicals.
increased molar ratios of aromatic mercaptans slightly
The reduction of aromatic nitro and nitroso compounds
increase the yield. The optimum concentration of the
has been extensively studied and it is well known that 35 mercaptan is usually about four moles per mole of the
from this reaction, according to the conditions, a variety
nitro or nitroso aromatic compound, although the ?nal
of products may be obtained. Generally, the control
product results from an equimolar combination of the
ling factors are the type of reducing agent used and the
reagents. The mercaptan serves a twoefold purpose in
acidity of the reaction mixture. In alkaline solutions and
that it not only substitutes into the aromatic ring, but
with a mild reducing agent, such as dry iron ?lings, the 40 also reduces the nitro and nitroso groups to the azo and
. ‘azoxy formations.
nitro compound is reduced to the nitroso compound,
The relative amounts of azo and
azoxy compounds produced are dependent upon the mer
which through condensation is further reduced to the cor
responding azo and azoxy compounds.
captan used and the conditions under which the reaction
is carried out.
In accordance with the present invention, a one step
Some type of basic material is essential to this syn
synthesis consisting of the reaction of a mercaptan and 45
1 thesis, the hydroxides of the alkali metals being prefer
a nitro or nitroso aromatic compound is carried out,
preferably in an aqueous alkaline solution, at tempera
able. Nevertheless, organic, basic materials such as al
kali metal alcoholates or amines may also be used, al—
tures between 25° C. and 250° C., to prepare para
alkylmercapto and para-arylrnercapto mono and disubsti 50 though they are not as effective as the inorganic bases
tuted azo and azoxyaromatic compounds.
_ for promoting the substitution of the mercaptan groups
into the aromatic nucleus.
It has been found that when a mercaptan is used as
The quantity of base used may range ‘from molar
the reducing agent, in alkaline solution, the nitro aromat
ic compound, which may be substituted in the meta posi
concentration slightly in excess of the mercaptan molar
tion, if desired, is not only reduced to the azo and/or 55 concentration to a saturated solution of the base in the
solvent employed. A molar ratio of alkali to mercaptan
azoxy form, but a para substitution of the aromatic ring
by the alkylmercapto or arylmercapto group also takes
greater than 4:1 is preferable in these reactions.
place, thus providing a convenient method of synthesiz~
Water is the most satisfactory medium in which to
in which the total number of carbon atoms does not ex
ing the afore described compounds.
,
carry out the reaction; however, alcohols, liquid amines,
The preparation described in the present invention is 60 or inert solvents may be used if desired.
carried out in one step and with reactants which are
The reaction may be operated at temperatures between
25° C. and 250° C. or below the decomposition tempera
readily available and relatively cheap. Furthermore,
ture of the desired product. Although reaction does take
yields as high as 85.6 percent, based upon the nitro
benzene charged, have been obtained from the reaction
place at temperatures below 25 ° C., the rate of reaction
of nitrobenzene with thiophenol and straight chain ali 65 is not sufficiently great to produce any yield of the prod
phatic mercaptans with one to four carbon atoms.
uct within a reasonable period of time. At temperatures
above about 250° C., excessive decomposition of the de
The starting materials involved in our method of syn
thesis embrace all the compounds in the mercaptan group
sired product occurs. For convenience in operation and
and the nitro and‘ nitroso aromaticrcompounds, which 70 to obtain the most desirable reaction rates, temperatures
ranging from 60° C. to 175° C. are preferable for the
comprise (l) aromatic nitro and nitroso compounds con
synthesis of the desired products from nitro compounds.
sisting of the nitro or nitroso group substituted onto the
Similar reactions carried out with nitroso compounds as
aromatic ring such as in. nitrobenzene ‘and nitrosoben
the starting material should be operated at temperatures
zene; (2) aromatic nitro and nitroso compounds con
sisting of a nitro or nitroso group substituted onto the 75 between 25° C. and 100° C.
5
6
More speci?cally, the procedure is as follows: the
nitro or nitroso aromatic compound, the mercaptan, and
The p,p’-bis(benzylmercapto)azobenzene was reduced
with stannous chloride and treated with acetic anhydride
the aqueous alkali are placed in a vessel. The vessel may
to form the previously reported derivative P'benzylmer
captoacetanilide (M.P. 117.5 °-—1 19° C.)
be glass if the temperature is not to exceed 105° C. If
the reaction is to take place at about room temperature,
no additional equipment is required.
EXAMPLE II
At temperatures
above room temperature, a re?ux condenser should be
Reaction of Nitrobenzene and n-Butyl Mercarp‘tan
used. At temperatures higher than 105° C., the water
tends to boil out of the reaction zone, and it, therefore,
A mixture of 0.2 mole of n-butyl mercaptan, 0.05 mole
becomes necessary to use some type of pressure equip 10
of nitrobenzene, 230 ml. of methanol and 0.5 mole of
ment, designed more to retain the water vapor in the
solid sodium methylate was placed in a glass ?ask. A
system than to exert pressure on the area of reaction.
re?ux condenser and a mechanical stirrer were attached.
Equipment such as a sealed bomb, an autoclave, or water
The mixture was then heated to a temperature of 65° C.
tight apparatus for continuous operation may be em
and re?uxed for seventeen hours. At the end of this
ployed. Throughout the temperature range agitation has 15 time
the mixture was steam distilled in a conventional
been found to be advantageous but not essential for the
manner to remove excess methanol, nitrobenzene, and
reaction to proceed. The preferred method is to heat the
the corresponding disul?de of the mercaptan. The prod
mixture containing an aromatic nitro starting material
ucts, consisting of p,p’-bis(n-butylmercapto) azoxyben
zene, p,p'-(n-butylmercapto)azobenzene, p-n-butylmer
to a temperature between 60° and 175° C. At tempera
tures between 80° C. and 105° C. the reaction will go to
completion in 20 to 48 hours, while at a temperature
of 140° C. the required reaction time is 5 to 15 hours.
Syntheses from aromatic nitroso starting materials re
quire l to 4 hours at temperatures of 25° C. to 50° C.
Upon completion of the reaction, the unreaoted aro
captoazoxybenzene, and p-n-butylmercaptoazobenzene,
were removed from the residue of the steam distillation
by extraction with chloroform and thereafter recovered
and separated by chromatography.
25
matic nitro or nitroso compound and/or the extraneous
disul?de of the mercaptan is removed by steam distillation
or any other convenient method. The para-alkylmer
capto or para-arylmercapto substituted azo and azoxy
The main products were of the disubstituted types, rep
resented by p,p’—bis(n-butylmercapto)azoxybenzene and
p,p'-bis(n-butylmercapto)azobenzene. The results found
in the analysis for the elements of these compounds agreed
well with the calculated theoretical values.
compounds are extracted with a suitable solvent or any 30
other applicable method.
COMPOSITION
The products are then recov
ered by recrystallization or chromatography.
Individual compounds, prepared by our method of
synthesis, and the starting materials used are compiled
in Table I. The operating data from some of the syn
theses carried out are compiled in Table II, to illustrate
more fully the variation of conditions employable for the
reaction.
The invention will be further illustrated by reference
to the following speci?c examples:
p,p’-Bis(butylmercapto)
p,p’-l3is(butylmercapto) azoben
azoxybenzene
zene
Percentages
Elements
Percentages
Elements
Found
Calculated
Found
40 Carbon_____
Hydrogem.
17'. 87
Nitrogen" _
EXAMPLE I
Calculated
Sulfur ____ __
Reaction of Benzylmercaptan with Nitrobenzene
A mixture consisting of 0.3 mole of nitrobenzene, 1.2 45
p,p'-Bis(n-butylmercapto)azoxybenzene was treated
moles of benzyl mercaptan, 480 ml. of water and 3 moles
with hydrogen peroxide and acetic acid to yield p,p'
of solid sodium hydroxide was placed in a glass ?ask.
bis(n-butylsulfonyl)azoxybenzene (M.P. 215.5°-216°
A re?ux condenser and a mechanical stirrer were con
C.) which was in turn analyzed for identi?cation. p,p'
nected. The mixture was then heated to a temperature
of 102° C. and the reaction of the components proceeded "
Bis(n-butylmercapto)azoxybenzene
was
also reduced
for twelve hours. At the end of that time, the mixture
with lithium aluminum hydride to yield p,p'-bis (n-butyl
mercapto)azobenzene, analysis of which agreed with the
was steam distilled in a conventional manner to remove
values found for the azo compound originally produced
the excess nitrobenzene. The products, p-benzylmercapto
in the synthesis‘.
azobenzene
and
p,p'-bis (benzylmercapto) azobenzene,
were then extracted from the residue with chloroform and 55
thereafter recovered through chromatography.
EXAMPLE III
In this
case no substituted azoxy compounds were formed. The
Reaction of Nitrosobenzene and Thiophenol
yield ‘of p,p’-bis(benzylmercapto)azobenzene was 6.7
percent and of p-benzylmercaptoazobenzene, 6.5 percent.
Thiophenol (16.5 g., 0.15 mole) was dissolved in 500
The products were analyzed for their element content and 60 grams of 10 percent sodium hydroxide solution and the
mixture was stirred at room temperature while nitroso~
the results obtained agreed well with the calculated the
benzene (10.0 g., 0.093 mole) was added in small quan
oretical values.
tities over a period of twenty minutes, during which brown
COMPOSITION
p,p’-B is (benzylmercapto) azoben-
p~B enzylmercaptoazobenzene
zene
Percentages
Elements
Percentages
Elements
Found
Calculated
Carbon_____
Hydrogem.
73. 10
5. 20
73. 20
5. 20
Sulfur ____ __
15. 03
14. 70
Found
Carbon.__.
Hydrogen.
74. 79
5. 40
fumes were evolved. The mixture was stirred but not
65 heated for an additional three hours. At the end of this
time it was steam distilled in a conventional manner to
remove excess nitrosobenzene. The products were then
extracted from the residue of the steam distillation with
benzene and separated chromatographically on alumina.
Calculated 70
74. 96
5. 30
N itrogen“
9. 42
9. 21
Sulfur...“
10. 32
10. 53
By identi?cation through melting points and mixed melt
ing points, the products were found to be P>p'-bis (phenyl
mercapto)azoxybenzene (5.0 percent yield), p-phenyl
mercaptoazoxybenzene (2,3 percent yield) and azoxyben
75 zene (39 percent yield).
3,052,667
7
EXAMPLE 1v
COMPOSITION
[p,p’-Bis(phenylrnereapto)-m,m’-bis(amino)azoxybenzene]
Reaction of Nitrobenzene and Thiophenol in
Percentages
Triethyl Amine
Elements
A mixture consisting of 0.05 mole nitrobenzene, 0.2
mole thiophenol and 1.14 moles triethyl amine was placed
in a glass ?ask‘. A reflux condenser and a mechanical
stirrer were attached. The mixture was then heated to
a temperature of 89°-90° C.,' which is the boiling tem
perature of triethyl amine, and re?uxed for thirty-six
Found
10
Calculated
Carbon
Hydrogen
64. 49
4. 48
64. 84
4. 54
Nitrmen
Sulfur
12. 94
14. 09
12. 60
14. 42
[p,p’-Bis(phenylmercapto)-m,m’-bis(methyl)azoxybenzene]
hours; At the end of this time, the triethyl amine was
removed by heating the mixture on a steam bath. The
Percentages
residue was then steam distilled in a conventional man
ner to remove unreacted nitrobenzene. The products 15
Elements
were removed from the residue of the steam distillation
Found
Calculated
by extraction with chloroform. The products were iso
lated chromatographically on alumina. There was no
evidence that substituted azo or disubstituted azoxy com
pounds were formed.
p-Phenylmercaptoazoxybenzene 20
was produced in a 2.6 percent yield. The results of the
Carbon
Hydrogen
N itrmzen
Sulfur
analysis of the percentage composition of this compound
70. 55
5. 0l
6. 33
14. 49
70. 65
4. 81
5. 77
14. 41
[p,p’-Bis(phenyl1nereapto)-m,m’-bis(ehloro)az0xybenzene]
agree well with the calculated values.
Percentages
25
Elements
C 0 MP 0 SI'l‘I ON
Found
[p-Phenylmercaptoazoxybenzene]
Percentages
Elements
30
Found
Carhnn
Hydrogen
Calculated
70.76
4. 70
Nitrogen ____________________________________ __
Sulfur
Carbon
Hydrogen
Nitrogen____
59. 62
3. 34
5. 80
59. 93
3. 90
6.04
'
14. 67
14. 92
[p,p’-Bis(phenylmercapto)-m,m'-bis(bromo)azoxybenzene]
70. 56
4. 61
9. 24
9. 15
10. 62
10. 46
Percentages
Elements
35
Found
Carbon
EXAMPLE V
Calculated
50. 36
Hydrogen ___________________________________ __
Reaction of Thiophenol With m-Sn‘bstitnted
Nitroaromatic Compounds
Calculated
40 Sulfur
49. 70
2. 82
2. 98
11. 20
10. 74
EXAMPLE V‘I
Reaction of Alpha-Nitronaphthalene and Thiophenol
A group of m-substi-tuted nitroaromatic compounds
consisting of m-nitrotoluene, m-nitroaniline, m—nitro-N,N1
dimethylaniline, m-nitroanisole, m-chloronitro‘oenzene,
and mercaptans. A mixture consisting of 0.40 mole of
and m-bromonitrobenzene were used as individual start
thiophenol, 0.10 mole of alpha-nitronaphthalene and 600
The procedure was the same as used with nitrobenzene
ing materials along with thiophenol in the same pro
g. of 20 percent aqueous sodium hydroxide solution was
stirred and re?uxed at a ‘temperature of 105° C. for 21
scribed in Example I. Thiophenol (0.40 mole) was dis
hours. In this case steam distillation was omitted. The
solved in 600 g. of 20 percent aqueous sodium hydroxide, 50 desired products were extracted directly ‘from the mixture
with benzene and were then isolated chromatographically
to this was added the nitro-aromatic compound (0.10
mole). The mixture was re?uxed for 20 to 48 hours.
on alumina. The main product conforms to the struc
In these cases steam distillation was omitted. The prod
ture con?guration,
ucts were extracted directly from the mixture with ben
zene and recovered chromatographically on alumina.
The compounds recovered in such a manner conformed
to the general formula:
cedure as used with nitrobenzene and mercaptans de
which is another meta-substituted form of the general
Y
RS
60
Y
O
Q T@
N=
Formula II. Analysis of the product yielded the follow
ing results:
COMPOSITION
SR
Percentages
Elements
which is the meta-substituted form of the general Formu 65
la VIII, previously described. The percentage yields
were: p,p’ _ bis(phenylmercapto) - m,rn' - bis(methyl)
Nitrogen ____________________________________ __
Sulfur
-
azoxybenzene, 16 percent; p,p' - bis(phenylmercapto)
m,m' - bis(amino)azoxybenzene, 30 percent; p,p’ - bis
(phenylmercapto) - m,m' - bis(chloro)azoxybenzene, 34
percent; p,p' - bis(phenylmercapto) - m,m’ - bis(bromo)
70
azoxybenzene, 40 percent. The results of the analysis
of these compounds agree well Withthe calculated values,
as can be observed below.
'
'
Found
75
5. 21
12. 18
Calculated
5. 44 I
12.46
EXAMPLE VII
Reaction of Nitrobenzene and Thiophenol at
Temperatures Above 105° C.
A mixture of 0.2 mole of thiophenol, 0.05 mole of
nitrobenzene, 80 ml. of water, and 0.5 mole of solid s0
3,052,667
9
l9
dium hydroxide was placed in a bomb. The mixture was
(phenylmercapto)azoxybenzene was obtained in a 12.1
then heated to 140° C. and agitated for eight hours. At
percent yield and p-phenylrnercaptoazoxybenzene in a
20.3 percent yield.
the end of this time, the mixture was steam distilled to
remove the unreacted nitrobenzene. From the residue of
the steam distillation, the products were extracted with
When this reaction was operated for 42 hours at a
temperature of 108° C., the percent yield was 27.7 per
cent of p,p'-bis(pheny1mercapto)azoxybenzene and 24.3
chloroform and recovered through recrystallization. The
products were predominately of the azoxy type. p,p'-Bis~
percent of p-phenylmercaptoazoxybenzene.
Table I
COMPOUNDS WHICH HAVE BEEN ISOLATED
Starting material
Mercaptan
Product
Nitro or nitroso
Structural formula
Empirical formula M.P.,°O.
0011117.
‘%
1
ThiophenoL. l/nitrosobenzene, 2/nitr0
QSC>vN=NOSC>
benzene.
CMIHISNzSzO ____ _- 121 -122
g
2 n-Bu’iylmerNitrobenzene__ CH3(CH¢)3S<
cap 811.
>—N=N\C>S(CH2)aCH3
CZOHQBNZSZO ____ __
79 —79.5
g
3
t-Butylmer.___.dQ ________ __
captan.
(CH3)3OSC>-N=NQSO(CH3)3
HsC
4
ThiophenoL- m-Nitrotoluene.
g
5
______ __
benzene.
120
CH3
Qs-QrmrzOsG
01
CzoHggNzSgO ____ __
19
C26H22N2S20 ____ -_ 104 -105
Cl
@_S<:>~N:N@_S@
Br
g
6 _____do ...... __ m~Br0monitro~
<:>-s_
benzene.
Br
—N=N‘®—S®
H2N
(1?
Cz4I'I1sN2BI‘2SZO___ us -120
NH2
7 ___>_d0 ______ __ m-Nitroaniline_ <:>~-SC>—N=NA©—S®
CitHtONiSBO .... _. 145 -14s.5
g
8
Benzyl
mercaptan.
Nitrobenzene” C>\N=N—OSCEDO 1'
C1
t-Butyl mercaptan.
11
n-Butylmer- _____dO ________ __
Nitrobenzene__ (OH3)3CS©—N=N—_
CH3(OH2)3S
64 — 65
C1
9 Thiophenol__ m-Nitrochloro®S©—N=N—C>SC>
benzene.
10
CwHmNzOS _____ ._
SO(CHa)z
N=N—
S(CI*I2)3CH3
C24HitN2O12S2----- 174 —175
CzoHzuNzSz ______ -_
CznHzeNzSz ______ _.
171
98
—99
captan.
12
Benzylmer_____do ________ __ Octane
captau.
—N=NOSCHZ<:>
13 _-...do ........... ._<1o ........ -_ c>—N=N-©scm<:>
i
14 Thiophenol" Nitronaphtha Os_
_N=1-r
CgoHzzNgSz ______ __ 182 -1s4
OIQHMNZS ....... -_
-s®
1015-108
Ca2H22N2S2O ____ _- 198 -200
ene.
.
g
15
p-ThiocresoL..Nitrobenzene__ HBCOSON=NOSQOHS
OII3O
T
0
16 ThiophenoL. m-Nitroanisole- <:>~S—<3—N=NC>—S—<3
(CHmN
O
l
17
_-_._d0 ______ __
m-Nitr0-N,N-
—-S
T
—N=N—
CwHzzNzOSz .... __ 135 —136
00113
CzeH22NzO3Sz___-_ 116 ~118
N(CH3)2
l
S
O2BH2BN2OS2 ____ __
138
--140
dimethyl
aniline.
T‘I‘he con?guration as shown is not to be construed so as to limit the position of the oxygen in the diazoxy group‘ It may be bonded to either nitro
gen atom.
3,052,667
Table II
OPERATION DATA OF ILLUSTRATIVE REACTIONS
Reactants
Mercaptan
Moles
Reaction media
Nitro or nitroso aromatic compound
Moles
Solvent
Vol.
in ml.
Conditions
Alkali
Primary
Secondary
product
product
Time Temp.
Moles h in
° C.
Type
Percont
Per
Type cont
ours
Methyl mercaptan.
0. 20
Do ___________ __
. 0
Nitrobenzene _______________ __
Ethyl mercaptan... ' .
Do
.
Do ___________ __
.
n-Propyl mercaptan
.
n-Butyl mercaptan_
.
D
.
.
.
.
.
.
. 10
.
.
1 No agitation.
0.05
H20
80
NaOH
0.5
0.5
H20
800
NaOH
5. 00
0. 10
0. 05
0.50
0. 15
O. 05
0. 10
0. 25
0.05
0. 50
0. 10
0.05
0. 05
0. 50
I110
H20
E20
I120
1120
E20
E20
MeOH
MeOH
E20
E20
I120
H20
160
80
800
360
80
480
240
325
230
70
80
80
800
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
LiOMe
NaOMe
NaOH
NaOH
NaOH
NaOH
1.00
0. 50
5. 00
2. 25
0. 50
3. 00
1. 50
0. 50
0. 50
0.50
0. 50
0. 50
5. 00
140
II
109
XII
4. 4
48
40
8
140
41
80
24 82-110
9
140
20
105
24
105
22
65
17
65
9
140
8
140
7
140
48
108'
II
XII
XII
XII
XII
XII
XII
XII
XII
XI
II
II
XII
11. 3
26. 3
48. 1
43. 1
11. 8
14. 4
3. 9
13. 4
16. 4
28. l
20. 3
10. 1
27. 7
0. 06
I120
240
NaOH
1.50
28
105
XII
5. 7
(2)
E10
H20
E20
1120
H20
E’I‘3N
E20
1120
I120
E20
E20
E20
E20
480
480
480
570
480
3.00
3. 00
3. 00
0.75
8. 00
1. 14
3. 00
0. 50
3. 00
3. 00
3. 00
3.00
3. 00
48
48
48
48
24
105
105
105
100
110
89
102
140
105
105
105
105
105
XII
XII
XII
XII
XII
II
XI
I
VIII
III
VIII
VIII
VIII
19.5
24. 5
35. 2
1. 5
28. 6
160
480
80
480
480
480
480
480
NaOH
NaOH
NaOH
NaOH
NaOH
ETQN
NaOH
NaOI-I
NaOH
NaOH
NaOH
NaOH
NaOH
II
II
II
II
II
(2)
I
XI
(a)
(2)
(5’)
VII
(2)
1 48
23. 6
XII
II
XII
II
II
II
XI
(2)
(2)
(2)
XI
XII
XII
XII
II
10.1
4.0
7.1
25.9
37. 5
20. 5.
10. 3
(2)
(2)
(1’)
14.8
20. 2
12. l
6.0
24. 3
(l)
8. 4
.
.
.
.
.
_
.
.
.
0. 40
0.40
O. 40
0. 40
rn-Nitrotoluene _____________ __
m-Nitl‘oaniline ______________ __
m-Nitroehlorobenzene...
_
m-Nitrobromobenzene ______ __
0.05
0. O5
0.05
0. 05
0. 05
0. 05
0.30
0.05
0. 10
0- 10
0. 10
0. 10
0. 10
0. 40
N,N-dimethyl-m-nitroaniline__
0. 10
E20
480
NaOH
3. 00
43
105
VIII
4. 0
(2)
(Z)
0. 40
m-Nitroanisol _______________ __
0. 10
H20
400
NaOH
2. 00
20
105
VIII
23. 5
(2)
(1)
36
12
8
30
36
24
29
2
2. 6
6. 7
12. 1
26. 6
16. 0
30.0
34.0
40. 0
18. 8
2. 0
1. 4
15. 7
(2)
6. 5
1.2
(2)
(2)
(2)
1. 5
(2)
2 None isolated.
EXAMPLE VIII
35
ThlS application 1s a contmuatron-m-part of copendmg
application Serial No. 282,716 ?led April 16, 1952, now
To demonstrate the efficacy of the compounds of the
abandoned.
invention as insecticides, test solutions of various com
It will be obvious to those skilled in the art that many
pounds of the invention were injected into the blood
modi?cations may be made within the scope of the pres
Mortality readings were made every 24 hours for a period 40 ent invention without departing from the spirit thereof,
and the invention includes all such modi?cations.
of six days, at which time total mortality was recorded.
We claim:
The standard concentration of material commonly used
1. Compounds having the formula:
in this test is 2.5 percent, but as the compounds of the
Y
Y
invention were insoluble to this extent, a saturated
supernatant liquid was used. The solvent consisted of
stream of the American roach (Periplaneta am‘ericana).
10 percent by weight acetone, 10 percent by weight xylene,
5 percent by weight ethanol, and 75 percent by weight
Deo Base.1 (Footnote at bottom of column 12.)
in which X is selected from the group consisting of azo and
azoxy ‘groups; R is selected from the group consisting of
The results are as follows:
50
AMERICAN ROAOH INJECTION
radicals in which the total number of carbon atoms in the
[Dosagez 0.008 and 0.012 ml. for male and female roach respectively of
saturated solutions. Six clay count]
Material
Sex
phenyl, diphenyl, naphthyl, halophenyl, and alkylphenyl
alkyl portion does not exceed 10, an alkyl radical having
from 1 to 20 carbon atoms, and a benzyl radical; and Y
is a dialkylamino radical in which each alkyl radical has
Percent
Mortality 55 not in excess of 10 carbon atoms.
2. Compounds having the formula:
4,4’-bis(phenylmercapto)azoxybenzene_____________ __ 5i
4,4’-bis(pheny1mercapt0)azobenzene
4- benz lmerca to azobenzene ____________________
________________ __ FM
F
(
y
p >
M
4,4’-bis(benzylmercapto)azobenzene
4,4’-bis(ethylsulionyl)azobenzene __________________
________________ -_
__ 1%
lF/l
4,4’ - bis(phenylmereapto) -3,3’ - bis (amino) azoxyben-
F
8%
0
100 60
in which X is selected from the group consisting of azo
and azoxy groups; R is a 'benzyl radical; and Y is selected
48
from the group consisting of halogen, alkoxy having not
0
zene.
M
F
60 65
20
M
40
4,4'-bis(phenylmercapto)~3,3’-bis(ch1oro)azobenzene._
4,4’ - bis(phenylmercapto) - 3,3’ - bis(methoxy) azoxy- lF/I
F
20
4,4’ - bis (phenylmercapto) -3,3’ -bis (chloro) azoxybenzone.
benzene.
in excess of 20 carbon atoms, alkyl having not in excess
of 20 carbon atoms, amino, alkylarnino having not in ex
cess of 20 carbon atoms in the alkyl portion, and hydrogen.
3. The compound p,p'-bis(benzylmercapto)azobenzene.
4. The compound p,p’-bis(phenylmercapto)-m,m'-bis
(N,N-dimethylamino) azoxybenzene.
M
4,4’-bis(ethylmercapto)-3,3’-bis(ch1oro)azoxybenzene_ {a
60 70
4g
NOTE.—-DDT male roach 0.075 ml., 80 percent mortality; DDT female
roach 0.04 ml. 100 percent mortality. Control, male 20 percent mortality;
fem ale 0 percent mortality.
1A light petroleum distillate which has been re?ned to
complete freedom from kerosene odor and which is used as a
solvent for waxes, oils and petrolatums and is miscible with
organic solvents. Deo Base as a product of L. Sonneborn
Sons, Inc. has an API speci?c gravity of 48/51 and other‘
properties reported in L. Sonneborn Sons’ Technical Data
' File DB entitled “Deo Base.”
3,052,667
13
having the formula
RSH
wherein R is selected from the group consisting of phenyl,
not in excess of 20 carbon atoms in the alkyl portion, and
hydrogen, which comprises reacting in an alkaline medium
diphenyl, benzyl, naphthyl, and halophenyl radicals, an
alkyl phenyl radical in which the total number of carbons
in the alkyl portion does not exceed 10, an alkyl radical
having not in excess of 20 carbon atoms, a branched chain
alkyl radical having from 4 to 7 carbon atoms, with a
substituted benzene compound having the formula
14
lected from the group consisting of halogen, alkoxy hav
ing not in excess of 20 carbon atoms, alkyl having not
in excess of 20 carbon atoms, amino, alkylamino having
5. A process which comprises reacting a mercaptan
at a temperature in the range of about 25° C. to about
250° C., a mercaptan having the formula
RSH
in
which
R
is
a
given
above
and a substituted benzene hav
10
ing the formula
Z
2
15
Y
Y
in which Z is selected from the group consisting of nitro
and nitroso radicals and Y is as given above, the molar
ratio of mercaptan to substituted benzene being in the
wherein Z is selected from the group consisting of nitro
and nitroso radicals and Y is selected from the group
consisting of hydrogen and halogen atoms, an amino
range of about 2:1 to about 8:1.
radical, an alkoxy, alkyl and alkylamino radicals having
8. A process for preparing compounds selected from
the group consisting of mercaptoazobenzenes and mer
not in excess of 20 carbon atoms in the alkyl portion;
in an alkaline medium at a temperature of between about
captoazoxybenzenes which comprises reacting, in an
25 ° C. and about 250° 0., the mol ratio of mercaptan
aqueous alkaline medium at a temperature in the range
to substituted benzene being in the range of from about 25 of about 25° C. to about 250° C., a mercaptan having
0:1 to about 8: 1, to produce the corresponding compounds
the formula
selected from the group consisting of a mercaptoazo ben
RSH
zene and a mercaptoazoxy benzene.
in which R is selected from the group‘ consisting of phenyl,
6. A process for preparing compounds selected from
diphenyl, naphthyl, halophenyl and alkyl phenyl radicals
the group consisting of mercaptoazobenzenes and mer
in which the total number of carbon atoms in the alkyl
captoazoxybenzenes, which comprises reacting a mer
portion does not exceed 10, an alkyl radical having not
captan having the formula
in excess of 20 carbon atoms, a branched chain alkyl
RSH
radical having from 4 to 7 carbon atoms and a benzyl
in which R is selected from the group consisting of 35 radical and a substituted benzene having the formula
naphthyl, diphenyl, phenyl, halophenyl, and alkylphenyl
Z
radicals in which the total number of carbon atoms in the
alkyl portion does not exceed 10, an alkyl radical having
from 4 to 20 carbon atoms, a branched chain alkyl radical
having from 4 to 7 carbon atoms and a benzyl radical,
in an aqueous alkaline medium at a temperature of be
tween about 25° C. and about 175° C. and a substituted
benzene having the formula
Z
Y
in which Z is selected from the group consisting of nitro
and nitroso radicals and Y is selected from the group con
sisting of halogen, alkoxy having not in excess of 20
carbon atoms, alkyl having not in excess of 20 carbon
45 atoms, amino, alkylamino having not in excess of 20 car
bon atoms in the alkyl portion, and hydrogen; the molar
ratio of mercaptan to substituted benzene being in the
Y
range of about 2:1 to 8:1.
9. A process according to claim 8 in which the alkaline
medium is an aqueous solution of an alkali metal hy
in which Z is selected from the group consisting of nitro
and nitroso radicals and Y is selected from the group
droxide.
consisting of halogen, alkoxy having not in excess of 20
10. A process according to claim 7 in which the alkaline
carbon atoms, alkyl having not in excess of 20 carbon
medium is a trialkyl amine.
atoms, amino, alkylamino having not more than 20 carbon
11. A process according to claim 7 in which the alkaline
atoms in the alkyl portion and hydrogen; the molar ratio 55 medium is an alcoholic solution of an alkali metal alco
of mercaptan to substituted benzene being in the range
holate.
of about 2:1 to 8:1.
7. A process for preparing compounds having the for
References Cited in the ?le of this patent
mula:
UNITED STATES PATENTS
Y
Y
in which X is selected from the group consisting of azo
and azoxy groups; R is selected from the group consist 65
ing of a phenyl, diphenyl, naphthyl, halophenyl, alkyl
2,064,332
2,200,006
2,213,218
2,647,113
Zwilgmeyer ___________ __ Dec. 15, 1936
McNally et a1 ___________ __ ‘May 7, 1940
Hester ________________ __ Sept. 3, 1940
Lanty et al _____________ __ July 28, 1953
OTHER REFERENCES
Bielstein, 4th ed., vol. 16 (1934), pp. 239, 240, 385,
phenyl radical in which the total number of carbon atoms
386.
in the alkyl portion does not exceed 10, alkyl having from
Frear et al.: Journal of Economic Entomology, vol. 40,
4 to 20 carbon atoms, branched chain alkyl having from
(1947),
p. 736-741.
70
4 to 7 carbon atoms, and benzyl radicals; and Y is se
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No‘, $052,667
<
September 4‘,
1962
William E‘, Hani‘ord et alo
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 61 line 20, for ‘"pgp’ =(n—-butylmercapto)azobenzene‘"
read —— p,p’ —bis(n—butylmercapto)azobenzene ——; line 74v for
"23" read ——~ 2,,3 ——; columns 9 and 10V Table Ia fourth columnq
the ninth formula should appear as shown below instead of as
in the patent:
C1
C1
same Table IY fourth columnE the sixtecrth formula should
appear as shown below instead of as in the patent:
CH3O
0
OCHS
same Table I, fourth column.V the seventeenth formula should
appear as shown below instead of as in the patent:
(CH3)2N
N(CH3)2
050E050
column 14,
line 9,
for "a",7
first occurrence‘,
read We as em.
Signed and sealed this 21st day of May 1963‘.
(SEAL)
Attest:
ERNEST We SWIDEII
Attesting Officer
DAVID L, LADD
Commissioner of Patents
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