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Патент USA US3053910

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United States Patent 0 F
1
3,053,901
Patented Sept. 11, 1962
2
The process is particularly suitable for the preparation
3,053,901
of 2,4,5,4'-tetrachlorodiphenylsulphide from l,2,4,5-tetra
Ian Hendrik Uhlenbrock, Weesp, Netherlands, assignor
to North American Philips Company, Inc-, New York,
rothiophenol-potassium. As alkyl-substituted aryl 'com
POLYARYL SULPHIDE
chlorobenzene and 4-chlorothiophenol-sodium- or 4-chlo
‘ pounds are to be considered particularly those aryl com
N.Y., a corporation of Delaware
No Drawing. Filed June 9, 1960, Ser. No. 34,869
Claims priority, application Netherlands June 13, 1959
6 Claims. (Cl. 260-609)
pounds substituted by a methyl group.
Applicants have found that the yield of diaryl sulphide
is favourably in?uenced to a considerable extent by using
a considerable excess of the reaction component of the
The invention relates to the preparation of polyaryl 10 Formula B. Favourable molar ratios of A and B are
sulphides, in particular of diaryl sulphides, from an alkali
1:4 to 1:40 and in particular 1:6 to 1:20.
compound or an aryl thiophenol and an aryl chloride.
The course of the reaction and the yield of polyaryl
In the literature some methods are described for the
sulphide according to the invention is in?uenced favour
ably by using a solvent in which both reaction components
preparation of diaryl sulphides which, however, are not
suitable for practical purposes. It is described, for exam~ 15 are soluble. As such are to be considered monovalent
ple, that in the conversion of aryl bromides with lead
alcohols, for example cyclohexanol, ethers, for example
mercaptides, Zinc mercaptides or mercury mercaptides at
dioxane, dimethyl sulphoxide and tertiary nitrogen bases,
and in particular aromatic tertiary nitrogen bases, such
225—230° C. aromatic thioethers are obtained in good
yields. For practical purposes this method is not very
as pyridines and quinoline. ' Dimethyl formamide is a
attractive, also because of the high costprice of the 20 particularly suitable solvent.
bromides. It is described that aryl chlorides are not very
Example 1
well useful for this method owing to the slight reactivity
of these compounds.
123.6 g. of 4-chlorothiophenol (0.8 mol) were dissolved
it is also described, that phenyl-iodide can be converted
in 150 cm.3 of a 30% by weight sodium methylate solu
into a thioether with a thiophenol in the presence of cop
25 tion in .methanol.
The solution was evaporated to dry
ness in vacuo. The residue, 4-chlorothiopheno1 sodium,
was dissolved in 1400 cm.3 dimethyl formamide, and added
per as a catalyst.
It is further described that reaction of a nitrobromo<
benzene and a nitrobromotoluene with sodium thiopheno
late results in thioethers only when the bromine atom oc
to a hot solution of 3600 g. of 1,2,4,S-tetrachlorobenzene
(16 mol) in 2600 cm? of dimethyl formamide, whilst
cupies the ortho-position or para-position with respect to 30 stirring. Then the resulting mixture was re?uxed for 90
the nitro group; as is known, the reactivity of such a
minutes, Whilst stirring. Subsequently, the reaction mix
bromine atom is increased by these nitro groups.
ture was cooled and stored at 0° C. for approximately
It is described in addition that 2-(2-methyl-5 halogeno
16 hours. Crystallized tetrachlorobenzene and sodium
phenylmercapto)-4 halogeno (or alkyl or alkoxy) benzoic
chloride were ?ltered Off and washed with 1000 cm.3 of
cold dimethyl formamide. The ?ltrate Was evaporated
acids can be prepared by heating a 2-halogeno-4-halogeno
(or alkyl or alkoxy) benzoic acid with a metal salt of a
until approximately 90% of the used dimethylfor-mamide
Z-methyl-S-halogeno thiophenol in the presence of a
catalyst, which are copper powder, copper halogenide and
had been recovered. The residue was then subjected to
a steam distillation to remove traces of tetrachlorobenzene.
copper oxide.
The residue of the steam distillation was taken up in 1.5
in contrast with what might ‘be expected on the basis of 40 liters of ether, ?ltered and washed twice with Water. After
what is known from the art, applicants have found that
polyaryl sulphides, and in particular diaryl sulphides, can
be prepared from aryl chlorides and alkali compounds of
thiophenols.
The invention relates to a process for the preparation
drying on sodium sulphate and evaporation, the 2,4,5,4’,
tetrachlorodiphenyl sulphide was obtained. Yield: 215
vg. (83%); melting point: approximately 84° C.
"
The compounds mentioned in Table I were prepared in
45
an analogous manner. Table 11 states the starting sub
stances (columns 2 and 3), the molar ratios in which the
compounds according to the Formulae B and A are used
(column 4), the solvent used (column 5), the melting
of polyaryl sulphides, and in particular of diaryl sulphides,
from alkali thiophenolates and aryl halogenides, char
acterized in that a compound of the formula
50
is prepared by causing to react a compound of the
formula
R,,.Ar.SMe
Clx.Ar.R’m
° C. at the pressure used in millimetres of mercury
(A)
column), and the yield of product obtained (column 7).
55
with a compound of the formula
(B)
in which formulae Ar may represent a phenyl radical or
point and/or the boiling point of the resulting products
(column 6) (the melting point is indicated by S and ex
pressed in ° C., the ‘boiling point by F and expressed in
The products obtained according to the process of the
invention often have an acaricidal activity and/ or may be
used as intermediates for the preparation of acaricidal
compounds. They may be converted into said com
pounds by oxidation to the corresponding sylphoxide and/
naphthyl radical, Me an alkali metal and preferably
sodium, Rn and R’m chlorine atoms or lower alkyl groups 60 or sulphones. The reaction products may be converted
or a combination thereof, x=l or 2, n is an integer
numeral of from 0 to 5 and is 1 if R represents chlorine
or also chlorine and m may be an integer numeral of
from 0 to 5 if x=l and of from 0 to 4 if x—2=2.
The reaction according to the invention is to be con—
sidered particularly for the preparation of diphenyl sul
into higher-chlorinated products by chlorination. For
example, 2,5-dichloro- and 2,5,4'-trichlorodipheny1 sul
phide may be chlorinated to 2,4,5,4’-tetrachlorodipheny1
sulphide and 2,5-dichloro-4'-methyldiphenyl sulphide to
5 2,4,5-trichloro-4’-methyldiphenyl sulphide. The thus ob
tained products, which may also be obtained ‘directly ac
cording to the process of the invention, have acaricidal
phides, in which R' represents chlorine and m=1, 2 or 3
activities. The 2,4,5,4’-tetrachlorodiphenyl sulphide is an
and of those in which R represents chlorine and n=1 or
interesting acaricide having an excellent activity against
R and R’ in these cases both represent chlorine.
70 eggs and larvae of red spider mites.
3,053,901
4
3
0 to 4 when x=2 comprising, condensing a compound of
the formula RnArSMe wherein Me is an alkali metal
with a compound of the formula ClxArRlm.
Table I
Products
2. The method of claim 1 wherein a compound of the
formula ClC6H4SMe is employed as a reactant.
3. The method of claim 1 wherein a compound of the
formula ClArClm, wherein Ar is a benzene radical and
m is an integer from 1 to 3, is employed as a reactant.
2.4.5i5t'-tetrachlorodlphenylsulphlde.
Do.
2.5.4;5trichlorodiphenylsulphide.
0.
0.
Do.
Do.
_
4. The method of preparing 2,4,5,41-tetrachl0rodipheny1
2.5-dichlorodiphenylsulphlde.
2-chl0ro-4’-methyldiphenylsulphlde.
2.5-dichloro—4’-methyldiphenylsulphide.
3.5~diehloro-4'-methyldiphenylsulphide.
2.4.5~trichloro4’-metliyldiphenylsulphide.
2.S-dichloro-2’.5’-dimethyldiphcnylsulphide.
2.ediehloro-il’.4’-dimethyldiphenylsulphide.
2.5-dicl11or0-3’.4’-dimethyldiphenylsulphide.
2.4.5~trich1oro-3.6.4’-trimethyldiphenylsulphide.
10
sul?de comprising condensing 1,2,4,5-tetrachlorobenzene
with an alkali metal 4-chlorothiophenolate wherein the
alkali metal has an atomic weight of from 23 to 39.1
inclusive.
5. The method of claim 4 wherein the reaction is car
S.S’-bis(4'-ch10rophenyl)-2.5-dichloropl1enylenedisulphide-IA.
5 ried out at a temperature of from 100° C. to 250° C. in
2A5A,_tetmchlorodiphenylsulphide,
a solvent selected from the group_consistmg_of dimethyl
Phenyl-a-naphtylsulphide.
.
Do.
-
-
-
amide, pyridine, qumohne, and triethanolarnme.
6. The method of claim 4 wherein the molar ratio of
Table 11
Ex.
Physical constants resulting
No.
Rn.Ar.SMe
ClxALR/m
I ______ __ 4~chl0rothiophenol-Na _____ _.
11..
_____do
LII.
____do
BzA
t.2.4.5-tetrachl0robenzene_____
(in
_____do
1.2.4»trlehlorobenzene..__ -__
_-___do
_____ __
_____do _____________________ __
Thiophenol-Na__-.
_____do _________ __
6
6
6
_ _ _ _ _ __
6. 2
1.2-diehlor0benzene __________ __
6.2
1.2.4-trichlorcbenzeno _______ __
6.4
1.3.5-trichlorobenzene _______ __
5.5
XII.-_-. ___-_do _____________________ -. 1.2.4.5-tetraehlorobenzene___._ 10
XIIL--. 2.5—dimethylthiophenoLNm. 1.2.4-trichlorobenzene...____-_ 6.3
XIV-_._ 2.4—dimethylthiophenol-Nai. _____
7.5
XV__....
Products
S=ca_1. 84° O_
S=8zr86° C..-
S=84.5-R5.5° C
65
--_-.d0.'_____
Quinol1ne.-_.
'I‘riethanolami
S=7§~76° CS=7a—76° C.
S=75~76° C.
(,3
69
50
BAdimethyIthiOphenoI-Na._ _--__do __________ __
XVL-.. p-Thiokresol-Na __________ -_ 1.2.4.5-tetrach1oro~p.
7.8
S=75~76° C
________ __
F=158-160°
. 1.1 mm. mercury...
55
Dimethylform?rniden S=93° O .......................... __
QuinOlme ........... -. S=60~61° (.2 _______________________ __
_
F=163—166 C.at1.0mm.mereury___
51
75
55
O. at 1.0 mm. mercury,S =
.---_do ____ _
.
_...I
.._
F=19°2° O. at 0.7mm. mercury ____ __
71
60
1.0
Pyridine _______ ._______ 8:222 C-
5
_____do
do
20
Dimethylformamldeu
68
S=96 a .................. _.
XVII..- 4~ch1orothiophen0l-Na_ _--_ 1.2.4.5-tetraehlorobeuzene_____
YY
75
52
XVIIL.
__ a-Chlomnaphtalene _________ __
62
S=67.5~09.5° C ____________________ __
D methylformamiden
XIX_.._ tehlorothiophenol-Na _____ __ 1.2.4.5-tetrachlorobenzene-.___ 20
33
(is
F=159—16l° C. at 1 mm. mcrcury_-___
8.5
Thiophenol-Na ______ __
yl
_
_____
Yield
111
percent
Dimethylformamiden
---._d0 ........ -_
Pyridine-..
6
___________ __do _ _ _ _ _ _ _ _ _ _ . _
p-Thiokresol-Nam
20
10
__________ __ 10
Diluent
S=38 05--
CYCl0he-Yan01----_----_ S=C=L 80 C
Dimethylsulphomdm. S=ca.80° C _______________________ __
78
60
42
45
the chlorinated benzene to the phenolate is from 6:1 to
20:1.
References Cited in the ?le of this patent
formula: (R,,.Ar.S)X.Ar.R1m wherein R and R1 are each
UNITED STATES PATENTS
members of the group consisting of chlorine and lower 45
alkyl, Ar is a member of the group consisting of phenyl
Gregory et a1. ________ __ Sept. 4, 1956
2,761,873
What is claimed is:
l. A method for preparing polyaryl sul?des of the
and naphthyl, x is a number selected from the group con
sisting of 1 and 2, n is an integer from 0 to 5, m is an
integer from 0 to 5 when x=1 and is an integer from
OTHER REFERENCES
Huisman et al.: Rec. Trav. Chim. 77, 103-122 (1958).
:UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 31053301
September 11, 1962
Jan'Hendrik Uhlenbroek
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 19 line 65, for Hif x—2:2" read -— if XIZ ~
0
Signed and sealed this 26th day of Febnuary 1963.
(SEAL)
Attest:
ESTON Go JOHNSON‘
Attesting Officer
’ DAVID L. LADD
Commissioner of Patents
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