DERIVES DU NITROARYLALCOYLSULFONE, GAMETOCYTOCIDES

NITROARYLALKYLSULFONE DERIVATIVES AS GAMETOCIDES

Abrégé anglais

ABSTRACT OF THE DISCLOSURE
New compounds have the formula:
< IMG >
wherein R1 is C1-C6 alkyl, R2 and R3, each independently of the
other are hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl,
halogen, cyano, nitro or amino or, both together in the ortho-
position to each other as a -(CH=CH)2- group, complete a
naphthalene ring, and R4 is a hydrazinium or ammonium ion.
The new compounds are useful as active components in gametocidal
compositions.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compounds having the formula:
< IMG > I
wherein R1 is C1-C6 alkyl, R2 and R3, each independently of the
other, are hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl,
halogen, cyano, nitro or amino or, both together in the ortho-
position to each other as a -(CH=CH)2- group, complete a naphtha-
lene ring, and R4 is a hydrazinium or ammonium ion.
2. Process for producing compounds of formula I as defined
in claim 1 comprising neutralising a free phenol of formula II:
< IMG > II
wherein R1, R2 and R3 have their previous significance, in the
temperature range from 0° to 180°C, and in the presence of an
inert solvent, with an aqueous hydrazinium or ammonium hydroxide
derivative, and isolating the resultant salt in conventional manner.
3. 4-Hydroxy-3-nitrophenylmethylsulfone-tetra(n-butyl)
ammonium salt.
-7-

Description

~ ~ 21489-6048D
This application is divided ou~ of Application No.
400,724, filed April 8, 1982.
The present invention relates to new nitroarylalkyl~
sulfone derivatives and their production.
The presen-t lnvention provides compounds having the
formula I:
02N
4 ~ SO2R
R3 R2
wherein Rl is Cl-C6 alkyl, R2 andR3, each independently of the
other, are hydrogen, Cl-C6 alkyl, Cl-C6 alkoxy, Cl-C6 haloalkyl,
halogen, cyano, nitro or amino or, both together in the ortho-
position to each other as a -(Ch=ClI~2- group, complete a naphtha-
lene ring, and R4 is a hydraziniumor ammonium ion.
Alkyl by itself or as moiety of another substituent
comprises e.g. the following groups: methyl, ethyl, propyl, bu-tyl,
pentyl and hexyl, and the isomers thereof e.g. isopropyl, isobutyl,
tert-butyl and isopentyl. Haloalkyl is a mono-- to perhalogenated
alkyl substituent e.g- CHC12, CH2Cl, CC13, CF3 or CH2CH2Cl. Halo-
gen denotes fluorine, chlorine, bromine or iodine, chlorine and
bromine being preferred. Examples of suitable ammonium ions are:
N~14, NH(alkyl)3, NH2(alkyl)2 and NH3(alkyl), such as NH(CH3)3,
2 5)3~ 2(CH3)2' NH2(C3H7-n)2~ NH3CH3, NH3c4H9-nr or quaternary
ammonium ions such as tetraethylammonium, tetrapropylammonium,
tetrabutylammonium, tetrapentylammonium, tetrahexylammonium,
tetraheptylammonium, tetraoctylammonium, tetranonylammonium,
tetradecylammonium, methyltributylammonium, dimethyldibutylammonium,
,,", ~f

- la -
trimethylbutylammonium, methyltrioctylammonium, benzyltrimethyl-
ammonium, benzyltriethylammonium, benzyltripropylammonium, benzyl-
tributylammonium, benzyldimethylhexadecylammonium, benzyl-

3Çj
-- 2
diethylhexadecylammonium, diisobutylcresoxyethyldimethylbenzylammonlum, trimethylphenylammonium, diphenyldimethyl-
a~monium, butyltripropylammonium, tributylphenylammonium
or tricaprylmethylammonium. Suitable hydrazinium ions
are unsubstituted or substituted hydrazinium ions, such as
3 2 Y )3, ~2~1(alkyl)2, NH2NH2(all;yl) etc
In addition to NH~, preferred am~.onium cations comprise,
in particular~ those of the type ~(4 a)(lower al~;yl)~, in
which a = 1, 2, 3, or 4, and among these, in particular
te~raal~ylammonium ions suc~ as N(CH3)4, N(C2H5)4,
(C4Hg_n)4~ N(CH3)2(C2Hs)2, ~(C3H7~ , N(C3~17_i)4 etc.
The compounds oE formula I are ~ils, resins or
mainly solids which are stable at room temperature and
have very valuable microbicidal and plant growth
regulating properties. They may there~ore preferably be
used in agriculture or related fields for selectively
influencing flower Eormation in plants and are also
suitable for controlling phytopathogenic microorganisms.
Copendin~ British Patent Application No. 8210563
~Serial No. 2102782)~ descri.bes and claims gametocidal
compositions containing, as active component, a compound of
formula I.
The present invention.also provides a process for
producing compounds ~f formula I comprising neutralising
a free phenol of formula II:
02N
HO ~ S2Rl II
R3 R2

53~
-- 3
wherein Rl, R2 and R3 have their previous significance, in
the temperature range from 0 to 180C, and in the presence
of an inert solvent~ with an aqueo~s hydrazinium or
ammonium hydroxide derivative, and isolating the resultant
salt in conventional manner.
The inv~ntion is further illustrated by the following
Exam~les.

Exam~le 1
. .
a) Preparation o
02N\
HO~ SO CH (2.1)
4-Hydroxy-3-nitrophenylmethylsulfone
-
25.6 kg of 4-chloro-3-nitrophenylmethylsuLfone are stirred
slowly into 4 kg of 30 % aqueous sodium hydroxide and the
mixture is diluted continuously with water to a volume of
about 50 litres. I~e reaction mixture is heated to 90 C
and th&n a -Eurther 29 kg of 30 % aqueous sodium hydroxide
ar~ added, ~7ith stirring, over 3 to 4 hours. ~he mixture
is then heated -for 90 minutes to 103 C. After it has
cooled to about 60 C, the solution is adiusted ~ith 16 ~/O
sulfuric acid to a pH value oE about 1.5, w'nereupon the
product precipitates. The precipitate is isolated by
-filtration, washed and recrystallised from ethanol.
~ield: 24 kg o~ colourless crystals with a melting point
o~ 166-168C.
b) Preparation oE
0 2N~
\.=~/ 2 3 (1.1~,)
~-Cycl_ol~rQP~rlcarbonyloxy- 3--nitrophenylmeth~lsuLone
32.6 g o ~-hydroxy-3-nitrophenylmethylsulone are
suspended in 250 ml o tetrahydro-Eurane and to this
suspension are added 21 ml of triethyLamine. With
stirring, 15~7 g o ~cyclopropanecarboxylic acid chloride
are added dropwise to the resultant solu~ion. ~ter the

wea~ly exothermic reaction has subsided, stirring is
continued for 3 hours at room temperature and the fiLtrate
is concentrated, affording 42 g of a viscous oil which is
digested with petroleum ether. Yield: 40.5 g of pale
yellow crystalline product with a melting point of
114 -116 CO
c) Preparation of
2 \ _ ~
\ _ / 2 3 ~(C4~9-n)4 (2.20)
_
4-~1ydroxy-3-nitrophenylme_h~lsulfone tetra-(n-butyl~
ammonium_sa].t
To a solution o-f 13.5 g of 4-hydroxy-3-nitrophenylmethyl-
sulfone in 100 ml of ethanol are added 41 g of a 40 %
aqu20us tetrabutyla~monium hydro~ide solution. T~le
resultant deep yello~ solution is evaporated in a rotovap
to give 28 g of yellow crystal product with a melting point
of 98-L00 C.
Examples 2 to 8
The compounds listed in the following Table can be
prepared using procedures similar to those descrlbed in
Example 1.
- 5 -

3536
-- 6 --
Table Compounds of the formula I
02N~ ~
R40- ~ ~ S2 1 ~I)
3 2
Rl R~ R3 R~ Physical data
(C)
_ _
2~CH3 H H N(CH3)4 m.p. 151-153
3.CH3 H H N(C4Hgn)4 m.p. 98-100U
4'CH3 H H N(C2HS)4 m.p. 130-137
5.CH3 H H N(CH3)3CH2C6H5 orange-yellow-resin
6. 3 ( 3)3 12 25 orange resin
7. 3 N(CH3)2N(CH3)3 orange resin
8. C1~3 H H NH2NH3
~r