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Патент USA US3029266

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iinited States hatent @thce
3,029,256
Patented Apr. 10, 1962
1
2
3,029,256
150° C. for a time sufficient to bring about essentially
complete reaction. Solvent can then be taken ed, as by
QUATERNARY AMMQNIUM COMPOUNDS HAV
ING A Z-(S-OXY-y-PYRONYDME'IHYL GROUP
Richard Sherrard (Took, Doylestown, Pa., assignor to
Rohm & Haas Company, Philadelphia, Pa., a corpo
filtration and/ or distillation, to leave a residue, which may
be an oil, a paste, or a solid. The product may be used
as thus obtained or it may be puri?ed, if so desired, as by
charcoaling, extracting, or in the case of some solids,
crystallizing from a suitable solvent.
ration of Delaware
No Drawing. Filed Oct. 23, 1959, Ser. No. 8¢l$,196
5 Claims. (Cl. 260-3453)
Solvents for reaction include acetone, methyl ethyl
ketone, methyl hexyl ketone, diethyl ketone, acetonitrile,
This invention concerns fungicidally active quaternary 10 nitrornethane, ethyl acetate, naphtha, benzene, toluene, or
ammonium compounds which have low phytotoxicity
toward growing plants. They have the structure
xylene.
Typical tertiary amines for reaction include n-dodecyl
15
dimethylamine, n-dodecyldiethylamine, n-dodecylmethyl~
hydroxyethylamine, n-dodecylmethylbenzylamine, cety1di~
methylamine, octadecyldimethylamine, octadecyl(hy
droxyethyl) amine, N~myristylmorpholine, n-dodecylpiper
idine, n-dodecylpyrrolidine, oleyldimethylamine, unde
wherein An represents an anion, R represents hydrogen, 20
an alkyl group up to four carbon atoms, or an acyl
cenyldiethylamine, (5,5,7,7-tetramethyl-2-octenyl)dimeth
ylamine, (nonylmethylbenzyl)diethylamine, (dodecylben
zyl) dimethylamine, 0ctylphenoxyethoxyethyldimethyl
amine,
group (R*CO—, where R* is alkyl, alkenyl, or aryl),
n o n ylphenoxyethoxyethoxyethylbenzylmethyl
amine, N-nonylphenoxyethoxyethylmorpholine, (diethyl
phenyl-Z-pentenyl)dimethylamine, nonyloxypentenyldi
R1 represents a lipophilic group of ten to 25 carbon atoms,
including alkyl groups of at least 10 carbon atoms, pref
methylamine, or nonylphenoxyethyldi('hydroxyethyl)
erably 12 to 18 carbon atoms, alkenyl groups of 11 to 25 amine.
18 carbon atoms, and arylaliphatic groups having at least
Typical Z-halomethyl-y-pyrones include 2-chlorometh
12 carbon atoms and preferably 15 to 25 carbon atoms,
yl-S-methoxy-y-pyrone,
Z-brOmomethyI-S-ethoxy-'y-pyr
and R2 and R3 when taken individually represent alkyl
one, Z-chloromethyl-S-hydroxy-y-pyrone, 2-chloromethyl
groups of 1 to 2 carbon atoms, the IS-hydroxyethyl group,
S-acetoxy-y-pyrone, 2-chloromethyl-S-benzoxy-y-pyrone,
or a benzyl group and when taken together, R2 and R3 30 Z-chloromethyl-S-propionoxy-v-pyrone, Z-chloromethyl-S
form a divalent aliphatic chain of 4 to 5 carbon atoms
acryloyloxy-ly-pyrone, 2-chloromethyl-S-crotonoxy-y-pyr
which with the nitrogen forms a heterocycle, as
one, and 2-chloromethyl-5-(ll-l-chlorobenzoxy)-'y-pyrone.
-~CHZCHZCHZCH2—, '_-CH2CH2CH2CH3CH2—, 01'
—CH2CH2OCH2CH2-, or the corresponding lower alkyl
Instead of the 'y-pyrone designation this nucleus is also
substituted chains, as found in C-methyl-pyrrolidine, 35
-piperidine, or -morpholine.
termed 4H-pyran-4-one.
The 2-chloromethyl-S-hydroxy-y-pyrone may be pre
pared by reacting Z-hydroxymethyl-S-hydroxy-y-pyrone
The lipophilic group is necessary for these quaternary
ammonium salts to be active against fungi. Somewhat
with thionyl chloride.
have proved to be, however, ineffective against fungi and
Thus 5-acetoxy-, 5-propionoxy-, 5-acryloxy-, 5-butyroxy-,
Likewise, 2-hydroxymethyl-5
methoxy-y-pyrone may be converted to the 2-chloro
structurally similar compounds have been prepared with
methyl derivative in the same way. The S-hydroxy
3 alkyl groups of one to two carbon atoms each. These 40 compound can readily be acylated with an acid anhydride.
rather toxic to plants. Other quaternary ammonium
compounds are known which have lipophilic groups, such
5-crotonoxy-, or S-benzoxy-derivatives may be prepared.
Instead of a carboxylic anhydride there may be used a
as (dodecylbenzyl)trimethylammonium chloride, dodecyl
(benZyDdimet'nyIammonium chloride, octylphenoxyeth
oxyethyl(benzyl)dimethylammonium chloride, and the
corresponding acyl halide together with a basic reagent
45 for taking up hydrogen halide.
In a typical preparation there are mixed 71 parts by
like. All of these at 1% in water when applied to young
tomato plants in the greenhouse have been observed to
weight of benzyldimethylamine, 80.3 parts of 2-chloro
methyl-5~hydroxy-'y-pyrone, and 500 parts of toluene at
be highly phytotoxic. Even at 0.1% these compounds
about 10° C. Over an hour there is added with stirring
have caused moderate to severe damage on tomato plants 50 97 parts of p-chlorobenzoyl chloride at 5 “~10‘’ C. The
in the hothouse.
mixture is heated to 50° C. and held at this temperature
The novel compounds of this invention are surprisingly
for two hours. Addition is made of 500 parts of Water.
effective against fungi which may attack various plants
An organic layer forms, is separated, is washed four
and yet are relatively safe when applied to plants at dilu
times each with 500 parts of water, and dried over mag
55
tions giving effective control of these fungi.
nesium sulfate. Toluene is stripped oil to yield 128 parts
Quaternary ammonium compounds of the above struc
of brown solid. This is recrystallized from isopropanol
ture are prepared by reacting a 2,-halomethyl-5-oxy-7
to give 2-chloromethyl-5-p~chlorobenzoxy-y-pyrone (melt
pyrone,
ing point 113 °—115° C.).
C
H
R0
to 1....
where R has the same signi?cance as above and X is a
halogen, chlorine, bromine, or iodine, with a tertiary
amine, R1R2R3N. Approximately equivalent quantities
of the two reactants are mixed, preferably in a volatile
organic solvent. The mixture is heated between 25° and
60
Details of the preparation of compounds of this inven
tion are presented in the following illustrative examples.
Parts are by weight unless otherwise designated.
EXAMPLE 1
A mixture of 80.5 parts of 2~ch1oromethyl-5-hydroxy
'y-pyrone, 151.5 parts of dimethyldodecylbenzylamine, and
500 parts acetone was re?uxed with agitation for ?ve
hours. The solid that separated on cooling was ?ltered
off, washed with acetone and dried for 18 hours at 50°
C./25 mm. There Was obtained 135.0 g. parts of tan
3,029,256
3%
4%
solid (M.P.=l96° C. with decomposition) of the follow
ing structure:
EXAMPLE 3
A mixture of 21.8 parts of 2-chloromethyl-S-hydroxy
'y-pyrone, 28.5 parts of dimethyldodecenylamine, and 200
parts of acetone was re?uxed with agitation for 24 hours.
The solid that separated on cooling was ?ltered 01f,
0
ll
washed with acetone and dried at 50° C./ 25 mm. There
was obtained 43 parts of white solid (M.P.=2l0° C.
(dodecylbenzyl-Z-(S-hydroxy-y-pyronyl)methy1)dimethyl
ammonium chloride.
with decomposition) of the following structure:
10
0
'
Analysis.--Calcd. for C27H42ClNO3Z Cl, 7.65; Cl“, 7.65;
N, 3.02. Found: CI, 8.0; Cl“, 7.7; N, 2.97.
110-‘
Thebiological data are as follows:
(a) Fungitoxicity (Slide-Germination)
Alt.
EDm __________________________ _ , _____ _ -
5-10
Mon.
5-10
II
15
(dodecenyl - 2 - (5 - hydroxy - v - pyronyl)methyldimeth
Stm.
5-10
NOTE.—-“Alt” is used as the abbreviation for Altemm‘t'a
solam‘, “Mon” for Monolt'm‘a fructicola, and “Stm” for Stem
ylamrnonium) chloride.
Analysis.—Calcd. for C20H34ClNO3: Cl, 9.6; Cl", 9.6;
N, 3.78. Found: Cl, 10.3; 01-, ‘10.3; N, 3.7.
20
The following are typical biological data:
Fungitoxicity (Slide-Germination)
phylium saroinaefm'me.
(1)) Tomato Phytotoxicity
Alt.
No injury at 11/4 lbs/‘r00 gal.
(0) Apple Scab (Venturia inaequalis)
now.-.‘ ______________________________ ._
On apple seedling (McIntosh) this compound gave
Stm
50-200
10~50
A mixture of 201 parts of 2-chlorornethyl-S-hydroxy
'y-pyrone, 41.5 parts of dimethyldodecylmethylbenzyl
The above procedure Was followed, but with use of
methyl isobutyl ketone as the solvent. The same com
amine, and 100 patrs of acetone was re?uxed for four
hours with agitation. The solid that separated on cool
ing was removed by ?ltration, washed with acetone and
pound was obtained. .
The procedure above is followed with substitution of
N-dodecylbenzylrnorpholine (173 parts). The product
10-50
EXAMPLE 4
100% eradication at ~74 lb./100 gal. and 68% at 1A
lb./100 gal. At 5% .lb./ 100 gal. there was no injury.
is
Mon.
25
35 dried at 50° C./25 mm.
There was obtained 54 parts
of tan solid (M.P.-_—97-100° C.) of the following ‘struc*
dodecylbenzyl - 2 - (5 - hydroxy - 7 - pyronyl)methyl
morpholinium chloride. Fungitoxicity of this compound
ture:
as determined by the slide-germination technique gives
ED50 values against the above test organisms of 10-50
p.p.rn.
40
EXAMPLE 2
A mixture of 80.5 parts of 2-chloromethyl-5-hydroxy
'y-pyrone, 160.5 parts of 18-(4-t-octylphenoxyethoxy) ethyl
dimethylarnine and 5 00 parts of acetone was re?uxed for
(dodecylmethylbenzyl - 2 - (5 - hydroxy - 'y - pyronyl)
6 hours with agitation. rThe solid that separated on 45 methyl)dimethylarnmonium chloride.
cooling was ?ltered off, washed with acetone and air
Analysis.-Calcd. for C28H44ClNO3: Cl, 7.42; Cl-,
dried. There was obtained 150 parts of tan solid
7.42; N, 2.92. Found: Cl, 7.42; Cl‘, 8.4; N, 2.86.
(M.P.=187° C. with decomposition) of the following
The biological data are as follows:
structure
50
Fungitoxicity (Slide-Germination)
Alt.
ED“) _________________________________ _.
CHzNHCHah-Cl“
Stm.
1-10
1-10
55
CHtCHzOCHzCHzO
EXAMPLE '5
A mixture of 15.0 parts of 2-chloromethyl-5~hydroxy
([5 - (4' - t - octylphenoxyethoxy)ethyl] - 2 - (5 - hy
droxy-y-)pyronyl) methyldimethylammonium chloride.
Analysis.-Calcd. for C2GH4OCINO: Cl, 7.35, Cl", 7.35,
N, 2.19. Found: C1, 8.3, C", 8.3, N, 2.86.
'y-pyrone, 20.0 parts of dimethyldodecylamine, and 150
60 parts of methyl ethyl ketone was re?uxed for 18 hours
with agitation. The solid that separated on cooling was
The biological data are as follows:
?ltered off, washed and dried at 50° C./.25 mm. There
was obtained 31 parts of white solid (M.P.=l85—l88° C.
(a) Fungitoxicity (Siide-Germination)
Alt.
10-50
Mon.
Mon.
with decomposition) of the following structure:
65
0
ll
E1350 _________________________________ -_
10-50
10-50
(b) Tomato Phytotoxicity
No injury at 1% lb./100 gal.
(c) Apple Scab
Percent eradication: 89 at 3%: lb./100 gal.; percent
protection: 87 at 1%; lb./1O0 gal.
70
(dodecyl - 2 - (5 - hydroxy' - 'y - pyronyl)methyldimethyl-v
ammonium chloride).
'
Analysis_.-Calcd. for C20H36ClNO3: CI, ‘9.5; Cl", 9.5;
76 N, 3.74. Found: Cl, 9.45; Cl", 9.42; N, 3.64.
v
3,029,256
6
(do decylbenzyl-2-(5-methoxy-7- pyronyl)methyldimethyl
' The biological data are as follows:
ammonium chloride.
Fungitoxicity (Slide-Germination)
Alt.
EDm _________________________________ ..
Mon.
10-50
7.42; N, 2.92. Found: Cl, 7.5; Cl“, 7.5; N, 2.78.
Stm.
10-50
The biological data are as follows:
1-10
(a) Fzmgitoxicity (Slide-Germination)
EXAMPLE ‘6
A mixture of 24.0 parts of 2-chloromethyl-S-hydroxy 10
q-pyrone, 36.3 parts of tetradecyldimethylamine, and
methyl ethyl ketone (300 parts) was re?uxed for 18
hours with agitation. The solid was removed by ?ltra
Alt.
ED“; _________________________________ _.
There was obtained 53 parts of light
\O
1-10
Strn
1-10
1-10
Percent eradication: ‘90 at 3%; lb./ 100 gal.
Very slight injury.
tan solid (M.P.=‘l87° C. with decomposition) of the
following structure:
HO ‘ l
Mon.
(12) Apple Scab
tion, washed with methyl ethyl ketone, and dried at
50° C./25 mm.
‘
Analysis.—Ca1cd. for C28H44ClNO3: Cl, 7.42; CI“,
The above procedure is followed with substitution of
20.6 parts of dodecyl(methyl)benzylmorpholine for the
above amine. The product is waxy without a sharp melt
20 ing point and corresponds in composition to N-dodecyl
(methyl)benzyl - 2 - (5 - methoxy-y-pyronyl)methylmor
phoiinium chloride. It gives ED5Q values of about 10
OHZN+(OHQ)ZCHHII;GI—
p.p.m.
in the same way N-substituted pyrrolidines and piperi
(tetradecyl - 2 - (5 - hydroxy - 'y - pyrone)methyldimeth
ylarnmonium chloride).
Analysis.—-Calcd. for C22H4OCINO3: Cl, 8.85; Cl",
25 dines may be used to give corresponding quaternary am
monium salts of similar properties.
8.86; N, 3.48. Found: Cl, 8.88; Cl-, 8.83; N, 3.41.
EXAMPLE 9
The biological data are as follows:
A mixture of 17.5 parts of 2-chloromethyl-5-methoxy
'y-pyrone, 33.0 parts of ,3-(4-tert-octylphenoxyethoxy)
ethyldimethylamine, and 100 parts of methyl ethyl ketone
was re?uxed for two hours. Removal of the solvent by
distillation under reduced pressure yielded 51.0 parts of
35 brown solid (M.P.=l24~l34° C.) of the following struc
ture:
Fmzgitoxicity (Slide~Germination)
Alt.
ED50 _________________________________ --
Mon.
1-10
1-10
EXAMPLE 7
A mixture of 20.1 parts of 2-chlorornethyl-S-hydroxy
ry-pyrone, 44.5 parts of cetyldimethylamine based on a
neutral equivalent of 363, and 200 parts of methyl ethyl 40
ketone was re?uxed for 20 hours with agitation. The
solid was removed by ?ltration, washed, and dried at 50°
C./ 25 mm. There was obtained 43 parts of brown solid
I
O I CH2N+(GHs):-C1'
C HzOHzO CHZCHZO G aH4CaH17-—Z
(M.P.=152-165° C.) of the following structure:
( [B- (4'-tert-octylphenoxyethoxy) ethyl] - 2 - (S-methoxy
0
45
I
HO 1 l
LO
(EH30
'y- ) pyronyl) methyldimethylammonium chloride.
Analysis.-—Calcd. for C27H42ClNO5: Cl, 7.16; Cl‘,
7.16; N, 2.82. Found: Cl, 7.16; Cl", 6.7; N, 2.7.
CHgN+ (G 1192C itHas- C1“
Fungitoxicity (Slide-Germination)
(cetyl - 2 - (5 - hydroxy-y-pyronyl)methyldimethylammo
50
nium chloride).
Alt.
Analysis.—Calcd. for a molecular weight of 524 (based
on the neutral equivalent of the amine): Cl, ‘6.76; Cl“,
ED“; _________________________________ . .
10-50
M011.
10-50
Stm.
<1
6.76; N, 6.76. Found: Cl, 6.70‘; Cl", 6.60; N, 6.60.
The biological data are as follows:
EXAMPLE 10
Fungz'toxiciz‘y (Slide-Germination)
Alt.
ED“: _________________________________ _ _
10-50
A mixture of 2-chloromethyl-S-acetoxy-y-pyrone (20.2
parts), 35.0 parts of dimethyldodecylbenzylarnine, and
methyl ethyl ketone (200 parts) was re?uxed for 18
Mon.
10-50
10-50
60 hours with agitation. The solid that separated on cooling
was ?ltered 01f, washed, and dried. There was obtained
33.0 parts of tan solid (M.P.=l86—189° C.) of the fol
EXAMPLE 8
lowing structure:
‘
A'mixture of 2-chloromethyl-5-methoxy-7-pyrone ( 17.5
parts), 34.9 parts of dimethyldodecylbenzylamine, and 65
100 parts of methyl ethyl ketone was re?uxed for 3 hours
with agitation. The solid was ?ltered off, washed and
dried. There was obtained 34.5 parts of white solid
(M.P.=l73-76°) of the following structure:
0
|
C1130 l
70
(do decylbenzyl-2- (S-acetoxy-y-pyronyl ) methyl) dimethyl
ammonium chloride.
Analysis.—-Calcd. for C29H44ClNO4: Cl, 7.04; Cl“,
75 7.04; N, 2.78. Found: Cl, 7.14; Cl“, 6.95; N, 2.73.
3,029,25e
7
(a) Fungitoxicity (Slide-Germination)
Alt.
ED5n _________________________________ __
1-—10
8
(M.P.=162-167° C. with decomposition) of the follow
ing structure:
The biological data are as follows:
Mon.
1-10
1-10
(1)) Phytotoxicity (Apple Seedlings)
10
1 lb./ 100 gal.=Very slight injury.
1/2 lb./ 100 gal.=Very slight injury.
([B-(4’-tert-octylphenoxyethoxy)ethyl] - 2 - (5 - propion
oxy-y-pyronyl)methyldimethylammonium chloride.
Analysis.-Calcd. for C29H44NO6Cl: Cl, 6.59; Cl",
6.59; N, 2.6. Found: Cl, 6.34; 01-, 6.36; N, 2.46.
EXAMPLE 11
A mixture of 20.2 parts of 2-chloromethyl-5-acetoxy
The biological data are as follows:
Fungitoxicity (Slide-Germination)
'y-pyrone, 54.5 parts of ,8-(4'-tert-octylphenoxyethoxy)
ethyldimethylamine, and methyl ethyl ketone (200 parts)
was re?uxed for 18 hours with agitation. The solid was
?ltered off, washed and dried. There was obtained 44.0
parts of white solid (M.P.=l7l—l75° C. with decom
Alt. ,
ED” _________________________________ __
1-10
1-10
20
position) of the following structure:
EXAMPLE 14
A mixture of 12.5 parts of 2-chloromethyl-5-crotonoxy
*y-pyrone, 19.3 parts of dimethyldodecylbenzylamine, and
150 parts of methyl ethyl ketone was re?uxed for 18
25
hours with agitation. The slurry was cooled and the solid
?ltered o?, washed with methyl ethyl ketone and dried
0
II
M\O/_CH2N+(CH3)TC1_
CHnCHzOCH2OHgOOuH4CsH17—t
‘at 50° C./ 25 mm. There was obtained 21.0 parts of white
([,8-(4'-tert - octylphenoxyethoxy)ethyl]-2-(5-acetoxy-'y-)
solid (M.P.=vl76—185° C. with decomposition) of the
following structure:
pyronyl)-methyldimethylammonium chloride.
Analysis.-Calcd. for C28H42ClNO6: Cl, 6.78; Cl",
0
0
6.78; N, 2.68. Found: Cl, 6.94; Cl—, 6.69; N, 2.63,
Fzmgitoxicity (Slide-Germination)
i l CHaN+(CHa)2CH2GAHACuHu'CI‘
35
Alt.
10-50
Mon.
1M0
||
CH3CH=CH(|§—'-O
The biological data are as follows:
E‘Dw ................................. -_
S01.
Stm
(dodecylbenzyl - 2 - (5 - crotonoxy - 'y - pyronyDmeth
yl) dimethylammonium chloride.
Analysis.—Calcd. for C31H4GCINO4: Cl, 6.65; Cl-,
10~50
6.65; N, 2.62. Found: Cl, 6.73; C11 6.74; N, 2.62.
EXAMPLE 1-2
The biological data are as follows:
A mixture of 21.7 parts of 2-chloromethyl-S-propion
oxy-y-pyrone, 35.0 parts of dimethyldodecylbenzylamine,
and 300 parts of methyl ethyl ketone was re?uxed for
18 hours with agitation. The solid was ?ltered off,
washed, and dried at 50° C./25 mm,
Fungitoxicity (Slide-Germination)
Alt.
There was ob
ED” _________________________________ __
taihed 39.0 parts of light tan solid (M.P.=187~189° C.
with decomposition) of the following structure:
1-10
Mon.
1-10
‘Stm.
1-10
EXAMPLE 15
A mixture of 11.0‘ parts of 2~chloromethyl-S-crotonoxy
50
y-pyrone, 16.0 parts of ?-(4-tert-octylphenoxyethoxy)eth
yldimethylamine, and 125 parts of methyl ethyl ketone was
re?uxed for 41/2 hours with agitation. The slurry was
cooled and the solid filtered off, washed with methyl ethyl
(dodecylbenzyl - 2 - (S-propionoxy-y-pyronyl)methyl)di
55 ketone, and dried ‘at 50° C./ 25 mm. There was obtained
17 parts of white solid (M.P.<=Il75° C. with decomposi
tion) of the following structure:
methylamrnonium chloride.
Analysis.-Calcd. for C30H46ClNO4: Cl, 6.83; Cl-,
6.83; N, 2.69. Found: Cl, 6.86; CI", 6.86; N, 2.68.
The biological data are as follows:
0
(I?
60
Fungitoxicity (Slide-Germination)
CHaCH=CHC-O I
l
0
’
Alt.
Mon.
Stm.
/I-OHEN+(CH3)TOI_
CI'IgCH?OCHQCH?OCQHQCSHH’t
([{3 - (4’ - tert - octylphenoxyethoxy)ethyl] - 2 - (5 - cro
E1350 _________________________________ -_
1-10
1-10
1-10
65
EXAMPLE 13
tonoxy-y-) pyronyl) -methylidimethylammonium chloride.
Analysis-Calm. for C3OH44CINOG: Cl, 6.47; CI-,
6.47; N, 2.56. Found: Cl, 6.47; C11 6.5; N, 2.41.
A mixture of 21.7 parts of 2-chloromethyl-5-propion
oxy-y-pyrone, 33.0 parts of p-(4'-tert-octylphenoxy 70
ethoxy)ethyldimethylamine, and 300 parts of methyl
The biological data are as follows:
ethyl ketone was re?uxed for 18 hours with agitation.
The solid that separated on cooling was ?ltered off,
washed with methyl ethyl ketone, and dried at 50° C./ 25
mm. There was obtained 43.0 parts of tan solid 75
Alt.
Fungitoxicity (Slide-Germination)
ED“) _________________________________ - _
10-50
Mon.
1U~50
Stm.
10-50
3,029,256
9
10
EXAMPLE 16
A mixture of 29.9 parts of 2-chloromethyl-5-(4’-chlo
nium bromides are at least as e?ective as the correspond
ing chlorides and in some instances are more active.
As is known in the art, the chloride or bromide ion
robenzoXy)-'y-pyrone, 35.0 parts of dodecylbenzyldimeth
may be replaced in known ways with other anions. Thus,
ylamine, and methyl ethyl ketone (300 parts) was re
?uxed for 5 hours with agitation. The slurry was cooled
a concentrated solution of a quaternary ammonium chlo
ride may be treated with a sodium phosphate solution
to exchange anions with formation of quaternary am
and the solid removed by ?ltration, washed with methyl
ethyl ketone and dried at 50° C./ 25 mm. There was ob
monium phosphate. Through conversion of halide to
hydroxide and subsequent neutralization any anion can
be introduced, including acetate or propionate, as typical
anions of organic acids. It is thus possible to have pres
tained 37 parts of tan solid (M.P.=1171-174° C.) of the
following structure:
ent any desired ‘anion.
I claim:
1. Compounds of the formula
15
0
I
(dodecylbenzyl - 2 - [5 - (4’ - chlorobenzoxy) - "y - py
ronyl] )methyldimethyl-ammoniuni chloride.
Analysis-Calm. for: C1, 11.7; Cl-, 5.87; N, 2.32.
Found: Cl, 11.3; C1“, 5.6; N, 2.3.
20
R0
CHaN-R2
0
The biological data ‘are as follows:
E1350 _________________________________ .._
lipophilic group selected from the class consisting of alkyl
groups of 12 to 18 carbon atoms, alkenyl groups of 11
Mon.
10-50
\R3
wherein An represents an inert anion, R1 represents a
Fungitoxicity (Slide-Germination)
Alt.
1 I if‘
<1
25 to 18 carbon atoms and alkylphenyl, alkylphenylalkyl,
alkylphenylalkenyl, alkylphenoxyalkoxyalkyl, alkylphen
<1
oxyalkoxyalkoxy, alkoxyalkenyl and alltylphenoxyalkyl
of 12 to 25 carbon atoms, R2 and R3 when taken individ
EXAMPLE ‘17
ually represent groups from the class consisting of alkyl
A mixture of 29.9 parts of 2-chloromethyl-5-(4'-chlo
groups of one to two carbon ‘atoms, the hydroxyethyl
robenzoxy)-'y-pyrone, 32.7 parts of ,B-(4'-tert-octylphe
noxyethoxy) -ethyldirnethylarnine, and methyl ethyl ketone
group, and the benzyl group and, when taken together,
a divalent chain from the class consisting of
(300 parts) was refluxed for ?ve hours with agitation.
The slurry was cooled and the solid ?ltered off, washed
with methyl ethyl ketone and dried at 50° C./25 mm. 35
There was obtained 54.5 parts of tan solid (M.P.=~170—
and the methyl-substituted derivatives thereof, and R is a
173° C.) of the following structure:
monocarboxylic group R*CO-— where R* is a member
of the class consisting of phenyl groups and alkyl and
40 alkenyl groups of one to three carbon atoms.
2. N - [e - (18' - (4’ - tert - octylphenoxy)ethoxy)eth—
yl] - N - (2 - (5 - acetoxy - 'y - pyronyl)rnethyl) - N,N
dimethylarnmonium chloride.
OHKOHQOOH2CHQOCGHAGBHI7¢t
3. N - dodecylbenzyl - N - (2 - (5 - propionoxy - 'y
45 pyronyl) - methyl) - N,N - dimethylammonium chloride.
[,8 - (4’ - tert - octylphenoxyethoxy) ethyl] - 2 - [5 - (4"
4. N - dodecylbenzyl - N - (2 - (5 - crotonoxy - 'y-py
chlorobenzoxy) - v - pyronyl] methyldimethylammonium
chloride.
ronyl) - methyl) - N,N - dimethylarnmoniurn chloride.
Analysis.—Calcd. for: C1, 11.4; Cl‘, 5.73; N, 2.26.
Found: Cl, 10.9; Cl: 5.4; N, 2.3.
oxy) -'y-pyronyl] methyl) N,N-dimethylammonium
5. N - dodecylbenzyl - N - (2 - [5 - (4' - chlorobenz
The biological data are as follows:
Fzmgitoxicity (Slide-Germination)
Alt.
Mon.
T21
EDM _________________________________ -
10-50
chlo
ride.
l-l0
1
References Cited in the ?le of this patent
UNITED STATES PATENTS
2, 8 12,3 50
Niederhauser _.._. _______ __ Nov. 5,
2,918,402
1957
Fredrick ____________ __ Dec. 22, 1959
OTHER REFERENCES
While in the examples there has been used the chloro~
methyl group, there may be used in the identical way the
Campbell et al.: Journ. Org. Chem, vol. 15, pages 221
bromomethyl group. The resulting quaternary ammo (it)
6 (1950).
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