PHENOXYACETIC ACID ESTER

TRADUCTION NON-DISPONIBLE

English Abstract

ABSTRACT
Propyl 3-t-butylphenoxyacetate, a hitherto
undisclosed compound, is useful for regulating the growth
of plants when applied to actively growing or dormant
tissues of the plant, for example crop-bearing trees to
increase the yield of the crop.

Claims

The embodiments of the invention, in which an
exclusive privilege or property is claimed, are defined as
follows:
1. Propyl 3-t-butylphenoxyacetate.
2. A process for the preparation of propyl
3-t-butylphenoxyacetate which comprises
(A) reacting a compound of the general formula:-
<IMG> II
(wherein X represents the hydroxy group, a halogen atom,
or an alkoxy group containing 1 to 6 carbon atoms other
than the propoxy group) with pxopanol, or
(B) reacting a compound of the general formula:-
<IMG> III
(wherein M represents an alkali metal atom) with a compound
of the generel formula:-
YCH2COOR IV
(wherein Y represents a halogen atom and R represents an
alkyl group containing from 1 to 6 carbon atoms, followed
by, when the reactant of general formula IV is other than
a compound wherein R is the propyI group, transesterifying
the resulting alkyl 3-t-butylphenoxyacetate to replace by
known methods the alkyl ester group by the propyl group.
- 24 -

3. A process according to claim 2(A) wherein
X represents the hydroxy group and the reaction is
effected in the presence of an acidic catalyst optionally
in the presence of an inert organic solvent, or using a
stoichiometric excess of propanol as solvent, under
substantially anhydrous conditions at elevated temperature.
4. A process according to claim 2(A) wherein
X represents a halogen atom and the reaction is effected
optionally in the presence of an acid-binding agent and
optionally in the presence of an inert organic solvent
at ambient or elevated temperature.
5. A process according to claim 2(A) wherein
X represents an alkoxy group other than the propoxy group
and the reaction is effected in the presence of an acidic
catalyst optionally in the presence of an inert organic
solvent, or a stoichiometric excess of propanol as
solvent, under substantially anhydrous conditions at
elevated temperature.
6. A process according to claim 2(B) in which
the reaction between the compounds of general formulae III
and IV is effected in the presence of an anhydrous inert
organic solvent at a temperature between 0°C and 100°C.
7. A method for regulating the growth of
plants which comprises the application to actively growing
or dormant tissues of the plant of an effective amount
of propyl 3-t-butylphenoxyacetate.
- 25 -

8. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to crop-bearing trees to increase the yield of
fruit therefrom.
9. A method according to claim 7 in which the
crop-bearing trees are apple, pear, cherry, plum, citrus
or oil palm trees.
10. A method according to claim 8 or 9 which
comprises applying to the crop-bearing trees a liquid
composition containing from 750 to 1500 ppm of propyl
3-t-butylphenoxyacetate.
11. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to one year old nursery fruit trees to encourage
feathering.
12. A method according to claim 11 which
comprises applying to the one year old nursery fruit
trees a liquid composition containing between 750 and
1500 ppm of propyl 3-t-butylphenoxyacetate to the top
20 cm to 50 cm of the growing tip of the tree.
13. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to two or three year-old fruit trees after replanting
in an orchard to produce secondary lateral branches.
14. A method according to claim 13 which
comprises applying to the fruit trees a liquid composition
containing between 1250 to 1500 ppm of propyl 3-t-butyl-
phenoxyacetate.
- 26 -

15. A method according to claim 13 or 14 in
which the trees are apple or pear trees.
16. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to ornamental plants to improve the shape of the
ornamental plants by encouraging a vigorous bushy growth
and, in the case of trees, feathering.
17. A method according to claim 16 which comprises
applying to the plant a liquid composition containing
from 750 to 4000 ppm of propyl 3-t-butylphenoxyacetate.
18. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is applied
to fruit-bearing plants to improve the quality of fruit
therefrom by thinning out full blossoms, young fruitlets and
intermediate stages when these growth stages are present.
19. A method according to claim 18 which comprises
applying to the fruit-bearing plants a liquid composition
containing from 250 to 1500 ppm of propyl 3-t-butylphenoxy-
acetate.
20. A method according to claim 18 or 19 in which
the fruit-bearing plants are apple trees or vines.
21. A method according to claim 13 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to a field crop to improve the yield therefrom.
22. A method according to claim 21 which comprises
applying to the field crop a liquid composition to give
a rate of application of propyl 3-t-butylphenoxyacetate
of from 0.56 to 2.24 kg per hectare.
- 27 -

23. A method according to claim 21 or 22
in which the field crop is cotton, soya beans, field
beans, dwarf beans, groundnuts, oil seed rape or sunflower.
24. A method according to claim 21 or 22 in
which the liquid composition containing propyl
3-t-butylphenoxyacetate is applied at the flowering
stage of the crop.
25. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate
is applied to a young plantation crop to chemically prune
the crop.
26. A method according to claim 25 which
comprises applying to the young plantation crop a liquid
composition containing from 750 to 3000 ppm of propyl
3-t-butylphenoxyacetate.
27. A method according to claim 25
or 26 in which the plantation crop is that of tea.
28. A method according to claim 7 in which
an effective amount of propyl 3-t-butylphenoxyacetate
is applied to nursery stock to cause defoliation.
29. A method according to claim 28 which
comprises applying to the nursery stock at the end of
the growing season or before flowering a liquid composition
containing from 1000 to 10000 ppm of propyl 3-t-butyl-
phenoxyacetate.
- 28 -

30. A method according to claim 7 in which
an effective amount of propyl 3-t-butylphenoxyacetate is
applied to potato plants to increase the number and
yield of potato tubers.
31. A method according to claim 30 which
comprises applying to the potato plants a liquid
composition containing from 1000 to 3000 ppm of propyl
3-t-butylphenoxyacetate.
32. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate is
applied to a crop of Brussels sprouts to improve the
yield of the crop and reduce wastage.
33. A method according to claim 32 which
comprises applying to the Brussels sprouts at the time
the sprouts are forming a liquid composition
containing from 4000 to 6000 ppm of propyl 3-t-butyl-
phenoxyacetate.
34. A method according to claim 7 in which
an effective amount of propyl 3-t-butylphenoxyacetate
is applied to tomato plants to suppress undesirable
lateral growth.
35. A method according to claim 34 which
comprises applying to the tomato plants a liquid
composition containing 3000 ppm of propyl 3-t-butyl-
phenoxyacetate.
- 29 -

36. A method according to claim 7 in which an
effective amount of propyl 3-t-butylphenoxyacetate
is applied to a monocotyledonous crop to increase the
yield therefrom by increasing the number of tillers and/or
reducing the number of blind heads.
37. A method according to claim 36 which
comprises applying to the crop a liquid composition
containing from 200 to 2000 ppm of propyl 3-t-butyl-
phenoxyacetate.
38. A method according to claim 36 or 37
in which the crop is wheat, barley or rice.
39. A method according to claim 7 in which
a liquid composition containing propyl 3-t-butylphenoxy-
acetate is applied to the plant or crop in the form
of a spray.
- 30 -

Description

~7'36
THIS INVE~TI0~ relates to a new agriculturally-
useful ester, to processes for it~ prleparation, to its use
as a plant-growth regulator and to compositions containing
it.
As a result of research and experimentation, it
has been found that p~opyl 3-t~butylp:henoxyacetate, which
has the formula:-
~ OC~2COO(CH2~2~H3
3 3
, exhibits valuable p1ant-growth regulatory propertie~ when
applied to actively growing or dormant plant tis~ue, and may be
used to influence beneficially the growth of economically
~aluable plant~, for example by improving the quan~ity or the
quality of the resulting cropl by enabling the grower to exercise
conveniently more control over the growing process or by
facilitating the handling, ~articularly khe mechanical
handling, o the crop, e.g. ~:t harve~ting. Depending upon
the rate of application and the growth stage of the plant-
tissue which is treated, the application of propyl 3-t-
butylphenoxyacetate may s~imulate and enhance plant growth
or inhibit plant growth. For example, the application of
the compound of formula I:
; ~a~ increases the yield of crop-bearing trees, e~pecially
apple, pear, cherry, plum, citru~ and oil palm txees,
~ 2 ~
.
.
. ; ,, ,.: ~. ;, . ~ -
. ,, : ~ .

~ 9~
(i) by improving the ~hape o the tree, encouraging
the ifeathering' of one year-old nur~ery stock by checking
stem tenminal growth without kilLing the apical growth
point and inducing vigorous lateral branching above the point
of app}ication (u~ually to the top 20 centimetres to 50
centimetre~ of the tree) with a desirable wide crotch angle
between these lateral branche~ and the stem o~ the rnaiden
tree, and~or the production of ~econdary lateral branche~
in two and three year-old tree~ after replanting in the
: lO orchard, by application during the annual period of
vigorou~ growth,
(ii) in the ca~e of fruit trees, e.g. apple, pear,
cherry and plurn trees, by reducing the vegetative growth
period before a significant crop i~ produced after replanting
the nur~ery stock in the orchard; genexally from two years
to one year in the case of apple trees, in trees treated
:~ a~3 de~cribed in
For the~e purpo~e~, ~.e. ~a)(i) and (ii), propyl
3-t-butylphenoxyacetate may suitably be applied in sprays
~: 20 and similar formulations containing ~rom 750 to 1500 part~
per million (pprn) c>f that compou~d.
(b) improv~ the 3hape of ornamental plarlt~ including
both container~grown plants, e.g. ornus sp (dogwood), and
.; .
ornamental nur~ery tree~, e.g. ~cer sp ~for exa~ple
. 25 sycamor~ ~ encouraging a vi~orou~ bushy growth and, in the ca~e of tree~ eathering'. For this purpo~e, propyl
~ ' ` ' . .
~. - 3 ~ .
.
.
;
. .

~9~736;
3 t-butylphenoxyacetate may suitably be applied in sprays
and similar formulations containin~ from 750 to 4000 ppm
of that compound.
(c) improves the quality of fruit, especially apples and
S grapes, by thinning out full blossoms, young fruitlets and
intermediate stages when applied when these growth stages
are present. For this purpose propyl 3~t-butylphenoxyacetate
may suitably be applied in sprays and similar formulations
containing from 250 to lSOO ppm of that compound,
(d) improves the yield of field crops, for example cotton,
soya beans, ~ield beans, dwarf beans, groundnuts, oil seed
rape and sunflower, more particularly when applied at the
10wering stage, e.g. of a crop o cotton. For this purpose,
propyl 3-t-butylphenoxyacetate may suitably be applled at
rates of application of from~0.56 to 2.24 kg of that
compound per hectare.
(e) chemically prunes young plantation crops, for example
tea, by enhancing lateral growth. For this purpose, propyl
3-t-butylphenoxyacetate may suitably be applied in sprays
and similar formulations containing 750 to 3QOOppm of that
compound.
(f) defoliates nursery stock
(i) by application at the end of the growing season,
which ~acilitates transplantation and control of disease,
for example o ornamental shrubs and trees, e.g. rose~ and
99~Es~@ rubra (red oak) and fruit trees, e.g. apples,and
-- 4 --
. , ~

~C~9~'73~
hedges, and
~ by application before flowering, e.g. of jasmine,
to increase the subsequent yield of fl.owers per bu~h.
For the~e purposes, i.e. ~f)~i~ and (ii~ propyl
3~t ~utylphenoxyacetate may ~uitably be applied in sprays
and similar formulations containing ~rom 1000 to 10000 ppm
of that compound.
(g) increases the number and yield of potato tubers. For
this purpose, propyl 3-t-butylphenoxyacetate may suitably
be applied in sprays and similar formulation~ co~taining
from 1000 to 3000 ppm of that compound.
(h) improve~ the yield and reduces wa~tage in crops of
:~ Brus~èls ~prouts by application at the time that the ~prout3are forming as a sub~titute for manual removal of the apical
: 15 tip of the plant. For this purpose, propyl 3-t-butyIphenoxy-
' ` :
acetate may suitable be applied in ~prays and similar
; formulation~ containin~ from 4000 to 6000 ppm o~ that
compound.
~i) suppr~sses unde~irable lateral growth, e.g. ~ide-shoots
`of to~ato pIants. For thi~ purpose, propyl 3-t-butyl-
phenoxyacetate may suitably be applied in ~pxay~ and ~imil~r
fonmulations containing 3000 ppm of that compound.
~(j) incxea~es the yield of monocotyledonou~ crops (e.g. wheat,
barley and rice) by increa3ing the numbex of tillers and/or
reducing ~he num~er of blind headq. Fox the~e purpo3e~,pxopyl
;
~ :3-t-butylpheno~yacetate may suitably be applied in sprays and
:
- S_
:: , , ., i
, ,. . : : .
: :: : .. ~ :.: : . : ~ ~ :

736
similar formulations containing from 200 to 2000 ppm of
that compound.
The valuable plant-growth regulatory properties
of propyl 3-t-butylpheIloxyacetate whe:rl applied to growing
plant tissue have, for example, been demonstrated in the
following representative experiments:-
A spray fluid containing 850 ppm of propyl
3-t-butylphenoxyacetate, cbtained by the dilution with
water of a liquid composition hereinafter described in
Example 5, was sprayed to 'run-off' on fruit trees 70 r
centimetres in height in early Summer. The effect on the
lateral branching of the trees in comparison with untreated
control tree~ was assessed in early Spring next year and the
results obtained, which are e~pressed as the mean of seven
trees per treatment, are given in the following Table I.
TA~LE I
_ _
Number of lateral branches at
Tree Variety lea~t 5 cm in length .
~ _, _
Untreated control Treated
_ ~__ ~ __ _
Pear Comice 1.1 3.7
,............... _ _ _ _ _ ,_
. ~pple Bramley 1.3 6.2
. _ __ . ___
~ Apple Red Miller. 2~8 6.7
. .. ~. ~__ _~ ~
Apple Spartan 1.0 3.3
__ ~ ~ ~
This experiment demonstr~tes the increase in the
-- 6 -- ~
,

:
~g736
number of lateral branches produced by the application of
propyl 3-t-butylphenoxyace~ate to apple and pear trees.
E~periment 2
A spray fluid containin~ 90() ppm of propyl 3-t-
butylphenoxyacetate, obtained ~y the dilution with water of
a liquid composition hereinafter de~cxibed in Example 5, was
sprayed to 'run-off' on nur~ery apple trees (variet.y
~; Bramley) in eaxly Summer and the treatment wa~ repeated
: in early Summer two years later. The mean number of blossom
cluqters per tree was assesqed in the Spring of t~e year
following the second treatment in comparison with trees
which had received conventional pruning by hand. The
results obtained are given in the following Table II.
TABL~
Mean number of blossom cluster~
. per ~ e 3 ~S ~e 9 9m 9nt
Spur and ~xillary
terminal clusters clusters
Hand pruned 6.14 2.42
.. , ~ -- ----
: 20 Treated 32.43 7.29
. ~ ~ ~ ~ _
This experiment demonstrate~ the increase in the
number of lateral branches a~d the improvement in the ~hape
of the trees as represented by the increase in the number
: of blossom clusters produced by the application of propyl
3-t-butylphenoxyacetate to two and three year-old apple
- 7 -
,
- ..,. ..: :.,. .;... . .. , , - ,
.. . ~. :. . :

36
trees in comparison with untreated control trees which
had received conventional hand pruniny.
E~periment 3
A liquid composition as described hereinafter
in Example 5 was diluted with water and applied at rate~
of 0.56 kg, 1.12 kg and 2.24 kg of pxopyl 3-t-butylpheno~y-
acetate per hectare to a crop of cotton two or four
weeX~ after full bloom. The increa~e in the yield of cotton
: per hectare in compari~on with untreated controls wa~
asses~ed at harvest and the reBUltS obtained are given in
the following Table III.
~' .
,
:.
.. ..
':

9~3~i
,~ .
:
~LE I II
_~ _~_
T~me of treatment (weeks after full bloom)
, ,_ ,..., ....
Treatment2 w~eek~ 4 week~
.Yield of s::ottor~ Yield of cotton
(kg/ha ) l ~kg/ha )
" ~-- - ~ ~
O. 56 kg te~t :
. compound per 999 1086 r
hectare
.~ ._ _
1.12 kg test .. .
compound per 1156 1064
hectare
~ . , ~ ~r - ~ . .
2.24 kg te~t .
~mpound per ~ 958 1014 .
hc~tar- ~ ~
15 ~ ~Untreated :~ 804 804
~ control
":~ : __
This experiment de~onstrate~ the increa~e in the
yield o cotton obtained by ~reatment with propyl 3-t-
butylp~enoxyacetate~
According to a feature of the present invention/
the compound of fonmula I i~ prepared by the reaction of a
compound of ~h~ g~neral fonmula:-
:
OCH2COX ' II
~ : ..
(~H ) C/
~: : :
_ 9 ,.
- , : : : : : . : . .: : .: .::,. .:. - : . . - :: :
". : : ~ !i ~', ." ' , : . : ~ '

736
(wherein X represents the hydroxy group, a halo~en atom,
preferably the chlorine atom, or an alkoxy group
containing 1 to 6 carbon ato~s other than the propox~
group) with propanol.
S The reaction of the compound of formula II wherein
X represents the hydroxy group with propanol may be ~fected
in the pre~ence of an acidic catalyst. e.g. hydrogen
chloride gas, ~ulphuric acid or ~ toluene~ulphonic acid,
: optionally in the presence of an inert organic ~olvent, e.g.toluene, or an exce~ of propanol may serve a3 ~he olvent,
under sub~tantially anhydrou~ conditions, at elevated
temperature, e.g. of between 80 and 120C, and ~referably
at the reflux temperature of the reaction ~ixture.
~he reaction of a compound of fonmula ~I wherein
X repre~ent~ a halogen at~m wi~h propanol may be ef~ected,
optionally in the presence of an acid bindin~ a~nt, e.g.
triethylamine or pyridine, optionally in the preuence of an
inert organic ~olvent, e~g. carbon tetrachloride, chloroform
: or toluene, at ambient or elevated temperature, e.g. betweenroom temperature and 120C, and preferably at the reflux
temperature of the reaction mixture.
~he tran~esterification reaction of a compound
of formula II wherein X represents an alkoxy group other
than the pr~poxy group with propanol may be effected in the
: pre6ence of an acidic ca~alyst, e.g. hydrogen chloride gas,
sulphuric aFid or p-toluenesulp~onic acid, optionally in
-- 10 --
- .
.
. . .
:: .
~. ,
.:; , .

~99~36
the presence of an inert organic solvent, or an excess
o~ propanol may serve as the solvent, under substantially
~ anhydrous conditions, at elevated te~mperature, e.g.
: between 60C and 120C, and preferably at the reflux
emperature of the reaction mixture.
According to a further fea~llre o~ the present
invention, the compound of fonmula I is prepared by the
re~ction o~ a compou~d of the general formula:-
: ~ OM III
(CH3)3c
:~ :
~wherein M represents an alkali metal atom, e.g. ~odium or
potas~ium) with a compound of the general formula:-
Y(~H2COOR :V
(wherein Y represents a halogen atom, e.gO the chlorine
atom, and R represents an alkyl group containing from 1 to 6
carbon atoms), followed by, when the reac~ant of general
fonmula IV is other than a compound wherein R is the propyl
group, the transesterifi.cation reaction hereinbefore
described~
The reaction between the compounds of general
formulae III and IV may be effected in the presence of an
anhydrous inert organic ~olvent, e.g. dimethylformamide or
propanol, at a temperature between 0C and 100C. ,
The compound of formula II wherein X represents

:
9~73~ ;
the hydroxy group may be prepared by the applicatio~ ~r
adaptation of known methods for the preparation of
phenoxyacetic acids.
The compounds of fo~rll1la ~I wherein X xepresents
a halogen atom may be prepared ~y the application or
adaptation of known methods for the pxeparation of acid
halides from carboxylic acids from the compound of formula
II wherein X represents the hydroxy group.
The compound~ of formula I~ wherein X represents
a halogen atom may be optionaily used unpurified.
The compounds of formula II wherein X represents
an a1koxy group other than the propoxy group may be prepared
by the application or adaptation of known methods for the
preparation~of carboxylic acid esters, for example the
methods hereinbe~ore described for the preparation o~ the
compound of formula I.
The compounds of formula I~I may be prepared from
; 3-t-butylphenol (a known compound) by the application or
adaptation of known methods for the preparation of alkali
metal salts from phenols.
The compounds of ~ormula IV may be prepared by ~he
application or adaptation of known methods for the preparation
of monohaloacetic acid esters.
By -the tenm;"known methods" as used in the pre~ent
~pecification ls meant methods heretofore used or ~escribed
in the chemical literature.
- 12 -

9~736
.
According to a further feature of the present
: invention, there is provided a method for regulating the growth
of plants, for ex~mple as hereinbeforle de~cribed, which
CQmprises the a~plication to actively growing or dormant
tissues of the plant of an ef~ective amount of the compound
of formula I~ For this purpose, it may be used alone or in
the fonm of plant-growth regulatory compositions (i.e. in
association with one:or ~ore compatible diluents or carriers
,
: ~uitable for use in such compositions), for example a~ herein~
after described. SuitabIe means of app~ication include:-
~: to one year-old nursery stock fruit trees by clirected
sprays, including ultra-low volume sprays, and foam~, and
to growing plants as foliar/stem sprays.
Especially important ~ethods include:-
a method for encouraging the feathering of one year
old nursery fruit trees, particularly apples and pear~,
: ~by the application of the compound of formula I, pr ferably
:: ~ in the form of a compositlon, for example a spray. containing
between 0.075% l750 ppm) and~0015% (1500 ppm) by weight of
th~ compound of formula I, to the top 20 cm to 50 cm of the
growing tip, to "run-off" in the case of sprays other than
tho~e of ultra-low volume, e.g. of 50 litres~of spray fluid
or less per hectare:
a method for producing secondary lateral branches in
:two and three year-old fruit trees after replanting in the
orchard by the applica~ion of the compound ~f fonmula I,~
- 13 -
~ ,:
:
, ' '~
.. .. . . ... , .. . .

` `` 1~95~36
preferably in the form of a composition, for example a
spray, containing between 0.125% (1250 ppm) and 0.15%
(150 ppm) by waight of the compound of formula I, to
'run-off' in the case of sprays.
Liquid compositions for use as plant growth
regulators containing as active ingredient the compound
of formula I, in association with one or more diluents
or adjuvants compatible with the compound of formula I
and suitable for use in such compositions, may take the
form of solutions, suspensions and emulsions, and preferably
incorporate wetting, dispersing or emulsifying agents.
rrhese emulsions, suspensions and solutions may be prepared
using aqueous, organic or aqueous-organic diluents, for
example acetophenone, cyclohexanone, isophorones toluene,
xylene, dimethylformamide and mineral, animal or vegetable
oils (and mixtures o~ these diluents), which may contain
wetting, dispersing or emulsifying agents of the ionic or
non-ionic types or mixtures thereof, for example those of
the types described hereafter. When desired, the emulsions
or solutions containing the compound of formula I may be
used in the form of self-emulsifying or self-solubilising
concentrates containing the active substance dissolved in
the emulsifying or wetting agents or in solvents containing
- 14 _
~' '

`
~9~73~ :
emulsifying or wetting agents compatible with the active
substance. the simple addition of water to such concentrates
producing compositions ready for use.
The wetting, dispersing and emulsifying agents
which may be present may be of the ionic or non-ionic
types, for example sulphoricinoleates, quaternary ammonium
derivatives or products based upon condensates of ethylene `
oxide with nonyl- and/or octyl-phenol, or carboxylic acid
esters of anhydrosorbitols which have been rendered
`
soluble by etherification of the free hydroxy yroups by
condensation with ethyLene oxide, or mixtures of these
types of agents~
Compositions suitable for the production of foams
containing the compound of formula I are also applicable~
~he~cornpositions may also contain auxiliary
compounds, the said compositions may contain mixtures of t~e
auxiliary compounds and compounds of formula I as comblned
. formulations or tank mixes. Examples of such auxiliary .
~compounds include insecticides such as organic phosphorus
esters, e.g. parathion, i.e. 0,0-diethyl 0-4-nitrophenyl
phosphorothionate, maIathion, i.e. S- E 1 i 2-di(ethoxy-
: carbonyl)ethyl~ 0,0-dimethyl phosphorothiolothionate,
: v~amidothion, i.e. 0,0-dimethyl 5-[2-(1-methylcarbamoyl-
ethylthio)ethyl~phosphorothiolate, diazinon, i.e. 0,0-diethyl
0-~2-isopropyl-6-methylpyrimidin-4-yl~phosphorothionate,
monocrotophos, i.e. 0,0-dimethyl cis-1-methyl-2-(N-
'~

methylcarbc~moyl)~inyl phosphate, dimethoate, i.e.
O,O-dime-thyl S~ methylcarbamoylmethyl)phosphorothiolo-
thionate, phosalone, i.e. S-(6-chLorc)-2-oxobenzoxazolin-3
yl)methyl O,O-diethyl phosphorothiolothionatP, bromopho~-
ethyl, i.e. 0-(4-bromo-2,5-dichlorophenyl) O,O-diethyl
phosphorothionate, carbamates, e.g. carbaryl, i.e.
l-naphthyl N-methylcarbamate, ~ormetanate, i.e. 3-
dimethylaminomethyleneimino-phenyl ~-methylcarbamat~,
pyrethrins (natural and synthetic), e.g. bioallethrin,
chlorinated hydrocarbons, e.g. D~T, i.e. l,l,l-tr.ichloro-
2,2-bis(~-chlorophenyl)ethane, as well as its mixtures with
its o, ~'-isomer, BHC, i.e. mixed isomers of 1,2,3,4,5,6-
hexachlorocyclohexane, toxaphene, i~e. camphechlor (an
isomeric mixt~re of chlorinated c~mphene3 containing 67-69%
chlorine), dichlorobenzene, acaricides, e.g. quinom~hiona~e~
i.e. 6-methyl-2,3-quinoxalinediyl cyclic S,S-dithiocarbonate,
dicofol, i.e. 2,2,2-trichloro~ bis(~chlorophenyl)ethanol,
and tetradifon, i.e. 2,4,4',5-tetrachlorodiphenyl sulphone,
n~n-inse~tic~dài ~p~unds, such as the synergi~tic
methylenedioxyphenol derivative~, e . g . piperonyl butoxide,
i.e. 5-[2-~2-butoxyethoxy~ethoxymethyl]-6-propyl-1,3-
benz~di~xole, se~amex, i.e. 2-(3,4-methylenedioxyphenoxy~-
3,6,9-~rioxaundecane, 0,O-dImethyl O-phenyl phosphorothioate;
~ngi~idal compounds, e.g. copper sulphate, dinocap, i~e. a
~i~ture o ~,6-dinitro-4-octylphenylcrotonates and,2,4-
dinitr~-6-octylphenylcrotonate~ ("octyl" signifying the
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1~39~736
isomerlc radicals l-methylheptyl, l-ethylhexyl and
l-propylpentyl), chloroxylenol, i.e. 4-chloro-3,5-
xylenol, thiophanatemethyl, i.e. 1,2-bis(3-methoxycarbonyl-
2-thioureido)benzene, dichlorophen, i.e. bis(5-chloro-2-
hydroxyphenyl)methane, and thiram, i.eO tetramethylthiuramdisulphide, preparations of Bacillus thurin~ieniss (toxins
and organisms), and insect viruses.
Many such auxiliary compounds are well known in
the art; the only requirement is that they should be
compatible with the compound of formula I and with other
components of the compositions.
The compositions generally contain between
0.05% and 90% w/v of the compound of formula I, and are
applied at such a rate as to g1ve the desired effect, as
judged by the farmer or other person skilled in the art
according to the plant to be treated.
The following Examples 1 to 4 illustrate the
preparation of the compound of the present invention.
EXAMPLE 1
3-t-Butylphenoxyacetic acid (10.4 g) was heated
at reflux in propanol (80 ml) for 2 hours, passing through
it a stream of hydrogen chloride gas. The excess o~
; propanol was removed by distillation and -the residue was
dissolved in diethyl ether (75 ml). The ethereal solution
was washed successively with saturated aqueous sodium
bicarbonate solution and water, dried over sodium sulphate,
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: :- . , . : . . : .

36
filtered and evaporated to drynes~. I'he oily residue was
di~tilled to give propyl 3-t-butylpheno~yacetate (8.S 9),
b.p. 179-180C/18 ~m Hg, as a colourle~s oil.
EX~MPLE 2
3-t-Butylphenoxyacetic acid ~920 g) was heated
at reflux for 2 hours with thionyl chloride (920 ml). The
excess of thionyl chloride was rem~ved by evaporatiQn.
Final traces of thionyl chloride were removed by evaporation
in the presence of toluene (~ x 500 ml~. ~he cxude 3-t-
butylphenoxyacetyl chloride was added ~lowly to refluxing
propanol (6.5 litre3 and, after addition, the solution wa~
heated at reflux for 2 hours. The *xces~ of propanol
wa~ removed by distillation i~ vacuo. The residue was
distilled to give propyl 3-t-but~l:phenoxyacetate (1068 g),
b.p. 170C/12 mm Hg, which was obtained a~ an almo~t
colourless oilO
Propyl chloroacetate (12.1 g) in dry dimethyl-
formamide (10 ml~ was added ~o a stirred solution of ~odium
3-t-butylphenoxide Cprepared from 3-t-butylphenol (10 g~
and ~oaium hydride (1.64 g)~ in dry dimethylformamide (50
ml) at 10~15C. The mixture wa~ ~tirred at room tempexature
for 2 hours and evaporated to dryness. The residue was
di~solved in a mixture of chloro~orm tlOO ml) and water
(1~0 ml~. The organic layer wa~ separated, dried ~ver
ma~nesium ~ulphate, filtered, evapora~ed and distilled to
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. .

73~;
give propyl 3-t-butylphenoxyacetate ~10.3 g), b.p.
176-178C/20 mm Hg, as a colourless oil.
EXAMæLE 4
Methyl 3-t-butylphenoxyacetate (27.9 g, b.p.
161-162C/20 mm Hg, prepared by proceeding in a manner
similar to that hereinbefore described in Example 2
but replacing the propanol by methanol) was dissolved in
propanol (45 ml). The solution was heated at reflux for
1.5 hours while a stream of hydrogen chloride gas was
passed through it. The excess of propanol was removed
by evaporation and the residue was dissolved in diethyl ether
(75 ml). The ethereal solution was washed successively with
saturated aqueous sodium bicarbonate solution and water,
dried over sodium sulphate, filtered and evaporated to
dryness. The oily residue was distilled to give propyl
3-t-butylphenoxyacetate (23 g), b.p. 173-175C/15 mm Hg,
as a colourless oil.
The following Examples illustrate suitable
compositions including the compound of formula I~
EXAMPLE 5
. n . ___
A liq~lid composition in the form of a concentrate
was prepared by mixing together:-
propyI 3-t-butylphenoxyacetate 90% w/v
: Duoteric MBl : 5% w/v
Duotexic MB2 5% w/v
-- 19 --
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' ' '

~9973~j
EXA~PLE 5
.
A liquid composition in the form of a concantrate
was prepared by mixing together:-
propyl 3~t-butylphenoxyacetate6C% w/v
S Arquad 2C-75 5~ w/v
E~ho~at 142~20 S% w/~
Aromasol ~ to 10~% by vol~me.
ExAMæLE 7
__ .
A liquid compo~ition in the ~onm of a concentrate
wa3 prepared by ~ixing together:-
propyl 3-t-butylphenoxyacetate20% w/v
Duotexi~ MBl 5% w/v
Duoteric MB2. 5% w/v
cyclohexanone - 3 volume~)
. ~ to 100% by volume.
~ylene ~ 1 volume )
Compositions of the type illu~trated b~ Bxamp1es
5-7 way be diluted with water ~o fonm e~ulsion~ containing
from 0.05% ~o 8.~h w/v of propyl 3-t-butylpheno~yacetate
~1-4 kg in from 50-2000 l) for spray appli~ation. For
exampleo-
(a) the liqui~ c~mpoAition o~ ~xample 5 may be ~iluted
with ~ater at a rate of 1 ml of compositio~ to 1
litre of water and ~prayed ~o 'run-off' on the top
20-30 cms of ~he growing ~ip~ of one year-old
nur~qery ~ruit ~xee~, e.~. apple~ and pear~. This
txeakment induce~ vigorous lateral branchlng with a
,
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. : ~ . .
.. .. . .

3~
desirable wide crotch angle between the lateral
branches and-the s~em o-f the txee.
(b) the liquid composi~ion of Example 6 may be diluted
with waker to a concentration of 10000 ppm (~000
ppm of propyl 3-~b~tylphenoxyacetate) and sprayed
on Brussels sprout plants when the first 5 or 6
basal sprouts are 1 cm in diameter~ This treatment
serves a~q a substitute for manual r~moval of the
apical tip of the plank and increa~es the yield and
reduces the wastage of the Brussels spro~lts crop.
(c~ the liquid concentrate of Exam~le 7 may be diluted
with water to a concentration o~ 1250 ppm ~250 ppm
of propyl 3-t-butylphenoxyacetate) and sprayed on
apple trees at the young fruitlet growth ~tage.
This treatmen~ reduce~ the number of fruit, which
increases the size and quality of the final crop
of fruit.
EX~MPLE 8
Propyl 3-t-butylphenoxyacetate may be applied
undiluted at a rate of 1~2 kg/ha using appropriate ultra-low
volume ~pray equip~ent. To improve spray cover, 1-5 lfha
of a non-phytotoxic spray oil may be mixed with propyl 3-t- ;
butylphenoxyacetate before application.
Propyl 3-t-butylphenoxyacetate may be applied at a
rate of 1 kg/ha to a orop of cotton two weeks afte~ full
bloom to increase the yield of cotton.
.
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~9973~;
EXA~MPL~9
A liquid composition in the form o a concentrate
wa~ prepared by mixing together:~
propyl 3~t butylphenoxyacetate lO~o W/V
S Ethylan KE0 19% wfv
Dimethylform~nide to 100% by voll~me~
This ~ompo~ition may be di~llted with water to
give a clear solution containing frQm 0.05% (500 pE)m) to
4.0% (40000 ppm~ w~v of propyl 3-t-butylphenoxyacetate
for spray applicatlon.
: A spray fluid thus obtained containing 40000 ~pm
of composition (4000 ppm o~ propyl 3-t-butylphenoxyacetate)
may be sprayed on sunflower plants about 40 days after
sowing. This treatment increases the yield of s~ed and mean
seed weight~ . ,,
E~AWPLE 10
Composition~ of th~ type illustrated by Exam~le~
5, 6, 7 and 9 may be added to an aqueou~ solution containing
1% Perla~krol ESD-60 to give a con~entration of 0.05~0 to
1.0% w/v of propyl 3-t-butylphenoxyacetate for application
as a foam using special foam producing hydraulic nozzles.
Te~ms used in the present specification have the
following meanings:-
Ethylan REo ~solubili~ing agen~) i5 a nonyl ph~nol ethylene
oxide condensat~ ~10 moles ethylene oxide);
Duoteri~s MBl and MB2 (emulsifying agents) are anionic~non-
- Z2 -
:: . ~.. . ., ~: .
: . .
: , ~. ~ :

9~3~;
ionic blended emulsifiers containin~ calcium a.Lkyl aryl
sulphonates and alkyl phenol ethylene oxide condensates;
Perlankrol ESD-60 ~foaming agent) is t:he ~odium salt of a
~ynthetic primary alcohol ether sulphate:
~thofat 14~/20 (emulsifying agent) is a fatty acid~ethylene
oxide condensate;
Arquad 2C-75 (emulsifying agent) is di-coco di~ethyl a~monium
chloride ("coco" signifie~ alkyl groups derived from
coconut oil):
Aromasol H is a hydrocarbon oil containing 95% v/Y aromatic
fraction tb.P. 168-200C).
23
: :.-., : :
- ;
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