This invention relates to derivatives of acrylic acid useful as fungicides, to processes for preparing them, to fungicidal compositions containing them, and to methods of combating fungi, especially fungal infections in plants, using them.

EXAMPLE 1 
This Example illustrates the preparation of 2E, 1"Z-methyl 
3-methoxy-2-[2'-(2"-phenylethenyl)phenyl]propenoate (compound Number 13 of 
Table I). 
Potassium tert-butoxide (5.30 g) was added in a single portion to a 
vigorously-stirred suspension of benzyltriphenylphosphonium chloride 
(21.02 g) in dry ether (250 ml). After 25 mins, the resulting orange 
mixture was treated with a solution of 2-bromobenzaldehyde (5.00 g) in dry 
ether (50 ml), and the mixture lightened in colour. After a further hour, 
the mixture was poured into water and extracted with ether. The extracts 
were washed with water, dried, concentrated under reduced pressure, and 
chromatographed using dichloromethane as eluent to give 
1-phenyl-2-(2-bromophenyl)ethylene (5.95 g, 85% yield), an almost 
colourless oil, as a 6:1 mixture of Z:E-isomers (by GC/MS). 
A solution of the Grignard agent prepared from part of the mixture of 
isomers of 1-phenyl-2-(2-bromophenyl)ethylene described above (5.58 g) and 
magnesium (0.63 g) in dry THF (20 ml) was added dropwise over 30 mins. to 
a stirred solution of dimethyl oxalate (5.06 g) in dry THF (40 ml) cooled 
to -15.degree. C. The resulting mixture was stirred at about -15.degree. 
C. for 30 minutes, then at room temperature for 1 hour, then poured into 
dilute hydrochlorice acid and extracted with ether. The extracts were 
washed with water, dried, concentrated under reduced pressure, then 
chromatographed twice [(i) 30% ether in petrol; (ii) 20% hexane in 
dichloromethane] to give isomerically pure Z-methyl 
2-(2'-phenylethenyl)phenylglyoxalate (1.76 g, 31% yield) as a yellow oil, 
.sup.1 H nmr (CDCl.sub.3): delta 3.87 (3H, s), 6.78 centre of 2 doublets, 
each 1 H, J 12 Hz) p.p.m. 
Potassium tert-butoxide (2.00 g) was added in a single portion to a stirred 
suspension of (methoxymethyl)-triphenylphosphonium chloride (6.78 g) in 
dry ether (80 ml). After 25 minutes, the resulting red suspension was 
treated with a solution of Z-methyl 2-(2'-phenylethenyl)-phenylglyoxalate 
1.76 g) in dry ether (20 ml), the colour lightening. After 1.5 hours, the 
reaction mixture was poured into water and extracted with ether. The 
extracts were washed with water, dried, flushed through a short column of 
silica gel with dichloromethane, then carefully chromatographed using 30% 
ether in petrol as eluant to give the title compound (0.46 g, 24% yield) 
as an oil, infrared (film): 1715, 1635 cm.sup.-1 ; .sup.1 H nmr 
(CDCl.sub.3): delta 3.62 (3 H, s), 3.73 (3 H, s), 6.48 (2 H, s), 7.50 (1 
H, s) ppm. 
EXAMPLE 2 
This Example illustrates the preparation of E- and Z-methyl 
3-methoxy-2-phenylpropenote (compounds numbers 1 and 2 of Table I). 
Potassium tert-butoxide (9.52 g) was added in a single portion to a stirred 
suspension of (methoxymethyl)-triphenylphosphonium chloride (34.3 g) in 
dry ether (300 ml). After 45 minutes, the resulting red suspension was 
treated with a solution of methyl benzoylformate (8.20 g) in dry ether 
(100 ml) (colour lightens; exotherm). After 3 hours, the mixture was 
diluted with water, treated with magnesium sulphate and charcoal, then 
concentrated under reduced pressure to give the crude produce (36.39 g) as 
a yellow oil which partially crystallised on standing. This was flushed 
through silica gel using dichloromethane, then carefully chromatographed 
using dichloromethane: petrol (2:1) to give E-methyl 
3-methoxy-2-phenylpropenoate (4.83 g, 50% yield) as a pale yellow oil, 
eluted first, infrared (film): 1710, 1630 cm.sup.-1, .sup.1 H nmr 
(CDCl.sub.3): delta 7.55 (s, olefinic proton), and Z-methyl 
3-methoxy-2-phenylpropenoate (3.43 g, 36% yield) as a pale yellow oil, 
eluted second, infrared (film): 1715, 1630 cm.sup.-1, .sup.1 H nmr 
(CDCl.sub.3): delta 3.76 (3H,s), 3.90 (3H,s), 6.65 (1H, s), 7.28 (5H,s) 
ppm. 
A sample of E-methyl 3-methoxy-2-phenylpropenoate prepared from methyl 
phenylacetate by the method described in Examples 4 and 7, that is by 
reaction with sodium hydride and methyl formate and treatment of the 
resulting enol with potassium carbonate and dimethyl sulphate, solidified 
on standing and had a melting point of 37.degree.-38.degree. C. 
EXAMPLE 3 
This Example illustrates the preparation of 2E, 1"E- and 2Z, 1"-methyl 
3-methoxy-2-[2'-(2"-phenylethenyl)-phenyl]propenoate (compounds numbers 9 
and 10 of Table I). 
A solution of 2-bromobenzaldehyde (18.50 g) in dry ether (20 ml) was added 
dropwise to a stirred solution of benzylmagnesium chloride [prepared from 
benzyl chloride (12.64 g) and magnesium (2.68 g)] in dry ether (120 ml), a 
thick precipitate forming during the addition. The mixture was stirred for 
1 hour at room temperature then poured into water, acidified with 2M 
hydrochloric acid, and extracted with ether. The extracts were washed with 
water, dried, concentrated and chromatographed using dichloromethane and 
petrol (1:1) as eluant to give 1-(2-bromophenyl)-2-phenylethan-1-ol (10.95 
g, 40%) as a white solid, melting point 84.degree.-85.degree. C. 
A stirring mixture of 1-(2-bromophenyl)-2-phenyl-ethan-1-ol (15.50 g) and 
orthophosphoric acid (150 ml) was heated at 170.degree. C. for 1 hour and 
then poured into iced water and extracted with ether. The extracts were 
washed with water, dried and concentrated to give the crude product as an 
orange oil (14.29 g). Evaporative distillation (0.3 torr; oven temperature 
140.degree. C.) gave E-1-phenyl-2(2bromophenyl)ethylene (12.53 g), 86% 
yield) as a pale yellow oil with a purity of 97% by GC. 
A solution of the Grignard reagent prepared from 
E-1-phenyl-2-(2-bromophenyl)ethylene (8.56 g) and magnesium (0.96 g) in 
dry tetrahydrofuran (20 ml) was added dropwise over 30 minutes to a 
stirred solution of dimethyl oxalate (7.76 g) in dry tetrahydrofuran (70 
ml) cooled to -15.degree. C. The resulting mixture was stirred at about 
-15.degree. C. for 30 minutes, then at room temperature for 1 hour, then 
poured into dilute hydrochloric acid and extracted with ether. The 
extracts were washed with water, dried and concentrated to give the crude 
product as a yellow oil (17.22 g). Purification by column chromatography 
using dichloromethane and petrol (1:1) as eluant then evaporative 
distillation (0.07 torr, oven temperature 170.degree. C.) gave E-methyl 
2-(2'-phenylethyl)phenylglyoxalate (2.01 g, 23% yield) as a yellow oil, 
pure by GC, .sup.1 H nmr (CDCl.sub.3): delta 3.78 (3 H, s), 6.88 (centre 
of 2 doublets, each 1 H, J 16 Hz) p.p.m. 
Potassium tert-butoxide (2.19 g) was added in a single portion to a stirred 
suspension of (methoxymethyl)triphenylphosphonium chloride (7.41 g) in dry 
ether (100 ml). After 25 minutes, the resulting red suspension was treated 
with a solution of E-methyl 2-(2'-phenylethenyl)phenylglyoxalate (1.92 g) 
in dry ether (20 ml), the colour lightening. After 15 minutes, the mixture 
was poured into water and extracted with ether. The extracts were washed 
with water, dried and chromatographed using 30% ether in petrol as eluant 
to give (i) the 2E,1"E-isomer of the title compound, eluted first, as a 
pale yellow oil (1.06 g, 50% yield) which crystallised on standing to give 
a white solid, melting point 103.degree.-104.degree. C. An analytical 
sample, recrystallised from an ether-petrol mixture, had melting point 
107.degree.-108.degree. C., infrared (nujol mull): 1700, 1630 cm.sup.-1 ; 
.sup.1 H nmr (CDCl.sub.3): delta 3.68 (3 H, s), 3.80 (3H, s), 7.06 (2H, 
s), 7.63 (1 H, s) p.p.m.; and (ii) the 2Z,1"E-isomer of the title 
compound, eluted second, as a viscous oil (0.260 g, 12% yield), infrared 
(film): 1710, 1625 cm.sup.-1 ; .sup.1 H nmr (CDCl.sub.3): delta 3.65 (3H, 
s), 3.92 (3H,s), 6.57 (1H, s), 6.99 and 7.24 (each 1H, d J 16 Hz) ppm. 
EXAMPLE 4 
This Example illustrates the preparation of E-methyl 
2-(2-chloro-6-fluorophenyl)-3-methoxypropenoate (compound No. 27 of Table 
I). 
A mixture of methyl (2-chloro-6-fluorophenyl)acetate (5.20 g) and methyl 
formate (31.4 ml) in dry DMF (40 ml) was added dropwise to a stirred 
suspension of sodium hydride (1.23 g) in dry DMF (40 ml) at a temperature 
between 0.degree. and 5.degree. C. Vigorous evolution of gas was observed. 
The reaction mixture was stirred at room temperature for 3.5 hours, then 
poured into a mixture of ice and aqueous sodium carbonate, and washed with 
ether. The resulting aqueous mixture was acidified with concentrated 
hydrochloric acid and extracted with ether. The extracts were washed with 
water, dried and concentrated to give methyl 
2-(2-chloro-6-fluorophenyl)-3-hydroxypropenoate (3.44 g) as a white solid. 
A stirred solution of this crude product in dry DMF (30 ml) was treated 
successively with potassium carbonate (4.11 g) and dimethyl sulphate (1.34 
ml). The resulting mixture was stirred at room temperature for 1 hour, and 
was then poured into water and extracted with ether. The extracts were 
washed with water, dried and concentrated to give the title compound (2.91 
g) as a white solid, melting point 77.degree.-78.degree.. Crystallisation 
from 60.degree.-80.degree. petrol gave colourless crystals [2.61 g, 42% 
yield from methyl (2-chloro-6-fluorophenyl)acetate], melting point 
79.degree.-80.degree., .sup.1 NMR (CDCl.sub.3) delta 3.69 (3H, s), 3.84 
(3H,s), 7.62 (1H,s) ppm. 
EXAMPLE 5 
This Example illustrates the preparation of E-methyl 
2-(2-phenoxy)phenyl-3-methoxyacrylate (compound number 1 of Table II). 
Potassium tert-butoxide (5.6 g) was added to a stirred solution of diphenyl 
ether (12.3 g) in dry ether (150 ml) at -70.degree. C. The resulting 
mixture was stirred at this temperature for 15 minutes, then 
n-butyl-lithium (30.5 ml of 1.62M solution in hexane) was added to give a 
red-brown suspension which was allowed to warm to room temperature. This 
mixture was added to a stirred suspension of dimethyl oxalate (11.8 g) in 
ether (250 ml) at -10.degree. over 20 minutes, then allowed to warm to 
room temperature. After 30 minutes, the mixture was poured into water and 
extracted with ether. The combined extracts were washed with water, dried, 
then concentrated to give a red oil (14.21 g). Chromatography using 20% 
ether in petrol as eluant gave methyl 2-phenoxybenzoylformate (2.23 g) as 
a yellow oil. 
Potassium tert-butoxide (2.64 g) was added to a vigouously stirred 
suspension of (methoxymethyl)triphenylphosphonium chloride (8.93 g) in dry 
ether (100 ml). After 20 minutes, the resulting red suspension was treated 
with a solution of methyl 2-phenoxybenzoylformate (2.23 g) in dry ether 
(20 ml), the colour lightening. After 15 minutes, the mixture was poured 
into water and extracted with ether. The combined extracts were washed 
with water, dried and concentrated to give a yellow oil (7.30 g). 
Chromatography using dichloromethane as eluant gave the title compound 
(0.61 g) as a colourless oil, infrared (film) 1 710, 1 635 cm.sup.-1, 
.sup.1 H nmr (CDCl.sub.3) delta 3.60 (3H, s), 3.75 (3H, s), 7.47 (1H, s) 
ppm. 
EXAMPLE 6 
This Example describes an alternative method for the preparation of 
E-methyl 2-(2-phenoxy)phenyl-3-methoxypropenoate (compound number 1 of 
Table II). 
A 1 M solution of borane-tetrahydrofuran complex (30 ml) was added dropwise 
to a stirred solution of 2-phenoxybenzoic acid (5.35 g) in dry THF (50 
ml), cooled to 0.degree. C. (effervescence). Following the addition, the 
mixture was stirred at 0.degree. C. for 15 minutes, then at room 
temperature for 1.5 hours. It was poured into water and extracted with 
ether. The extracts were washed successively with water, aqueous sodium 
bicarbonate, aqueous sodium carbonate, then dried and concentrated under 
reduced pressure to give 2-phenoxybenzyl alcohol (4.83 g, 97%) as a 
colourless oil. 
Thionyl chloride (1.92 ml) was added in one portion to a solution of 
2-phenoxybenzyl alcohol (4.80 g) in dry dichloromethane (50 ml). The 
resulting mixture was stirred at room temperature for 2 hours, then washed 
with water (.times.2), aqueous sodium bicarbonate (.times.2) and aqueous 
sodium chloride, dried and concentrated under reduced pressure to give 
2-phenoxybenzyl chloride (4.87 g, 93%) as a colourless oil. 
Carbon dioxide was bubbled into a solution of 2-phenoxybenzylmagnesium 
chloride [from 2-phenoxybenzyl chloride (4.80 g) and magnesium turnings 
(0.64 g)] in dry ether (15 ml), cooled to 0.degree. C. Dry THF was added 
to aid solubility. When exothermic reaction had subsided, no further 
carbon dioxide was passed through the mixture and it was allowed to warm 
to room temperature. The mixture was poured into water, washed with ether, 
then treated with hydrochloric acid and extracted with ether. The extracts 
were washed with water, dried and concentrated under reduced pressure to 
give 2-phenoxyphenylacetic acid (3.06 g, 61%) as a solid, melting point 
82.degree.-85.degree. C. An analytical sample, recrystallised from 
ether/petrol, had a melting point of 85.degree.-86.degree. C. 
A solution of 2-phenoxyphenylacetic acid (2.75 g) in dry methanol (30 ml) 
containing concentrated sulphuric acid (0.3 ml) was heated under reflux 
for 2 hours then allowed to cool, poured into water and extracted with 
ether. The extracts were washed with water, dried and concentrated under 
reduced pressure to give methyl 2-phenoxyphenylacetate (2.65 g, 91%) as a 
pale yellow oil. 
This ester was converted in 2 steps into the title compound by the method 
described in Example 4, that is, by reaction with sodium hydride and 
methyl formate and treatment of the resulting enol with potassium 
carbonate and dimethyl sulphate (overall yield=65%). 
EXAMPLE 7 
This Example illustrates the preparation of E-methyl 
2-(2-benzyloxy)phenyl-3-methoxyacrylate (compound number 177 of Table II). 
A mixture of methyl formate (24.4 ml) and methyl o-(benzyloxy)phenylacetate 
(5.10 g) in dry DMF (30 ml) was added dropwise to a stirred suspension of 
sodium hydride (0.95 g) in dry DMF (30 ml) at between 0.degree. and 
5.degree. C. A vigorous evolution of gas was observed. The reaction 
mixture was stirred at room temperature for 3.5 hours, then poured into a 
mixture of ice and aqueous sodium carbonate. The resulting aqueous 
solution was washed with ether (.times.3) then acidified with concentrated 
hydrochloric acid and extracted with ether. The extracts were washed with 
water, dried and concentrated to give methyl 
2-(2-benzyloxy)pheny-3-hydroxyacrylate (4.38 g) as a yellow oil. 
Potassium carbonate (4.26 g) and dimethyl sulphate (1.38 ml) were added 
successively to a stirred solution of methyl 
2-(2-benzyloxy)pheny-3-hydroxyacrylate (4.38 g) in dry DMF (40 ml). After 
an hour at room temperature, the reaction mixture was poured into water 
and extracted with ether. The extracts were washed with water, dried, 
concentrated and triturated with petrol to give the title compound (3.38 
g, 57% yield from methyl o-(benzyloxy)phenylacetate) as a white solid, 
melting point 74.degree.-75.degree. C. Crystallisation of the whole sample 
from methanol gave colourless crystals (2.35 g), melting point 
76.degree.-77.degree., .sup.1 H nmr (CDCl.sub.3) delta 3.63 (3H, s), 3.76 
(3H, s), 5.05 (2H, s), 7.49 (1H,s) ppm. 
EXAMPLE 8 
This Example illustrates the preparation of E-methyl 
2-(4-chlorophenyl)-3-methoxypropenoate (compound number 22 of Table I). 
A solution of methyl 4-chlorophenylacetate (3.51 g) in dry THF (25 ml) was 
added dropwise to a stirred solution of lithium di-isopropylamide [from 
di-isopropylamine (2.88 g) and n-butyl-lithium (16.4 ml of 1.62 M solution 
in n-hexane)] in dry THF (25 ml) at -70.degree. C. After 0.5 hours at the 
same temperature, a solution of trimethylsilyl chloride (5.16 g) in dry 
THF (5 ml) was added and after 10 minutes the solution was allowed to warm 
to room temperature. Volatile components of the resulting mixture were 
removed under reduced pressure, and the ether-soluble fraction of the 
residue was collected by repeated trituration with dry ether, filtering, 
and concentrating the filtrate under reduced pressure. This left the crude 
methyl silyl enol ether (5.18 g) as an orange oil whose infrared spectrum 
showed almost no carbonyl absorption and a peak at 1 640 cm.sup.-1. 
A solution of titanium tetrachloride (3.60 g) in dry dichloromethane (5 ml) 
was added dropwise to a stirred solution of trimethylorthoformate (1.92 g) 
in dry dichloromethane (30 ml) at -70.degree. C. After 15 minutes at the 
same temperature, a solution of the crude methyl silyl enol ether 
described above (5.18 g) in dry dichloromethane (20 ml) was added, still 
at -70.degree. C. After 0.5 hours, aqueous potassium carbonate was added 
to the reaction mixture, still at -70.degree. C., and it was extracted 
with ether. The extracts were washed with water, dried, concentrated under 
reduced pressure, and chromatographed using ether: petrol (1:1) as eluant 
to give methyl 2-(4-chlorophenyl)-3,3-dimethoxypropanoate (2.26 g, 46% 
yield from methyl 4-chlorophenylacetate) as a solid, melting point 
61.degree.-62.degree. C. 
A solution of methyl 2-(4-chlorophenyl)-3,3-dimethoxypropanoate (1.65 g) in 
dry THF (20 ml) was added dropwise at -70.degree. C. to a stirred solution 
of lithium di-isopropylamide [from di-isopropylamine (0.84 g) and 
n-butyl-lithium (4.7 ml of 1.62 M solution in n-hexane)] in dry THF (20 
ml). After 0.5 hours at -70.degree. C., the reaction mixture was poured 
into water and extracted with ether. The extracts were washed with water, 
dried, concentrated under reduced pressure, and chromatographed using 40% 
ether in petrol as eluant to give the title compound (0.31 g, 21%) as a 
pale yellow solid, melting point 61.degree.-62.degree. C., infrared 
(nujol) 1 685, 1 615 cm.sup.-1, .sup.1 H nmr (CDCl.sub.3)delta 3.74 and 
3.88 (each 3H, s), 7.56 (1H,s) ppm. 
EXAMPLE 9 
This Example illustrates the preparation of E-methyl 2-(4-methlphenoxy)] 
phenyl-3-methoxypropenoate (compound number 16 Table II). 
4-Methylphenol (8.40 g) was added to a stirred methanolic solution of 
sodium methoxide [from sodium (1.78 g) and dry methanol (50 ml)]. After 
0.5 hours, the methanol was removed under reduced pressure and the residue 
was mixed with 4-methylphenol (4.20 g), 2-chloroacetophenone (6.00 g), and 
a catalytic quantity of cooper bronze. The resulting mixture was heated at 
135.degree. C. for 1.5 hours, then allowed to cool, diluted with water and 
extracted with ether. The extracts were washed successively with aqueous 
sodium hydroxide and aqueous sodium chloride, then dried and concentrated 
under reduced pressure to give a dark oil (8.20 g). This crude product was 
purified by evaporative distillation (130.degree.-135.degree. C. at 0.02 
torr) to give 2-(4-methylphenoxy)acetophenone (7.29 g, 83%) as a 
colourless liquid, infrared (film) 1 670 cm.sup.-1. 
A solution of boron trifluoride etherate (18.06 g) and 
2-(4-methylphenoxy)acetophenone (7.29 g) in dry methanol (8.3 ml) was 
added to a stirred ice-cooled suspension of lead tetra-acetate (14.97 g) 
in dry ether (70 ml). The resulting mixture was stirred at room 
temperature for 18 hours, then poured into water and extracted with ether. 
The extracts were washed successively with water and aqueous sodium 
bicarbonate, dried and concentrated under reduced pressure to give a red 
oil (7.53 g) containing methyl 2-(4-methylphenoxy)phenylacetate and the 
starting acetophenone (4:1 by GC). The mixture was treated with aqueous 
potassium hydroxide, and the resulting substituted phenylacetic acid was 
purified by acid-base extractions, and re-esterified in acidic methanol to 
give methyl 2-(4-methylphenoxy)phenylacetate (5.00 g) as a thick oil, 
infrared (film) 1 730 cm.sup.-1. 
This ester was converted in 2 steps into the title compound by the method 
described in Examples 4 and 7, that is, by reaction with sodium hydride 
and methyl formate and treatment of the resulting enol with potassium 
carbonate and dimethyl sulphate (overall yield=32%). The product, after 
recrystallisation from methanol, had a melting point of 
80.degree.-81.degree. C., infrared (nujol) 1 690, 1 620 cm.sup.-1, .sup.1 
nmr (CDCl.sub.3) delta 2.30 (3H, s) 3.62 (3H,s), 3.77 (3H,s), 7.50 (1H,s), 
ppm. 
EXAMPLE 10 
This Example describes the preparation of E- and Z-methyl 
3-methoxy-2-(2-phenylethyl)phenylpropenoate (compounds numbers 1 and 177 
of Table IV). 
Trifluoroacetic acid (46 ml) was added in one portion to a stirred mixture 
of 1-(2-bromophenyl)-2-phenylethan-1-ol (16.51 g, prepared as described in 
Example 3) and triethylsilane (13.80 g). The resulting mixture was stirred 
at room temperature for about 22 hours, then the excess trifluoroacetic 
acid was removed under reduced pressure. The residue was dissolved in 
ether and washed successively with water, aqueous sodium bicarbonate 
(.times.3) and water (.times.2), then dried, concentrated under reduced 
pressure, and chromatographed using 10% dichloromethane in petrol as 
eluant to give 1-(2-bromophenyl)-2-phenylethane (8.02 g, 52%) as a 
colourless oil. 
This sample of 1-(2-bromophenyl)-2-phenylethane was converted in 2 steps 
into the title compounds by the method described in Examples 1 and 3, that 
is, by reaction of the magnesium derivatives with dimethyl oxalate, and 
treatment of the resulting ketoester with 
methoxymethylenetriphenylphosphorane. The E-isomer, eluted first in 30% 
ether in petrol, was an oil, infrared (film) 1 705 and 1 630 cm.sup.-1, 
.sup.1 H nmr (CDCl.sub.3) delta 2.79 (4H, s), 3.69 (3H,s), 3.79 (3H,s), 
7.59 (1H,s) ppm. The Z-isomer, eluted second, was also an oil, infrared 
(film) 1 715, 1 695 and 1 630 cm.sup.-1, .sup.1 H nmr (CDCl.sub.3) delta 
2.84 (4H,s), 3.68 (3H,s), 3.84 (3H,s), 6.24 (1H,s) ppm. 
EXAMPLE 11 
This Example illustrates the preparation of 2E, 1"E- and 2Z, 1"E-methyl 
2-[2'-(2"'-furyl]ethenyl)phenyl]-3-methoxypropenoate (compounds numbers 55 
and 56 of Table I). 
A mixture of 2-bromobenzyl bromide (12.10 g) and trimethylphosphite (8.56 
ml) was stirred in a flask fitted via a still head to a condensor. This 
reaction mixture was heated at 110.degree. C. for 1 hour [then further 
trimethylphosphite (5 ml) was added] then at 130.degree. C. for 2.5 hours, 
the temperature at the still head remaining at less then 40.degree. C. 
throughout. The mixture was allowed to cool, and the volatile fraction was 
removed under reduced pressure to leave an almost colourless liquid (21.65 
g). Evaporative distillation of part of this liquid (18.35 g) gave 
dimethyl 2-bromobenzylphosphonate (8.02 g, 55%) as a colourless liquid, 
collected at 175.degree.-180.degree. C. (0.15 mbar), with a purity of 78% 
by GC. An analytical sample, purified by chromatography using ethyl 
acetate: 60.degree.-80.degree. C. petrol (2:1) as eluant, had .sup.1 H nmr 
(CDCl.sub.3) delta 3.43 (2H, d J 23 Hz), 3.72 (d J 11 Hz) ppm. 
A solution of dimethyl 2-bromobenzylphosphonate (10.35 g) in dry DMF (50 
ml) was added dropwise at room temperature to a stirred suspension of 
sodium hydride (0.979 g) in dry DMF (100 ml) (effervescence). After 20 
minutes, a solution of furfural (3.56 g) in dry DMF (50 ml) was added 
(exotherm) and the resulting mixture was stirred at room temperature for 4 
hours, then diluted with water and extracted with ether. The extracts were 
washed with water, treated with magnesium sulphate and charcoal, filtered, 
concentrated under reduced pressure, and chromatographed using 
40.degree.-60.degree. C. petrol as eluant to give 
E-1-(2-furyl)-2-(2-bromophenyl)-ethylene (3.755 g), a pale yellow liquid 
(containing about 6% of the corresponding Z-isomer by GC). 
This ethylene was converted in 2 steps into the title compounds by the 
method described in Examples 1 and 3, that is, by reaction of the 
magnesium derivative with dimethyl oxalate, and treatment of the resulting 
ketoester with methoxymethylenetriphenylphosphorane. The E,E-isomer, 
eluted first in 30% ether in petrol, was an oil, infrared (film) 1 715 and 
1 637 cm.sup.-1, .sup.1 H nmr (CDCl.sub.3) delta 3.68 (3H,s), 3.81 (3H, 
s), 6.31 (1H,d J 3.5 Hz), 6.40 (1H, dd J 3.5 and 2 Hz), 6.83 and 6.98 
(each 1H, d J 16 Hz), 7.63 (1H,s) ppm; the Z,E-isomer was a solid, melting 
point 107.5.degree.-110.degree. C., infrared (nujol) 1 717 and 1 625 
cm.sup.-1, .sup.1 H nmr (CDCl.sub.3) delta 3.65 (3H,s), 3.93 (3H, s), 6.33 
(1H, d J 3.5 Hz), 6.40 (1H, dd J 3.5 and 2 Hz), 6.56 (1H, s), 6.82 and 
7.10 (each 1H, d J 16 Hz) ppm. 
EXAMPLE 12 
An emulsifiable concentrate was made up by mixing the ingredients, and 
stirring the mixture until all the constituents were dissolved. 
______________________________________ 
Compound of Example 5 10% 
Ethylene dichloride 40% 
Calcium dodecylbenzenesulphate 
5% 
"Lubrol" L 10% 
"Aromasol" H 35% 
______________________________________ 
EXAMPLE 13 
A composition in the form of grains readily dispersible in a liquid, eg. 
water, was prepared by grinding together the first three ingredients in 
the presence of added water and then mixing in the sodium acetate. The 
resultant mixture was dried and passed through a British Standard mesh 
sieve, size 44-100, to obtain the desired size of grains. 
______________________________________ 
Compound of Example 3 
50% 
"Dispersol" T 25% 
"Lubrol" APN5 1.5% 
Sodium acetate 23.5% 
______________________________________ 
EXAMPLE 14 
The ingredients were all ground together to produce a powder formulation 
readily dispersible in liquids. 
______________________________________ 
Compound of Example 5 
45% 
"Dispersol" T 5% 
"Lissapol" NX 0.5% 
"Cellofas" B600 2% 
Sodium acetate 47.5% 
______________________________________ 
EXAMPLE 15 
The active ingredient was dissolved in a solvent and the resultant liquid 
was sprayed on to the granules of China clay. The solvent was then allowed 
to evaporate to produce a granular composition. 
______________________________________ 
Compound of Example 3 
5% 
China clay granules 
95% 
______________________________________ 
EXAMPLE 16 
A composition suitable for use as a seed dressing was prepared by mixing 
the three ingredients. 
______________________________________ 
Compound of Example 5 
50% 
Mineral oil 2% 
China clay 48% 
______________________________________ 
EXAMPLE 17 
A dusting powder was prepared by mixing the active ingredient with talc. 
______________________________________ 
Compound of Example 3 
5% 
Talc 95% 
______________________________________ 
EXAMPLE 18 
A Col formulation was prepared by ball-milling the constituents set out 
below and then forming an aqueous suspension of the ground mixture with 
water. 
______________________________________ 
Compound of Example 5 
40% 
"Dispersol" T 10% 
"Lubrol" APN5 1% 
Water 
______________________________________ 
EXAMPLE 19 
A dispersible powder formulation was made by mixing together the 
ingredients set out below and then grinding the mixture until all were 
thoroughly mixed. 
______________________________________ 
Compound of Example 3 
25% 
"Aerosol" OT/B 2% 
"Dispersol" A.C. 5% 
China clay 28% 
Silica 40% 
______________________________________ 
EXAMPLE 20 
This Example illustrates the preparation of a dispersible powder 
formulation. The ingredients were mixed and the mixture then ground in a 
comminution mill. 
______________________________________ 
Compound of Example 5 
25% 
"Perminal" BX 1% 
"Dispersol" T 5% 
Polyvinylpyrrolidone 
10% 
Silica 25% 
China clay 34% 
______________________________________ 
EXAMPLE 21 
The ingredients set out below were formulated into a dispersible powder by 
mixing then grinding the ingredients. 
______________________________________ 
Compound of Example 3 
25% 
"Aerosol" OT/B 2% 
"Dispersol" A 5% 
China clay 68% 
______________________________________ 
In Examples 12 to 21 the proportions of the ingredients given are by 
weight. 
The compounds set out in Tables, I, II, III, IV and V are similarly 
formulated as specifically described in Examples 12 to 21. 
There now follows an explanation of the compositions or substances 
represented by the various Trade Marks and Trade Names mentioned above. 
LUBROL L: a condensate of nonyl phenol 1 mole) with ethylene oxide (13 
moles) 
AROMASOL H: A solvent mixture of alkylbenzenes 
DISPERSON T & AC: a mixture of sodium sulphate and a condensate of 
formaldehyde with sodium naphthalene sulphonate 
LUBROL APN5: a condensate of nonyl phenol (1 mole) with naphthalene oxide 
(5.5 moles) 
CELLOFAS B600: a sodium carboxymethyl cellulose thickener 
LISSAPOL NX: a condensate of nonyl phenol (1 mole) with ethylene oxide (8 
moles) 
AEROSOL OT/B: dioctyl sodium sulphosuccinate 
PERMINAL BX: a sodium alkyl naphthalene sulphonate 
EXAMPLE 22 
The compounds were tested against a variety of foliar fungal diseases of 
plants. The technique employed was as follows. 
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm 
diameter minipots. The test compounds were formulated either by bead 
milling with aqueous Dispersol T or as a solution in acetone or 
acetone/ethanol which was diluted to the required concentration 
immediately before use. For the foliage diseases, the formulations (100 
ppm active ingredient) were sprayed on to the foliage and applied to the 
roots of the plants in the soil. The sprays were applied to maximum 
retention and the root drenches to a final concentration equivalent to 
approximately 40 ppm a.i./dry soil. Tween 20, to give a final 
concentration of 0.05%, was added when the sprays were applied to cereals. 
For most of the tests the compound was applied to the soil (roots) and to 
the foliage (by spraying) one or two days before the plant was inoculated 
with the disease. An exception was the test on Erysiphe graminis in which 
the plants were inoculated 24 hours before treatment. Foliar pathogens 
were applied by spray as spore suspensions onto the leaves of test plants. 
After inoculation, the plants were put into an appropriate environment to 
allow infection to proceed and then incubated until the disease was ready 
for assessment. The period between inoculation and assessment varied from 
four to fourteen days according to the disease and environment. 
The disease control was recorded by the following grading: 
4=no disease 
3=trace-5% of disease on untreated plants 
2=6-25% of disease on untreated plants 
1=26-59% of disease on untreated plants 
0=60-100% of disease on untreated plants 
The results are shown in Tables VII, VIII and IX. 
TABLE VII 
__________________________________________________________________________ 
Data in this Table refer to compounds listed in Table I 
ERYSIPHE 
PUCCINIA 
GRAMINIS 
VENTURIA 
PYRICULARIA 
CERCOSPORA 
PLASMOA 
COMPOUND 
RECONDITA 
HORDEI INAEQUALIS 
ORYZAE ARACHIDICOLA 
VITICOLA 
NUMBER (WHEAT) (BARLEY) 
(APPLES) 
(RICE) (PEANUT) (VINES) 
__________________________________________________________________________ 
1 4 4 4 0 2 4 
2 2 0 0 0 0 0 
3 0 0 0 0 0 4 
4 0 0 1 0 0 0 
5 0 0 0 0 0 1 
7 0 0 1 0 0 0 
9 4 4 4 3* 4 4 
10 4 4 4 3* 4 4 
11 0 0 0 0 0 3 
12 0 0 0 0 0 2 
13 4 2 4 2 4 4 
14 4 4 4 4 4 4 
19 4 4 4 3 0 4 
20 0 2 4 3 3 4 
21 0 4 0 0 4 4 
22 0 0 0 0 0 4 
23 4 0 0 0 4 4 
24 4 2 4 0 0 4 
25 2 0 0 0 -- 3 
26 1 0 -- 0 -- 1 
27 3 2 4 2 2 4 
28 3 4 4 3 4 4 
29 2 3 4 0 0 3 
30 4 4 4 3 3 4 
31 0 4 2 0 0 3 
32 3 0 3 1 3 0 
35 0 2 0 2 4 0 
40 4 4 4 4 4 4 
42 3 4 4 4 1 4 
52 4 1 4 4 3 4 
53 0 0 4 0 2 4 
54 0 0 -- 0 -- 0 
55 0 0* 4 3 1* 4* 
56 4 0* 4 4 0* 4* 
57 3 0 -- 4 -- 0 
58 0 0 0 0 -- 3 
60 4 3 4 4 4 4 
61 3 0 2 2 -- 4 
66 0 3 0 0 -- 0 
__________________________________________________________________________ 
*= tested as a foliar spray at 25 ppm 
TABLE VIII 
__________________________________________________________________________ 
Data in this Table refer to compounds listed in Table II 
ERYSIPHE 
PUCCINIA 
GRAMINIS 
VENTURIA 
PYRICULARIA 
CERCOSPORA 
PLASMOA 
COMPOUND 
RECONDITA 
HORDEI INAEQUALIS 
ORYZAE ARACHIDICOLA 
VITICOLA 
NUMBER (WHEAT) (BARLEY) 
(APPLES) 
(RICE) (PEANUT) (VINES) 
__________________________________________________________________________ 
1 4 4 4 3 4 4 
7 4 4 4 4 4 4 
66 3 4 4 0 0 3 
153 4 4 4 0 3 4 
160 0 4 4 3 4 4 
161 0 0 4 0 3* 3 
177 4 4 4 2 4 4 
180 0 0 0 0 0 3 
181 4* 0* 4* 0* 0* 0* 
__________________________________________________________________________ 
*= tested as foliar spray at 25 ppm 
TABLE IX 
__________________________________________________________________________ 
Data in this Table refer to compounds listed in Table IV 
ERYSIPHE 
PUCCINIA 
GRAMINIS 
VENTURIA 
PYRICULARIA 
CERCOSPORA 
PLASMOA 
COMPOUND 
RECONDITA 
HORDEI INAEQUALIS 
ORYZAE ARACHIDICOLA 
VITICOLA 
NUMBER (WHEAT) (BARLEY) 
(APPLES) 
(RICE) (PEANUT) (VINES) 
__________________________________________________________________________ 
1 4 4 4 2 3 3 
177 0 4 3 0 0 0 
__________________________________________________________________________