CA1122522A - Fungicide containing a 3-cyclohexane-1-aminopropane derivative, its manufacture, and its use for combating fungi - Google Patents
Fungicide containing a 3-cyclohexane-1-aminopropane derivative, its manufacture, and its use for combating fungiInfo
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- CA1122522A CA1122522A CA351,346A CA351346A CA1122522A CA 1122522 A CA1122522 A CA 1122522A CA 351346 A CA351346 A CA 351346A CA 1122522 A CA1122522 A CA 1122522A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
- Pyridine Compounds (AREA)
Abstract
O.Z. 0050/033880 ABSTRACT OF THE DISCLOSURE: Fungicide for crop protection, con-taining a trans compound of the formula
Description
2~
o,z. ooso/033880 FUNGICIDE CONTAINING A 3-CYCLOHEXANE-1-~MINOPROPANE DERIVATIVE, ITS MANUFACTURE, AND ITS USE FOR COMBATIN~t FUNGI
The present invention relates to a fungicide for crop protection containing the trans compound, or a salt thereof, of a 3-~p-tert--butylcyclohexyl)-2-methylpropane compound to which is attached, in the 1-position, the nitrogen atom of a nitrogenous heterocycle.
It has been disclosed (German Laid-Open Application `
DR-OS 2,752,135) that 3-(4'-tert-butylcyclohexyl-1')-2-methyl-1--piperidinopropanes and salts thereof may be used to combat plant--pathogenic fungi.
The said compounds are, with respect to the two substituents in the 1- and 4-positions on the cyclohexane ring, in the form of cis-trans isomer mixtures.
We have found that trans compounds of the formula CH -C ~ CH2-CX-CH2-R
J
2 Z ~ ~ ~
O Z, 0050/033880 where R denotes the radical of a saturated~ 5-, 6- or 7-membered nitrogenous heterocyclic radical which is attached at the nitrogen, is unsubstituted or mono- or polysubstituted by methyl, and may bear, in the 4-position to the nitrogen atom , an oxygen atom or a C=0 radical instead of the methylene radical, and salts thereof, have a better fungicidal action than the corresponding cis compound.
It is surprising that the trans compounds have a fungicidal action on rusts (Puccinia species) in, inter alia, cereals and beans which is from 10 to 100 times greater than that of the corresponding cis compounds. By trans compound, we mean not only the pure trans compound but also mixtures containing more than 50% (wt~) of the trans compound. Examples of the radical R are the radicals of piperidine, hexamethylenimine, 3~5-dimethyl-4-piperidone and 2,6-dimethylmorpholine. Examples o~ salts are those with hydrohalic acids, e.g., hydrochloric and hydrobromic acid, or salts with sulfuric acid, acetic acid and p-toluenesulfonic acid.
The trans compounds are obtained in salt ~orm when the cis--trans mixture obtained on hydrogenation of the corresponding 1,4-disubstituted phenyl compound to the cyclohexane compound is, a~ter distilling off the solvent used ~or the hydrogenation, enriched to a trans fraction of more than 85~ by fractional distillation in a 10- to 100-tray column (reflux ratio from 1:1 to 1:100 and pressure of from 0.05 to 50 mm at top of column), and the pure trans isomer is reacted with a strong acid to give an addition salt which is then allowed to crystallize out in an organic solvent.
3o ~'12ZSZ~
O.Z. 0050/033880 Manufacturing processes 1. Manufacture of cis- and trans-3-(4-tert-butylcyclohe~yl-1)-2--methyl-1-(3~-methyl-1-piperidino)-propane.
- a) Synthesis of the aromatic amine 306 g of 3-(p-tert-butylphenyl)-2-methylpropanal is introduced into a 2-liter, 3-necked flask, and 72.5 g of 98~ (wt~) strength formic acid is dripped in. O~er a period of 3 hours, 149 g of
o,z. ooso/033880 FUNGICIDE CONTAINING A 3-CYCLOHEXANE-1-~MINOPROPANE DERIVATIVE, ITS MANUFACTURE, AND ITS USE FOR COMBATIN~t FUNGI
The present invention relates to a fungicide for crop protection containing the trans compound, or a salt thereof, of a 3-~p-tert--butylcyclohexyl)-2-methylpropane compound to which is attached, in the 1-position, the nitrogen atom of a nitrogenous heterocycle.
It has been disclosed (German Laid-Open Application `
DR-OS 2,752,135) that 3-(4'-tert-butylcyclohexyl-1')-2-methyl-1--piperidinopropanes and salts thereof may be used to combat plant--pathogenic fungi.
The said compounds are, with respect to the two substituents in the 1- and 4-positions on the cyclohexane ring, in the form of cis-trans isomer mixtures.
We have found that trans compounds of the formula CH -C ~ CH2-CX-CH2-R
J
2 Z ~ ~ ~
O Z, 0050/033880 where R denotes the radical of a saturated~ 5-, 6- or 7-membered nitrogenous heterocyclic radical which is attached at the nitrogen, is unsubstituted or mono- or polysubstituted by methyl, and may bear, in the 4-position to the nitrogen atom , an oxygen atom or a C=0 radical instead of the methylene radical, and salts thereof, have a better fungicidal action than the corresponding cis compound.
It is surprising that the trans compounds have a fungicidal action on rusts (Puccinia species) in, inter alia, cereals and beans which is from 10 to 100 times greater than that of the corresponding cis compounds. By trans compound, we mean not only the pure trans compound but also mixtures containing more than 50% (wt~) of the trans compound. Examples of the radical R are the radicals of piperidine, hexamethylenimine, 3~5-dimethyl-4-piperidone and 2,6-dimethylmorpholine. Examples o~ salts are those with hydrohalic acids, e.g., hydrochloric and hydrobromic acid, or salts with sulfuric acid, acetic acid and p-toluenesulfonic acid.
The trans compounds are obtained in salt ~orm when the cis--trans mixture obtained on hydrogenation of the corresponding 1,4-disubstituted phenyl compound to the cyclohexane compound is, a~ter distilling off the solvent used ~or the hydrogenation, enriched to a trans fraction of more than 85~ by fractional distillation in a 10- to 100-tray column (reflux ratio from 1:1 to 1:100 and pressure of from 0.05 to 50 mm at top of column), and the pure trans isomer is reacted with a strong acid to give an addition salt which is then allowed to crystallize out in an organic solvent.
3o ~'12ZSZ~
O.Z. 0050/033880 Manufacturing processes 1. Manufacture of cis- and trans-3-(4-tert-butylcyclohe~yl-1)-2--methyl-1-(3~-methyl-1-piperidino)-propane.
- a) Synthesis of the aromatic amine 306 g of 3-(p-tert-butylphenyl)-2-methylpropanal is introduced into a 2-liter, 3-necked flask, and 72.5 g of 98~ (wt~) strength formic acid is dripped in. O~er a period of 3 hours, 149 g of
3-methylpiperidine is then added dropwise, the temperature rising from 25 to over 50C. The reaction mixture is subsequently refluxed for 12 hours, whereupon C02 is evolved.
Upon completion of the reaction, the mixture is subjected to fractional distillation. After first runnings of 47 g, which distil over at 130C/0.2 mm, 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl--1'-piperidino)-propane distils over at from 130 to 133C/0.2 mm.
A total of 355 g is obtained, which is equivalent to a yield, based on the aldehyde used, of 82.4~.
b) Hydrogenation to the cyclohexane derivative 309 g of 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl~
-piperidino)-propane is hydrogenated in 1,000 g of dioxane with the aid of 0.5 g of Ru203 hydrate in a ~-liter rotating autoclave.
At a hydrogen pressure of 100 bars and a temperature of 120C, no more hydrogen is absorbed a~ter 3 hours. Subsequently at 140C
and 120 bars hydrogen pressure, a pressure drop of 35 bars over 12 hours is recorded; after readjustment of the hydrogen pressure : to 160 bars and at 160C, another pressure drop of 10 bars is registered over a period of 10 hours. No more hydrogen is absorbed when the hydrogen pressure is reset to 160 bars and the temperature raiseà to 180C.
c) Fractional distillation 3 The reaction mixture, 1,310 g, is subjected to fractional -~1~2SZZ
o.Z. 0050/033880 distillation at 10 mbars in a column containing 10 sieve trays.
After the dioxane has been distilled off, the following fractions are obtained at a reflux ratio of 1:5:
1. up to 185C - 27 g, 85g of which is cis and 10% of which is trans compound (remainder of 5% is first runnings);
2. at 185C - 114 g, 75% of which is cis and 25% of which is trans compound;
3. up to 186C - 60 gg 40% of which is cis and 60% of which is trans compound;
5. up to 187C - 55 g, 30~ of which is cis and 70% of which is trans compound.
The distillation residue (40 g) is subjected to molecular distillation at 10 mbars and 187C. There is obtained 38 g, 92%
of which is trans and only 8% cis. 2 g of distillation residue remains.
The cis:trans ratio is determined by gas chromatography.
504 g of 3-(4~-tert-butylcyclohexyl-1~)-2-methyl-1-(3~-methyl--1'-piperidino)-propane produced by the method described above and which contains a total of 425 g of cyclohexane derivative (54g cis and 46~ trans) is rractionated in a column having 20 sieve trays. The reflux ratio i5 adjusted to 1:3.
~ Up to a temperature of 192C, 70 g of first runnings distil over. Thereafter, the following fractions are obtained:
1. up to 197C~28 mbars - 13 g, 85% of which is cis and 3% of which is trans (remainder of 12% is first runnings);
2. up to 198C/26mbars - 52 g, 93~ of which is cis and 7% of which is trans;
3. up to 197 C/25 mbars - 87 g, 90% of which is cis and 10~ of which is trans;
o O.Z. 0050/033880
Upon completion of the reaction, the mixture is subjected to fractional distillation. After first runnings of 47 g, which distil over at 130C/0.2 mm, 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl--1'-piperidino)-propane distils over at from 130 to 133C/0.2 mm.
A total of 355 g is obtained, which is equivalent to a yield, based on the aldehyde used, of 82.4~.
b) Hydrogenation to the cyclohexane derivative 309 g of 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl~
-piperidino)-propane is hydrogenated in 1,000 g of dioxane with the aid of 0.5 g of Ru203 hydrate in a ~-liter rotating autoclave.
At a hydrogen pressure of 100 bars and a temperature of 120C, no more hydrogen is absorbed a~ter 3 hours. Subsequently at 140C
and 120 bars hydrogen pressure, a pressure drop of 35 bars over 12 hours is recorded; after readjustment of the hydrogen pressure : to 160 bars and at 160C, another pressure drop of 10 bars is registered over a period of 10 hours. No more hydrogen is absorbed when the hydrogen pressure is reset to 160 bars and the temperature raiseà to 180C.
c) Fractional distillation 3 The reaction mixture, 1,310 g, is subjected to fractional -~1~2SZZ
o.Z. 0050/033880 distillation at 10 mbars in a column containing 10 sieve trays.
After the dioxane has been distilled off, the following fractions are obtained at a reflux ratio of 1:5:
1. up to 185C - 27 g, 85g of which is cis and 10% of which is trans compound (remainder of 5% is first runnings);
2. at 185C - 114 g, 75% of which is cis and 25% of which is trans compound;
3. up to 186C - 60 gg 40% of which is cis and 60% of which is trans compound;
5. up to 187C - 55 g, 30~ of which is cis and 70% of which is trans compound.
The distillation residue (40 g) is subjected to molecular distillation at 10 mbars and 187C. There is obtained 38 g, 92%
of which is trans and only 8% cis. 2 g of distillation residue remains.
The cis:trans ratio is determined by gas chromatography.
504 g of 3-(4~-tert-butylcyclohexyl-1~)-2-methyl-1-(3~-methyl--1'-piperidino)-propane produced by the method described above and which contains a total of 425 g of cyclohexane derivative (54g cis and 46~ trans) is rractionated in a column having 20 sieve trays. The reflux ratio i5 adjusted to 1:3.
~ Up to a temperature of 192C, 70 g of first runnings distil over. Thereafter, the following fractions are obtained:
1. up to 197C~28 mbars - 13 g, 85% of which is cis and 3% of which is trans (remainder of 12% is first runnings);
2. up to 198C/26mbars - 52 g, 93~ of which is cis and 7% of which is trans;
3. up to 197 C/25 mbars - 87 g, 90% of which is cis and 10~ of which is trans;
o O.Z. 0050/033880
4. up to 192CJ22 mbars - 82 g, 85~ of which is cis and 15 of which is trans;
5. up to 196C~22 mbar~ - 81 g, 80% of which is cis and 20%
of which is trans;
of which is trans;
6. up to 202C/28 mbars - 87 g, 30% of which is cis and 70%
of which is trans;
of which is trans;
7. up to 196C/22 mbars - 73 g, 97% of which is trans and 3%
of which is cis.
The distillation residue-(27 g) is subjected to molecular distillation. There is obtained 24 g, 98~ of which is trans com-pound.
The initial and/or final fractions are further purified to the pure cis form by recrystallization of the hydrobromide in acetic acid/water and to the brans compound with the aid of hydrogen chloride in methanol.
d) Manufacture of the HBr salt of the pure cis ~orm 20 g of aqueous 48~ strength hydrobromic acid is added to 25 g of the first fraction obtained above. 50 g of acetic acid is then added and all the crystalline product is dissolved by heating.
Upon cooling, the hydrobromide of the cis form crystallizes out.
NMR analysis confirms that it is the pure cis form. There is obtained 28 g of melting point 210C.
C H N Br calc.: 64.15~ 10.77% 3.74% 20~34~o found: 64.5% 10.3~ 3.60% 20.6~
e) Manufacture of the HCl salt of the pure trans form 60 g of hydrogen chloride is added to 35 g of fraction 5, obtained above, in metAanol. Upon cooling, 28 g of hydrochloride having a melting point of 168C crystallizes out. NMR analysis 3 confirms the trans form.
1 2 Z S ~ ~
o.z. 0050/033880 2. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')-2--methyl-1-t 3~, 5'-dimethyl-1'-piperidino)-propane a) 361 g of 3-(p-tert-butylphenyl)-2-methylpropanal is reacted, as described in Manufacting Process 1, with 200 g of 3,5-dimethyl-piperidine and 86 g of 98% strength formic acid. The amine is purified by fractional distillation in a 10-tray column at a pressure of 0.2 mbar. 406 g of pure amine distils over at 136C.
b) Hydrogenation to the cyclohexane compound 80 g of dioxane is added to 70 g of 3- (p-tert-butylphenyl)--2-methyl-1-(3',5'-dimethyl-1'-piperidino)-propane in a shaker autoclave having a reaction volume of 250 ml. 0.5 g of ruthenium oxide hydrate is added as hydrogenation catalyst. At 120C, the pressure is kept at 100 bars hydrogen by topping up over a period of 37 hours with 358 bars.
Fractional distillation of the reaction mixture (139 g) gives 64 g of the cyclohexane derivative, which distils over between 136 and 146C/3 mm. Gas chromatographic analysis shows an isomer mixture of the cis and trans forms o~ the cyclohexane derivative.
c) Fractional distillation 562 g of the aromatic amine which was hydrogenated in 1,000 g of dioxane with the aid of Ru203.hydrate at a hydrogen pressure of 140 bars and at 120C over a period of 20 hours is separated as described in Manufacturing Process 1 in a column with 10 sieve trays, the reflux ratio being 1:5.
The more than 90% cis cyclohexane derivative distils over at 124-125C/0.1 mm. The trans cyclohexane derivative tenriched to more than 90% trans) distils over at 129-131C.
A repeat of the fractional distillation at 12-13 mm in a column 80 cm long and packed with silver wire coils gives 154 g of cis 3 compound enriched to more than 90%. A mid-fraction of 1~6 g was ~Z2522 o. Z. 0050/033880 a 1:1 mixture of cis and trans cyclohexane derivative. The yield of trans-enriched cyclohexane derivative (more than 90~ enrichment) is 98 g.
The mid-fraction is again fractionated. Only a very small amount of residue was formed - on fractional distillation of the cis-trans isomer mixture (390 g) only 2 g of high boilers is formed. At a pressure of 12 mm, the cis derivative distils over a~ 193-195C and the enriched trans product at 199-200C.
d) Crystallization of the pure cis compound via the HCl salt 20 g of the cis product enriched to m~re than 90% is taken up in 25 g o~ methanolic hydrogen chloride solution, whereupon the solution heats up to almost boiling. Upon cooling, 12 g of hydrochloride cr~stallizes out (active ingredient 19). The melting point o~ the recrystallized cis cyclohexane derivative is 240C.
A sample of the salt decomposed with KOH revealed on gas chromato-graphic analysis that the compound is trans-free cis.
e) Crystallization of the pure trans compound via the HCl salt 20 g of the trans product enriched to more than 90% is taken up in 30 g of ethanolic hydrogen chloride solution. Upon cooling, 13 ~ of the hydrochloride of the pure trans compound (m.p.: 202C) arystallizes out tactive ingredient 20). The free base, obtained by decomposing a sample of the salt, re~eals on gas chromatographic analysis that the compound is cis-free trans. NMR analysis con-firms the gas chromatography findings.
3. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')--2-methyl-1-~2',6l-cis-dimethylmorpholyl)-propane a~ 3-(p-tert-butylphenyl)-2-methyl-1-(2',6'-cis-dimethylmorpholyl)--propane is manufactured as described in Manufacturing Process 1 by reaction of 3~(p-tert-butylphenyl)-2-methylpropanal with 2,6-3 -cis-dimethylmorpholine and formic acid. The aromatic amine is llZZ~2~:
purified by distillation (it distils over at 170-175C/3.Ombars.
b) Hydrogenation to the cyclohexane compound 500 g of dioxane is added to 720 g of the morpholine derivative described above. 0.5 g of ruthenium oxide hydrate is added as hydrogenation catalyst. Hydrogenation is carried out in a 2.6 liter rotating autoclave at a hydrogen pressure of 120 bars and a tem-perature of 140C. Over a period of 24 hours, a total of 130 bars of hydrogen is pressured in.
c) Fractional distillation 623 K Of the cis-trans isomer mixture (60% cis, 40% trans) obtained is fractionated at a pressure of 3.0 mbars in an 80 cm column packed with silver wire coils. The reflux ratio is set at 1:5. The cis compound distils over at 144-145C/3.0 mm. The cis compound in the firs~ 3 fractions, each of about 70 g, was enriched to more than 90%. The last 3 fractions (71 g, 54 g and 38 g) contain the enriched (more than 85~) trans compound.
d) Crystallization of the pure cis and trans HC1 salt The pure hydrochloride of the cis compound may be obtained by the method described in Manufacturing Processes 1 and 2, with ethanolic hydrogen chloride solution; m.p.: 161C (active ingredient 23~.
The pure trans compound forms a hydrochloride having a melting point Of 199C (active ingredient 24), Gas chromatogl~aphic analysis of the 2 free bases prepared from the 2 salts by reaction with KOH reveals that the bases are pure.
The cis cyclohexane derivative thus prepurified contains less than 0.5g Qf trans product; the trans compound contains less than 1%
of cis compound. NMR analysis confirms the gas chromatography findings.
3 The remaining active ingredients are prepared in the same way.
of which is cis.
The distillation residue-(27 g) is subjected to molecular distillation. There is obtained 24 g, 98~ of which is trans com-pound.
The initial and/or final fractions are further purified to the pure cis form by recrystallization of the hydrobromide in acetic acid/water and to the brans compound with the aid of hydrogen chloride in methanol.
d) Manufacture of the HBr salt of the pure cis ~orm 20 g of aqueous 48~ strength hydrobromic acid is added to 25 g of the first fraction obtained above. 50 g of acetic acid is then added and all the crystalline product is dissolved by heating.
Upon cooling, the hydrobromide of the cis form crystallizes out.
NMR analysis confirms that it is the pure cis form. There is obtained 28 g of melting point 210C.
C H N Br calc.: 64.15~ 10.77% 3.74% 20~34~o found: 64.5% 10.3~ 3.60% 20.6~
e) Manufacture of the HCl salt of the pure trans form 60 g of hydrogen chloride is added to 35 g of fraction 5, obtained above, in metAanol. Upon cooling, 28 g of hydrochloride having a melting point of 168C crystallizes out. NMR analysis 3 confirms the trans form.
1 2 Z S ~ ~
o.z. 0050/033880 2. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')-2--methyl-1-t 3~, 5'-dimethyl-1'-piperidino)-propane a) 361 g of 3-(p-tert-butylphenyl)-2-methylpropanal is reacted, as described in Manufacting Process 1, with 200 g of 3,5-dimethyl-piperidine and 86 g of 98% strength formic acid. The amine is purified by fractional distillation in a 10-tray column at a pressure of 0.2 mbar. 406 g of pure amine distils over at 136C.
b) Hydrogenation to the cyclohexane compound 80 g of dioxane is added to 70 g of 3- (p-tert-butylphenyl)--2-methyl-1-(3',5'-dimethyl-1'-piperidino)-propane in a shaker autoclave having a reaction volume of 250 ml. 0.5 g of ruthenium oxide hydrate is added as hydrogenation catalyst. At 120C, the pressure is kept at 100 bars hydrogen by topping up over a period of 37 hours with 358 bars.
Fractional distillation of the reaction mixture (139 g) gives 64 g of the cyclohexane derivative, which distils over between 136 and 146C/3 mm. Gas chromatographic analysis shows an isomer mixture of the cis and trans forms o~ the cyclohexane derivative.
c) Fractional distillation 562 g of the aromatic amine which was hydrogenated in 1,000 g of dioxane with the aid of Ru203.hydrate at a hydrogen pressure of 140 bars and at 120C over a period of 20 hours is separated as described in Manufacturing Process 1 in a column with 10 sieve trays, the reflux ratio being 1:5.
The more than 90% cis cyclohexane derivative distils over at 124-125C/0.1 mm. The trans cyclohexane derivative tenriched to more than 90% trans) distils over at 129-131C.
A repeat of the fractional distillation at 12-13 mm in a column 80 cm long and packed with silver wire coils gives 154 g of cis 3 compound enriched to more than 90%. A mid-fraction of 1~6 g was ~Z2522 o. Z. 0050/033880 a 1:1 mixture of cis and trans cyclohexane derivative. The yield of trans-enriched cyclohexane derivative (more than 90~ enrichment) is 98 g.
The mid-fraction is again fractionated. Only a very small amount of residue was formed - on fractional distillation of the cis-trans isomer mixture (390 g) only 2 g of high boilers is formed. At a pressure of 12 mm, the cis derivative distils over a~ 193-195C and the enriched trans product at 199-200C.
d) Crystallization of the pure cis compound via the HCl salt 20 g of the cis product enriched to m~re than 90% is taken up in 25 g o~ methanolic hydrogen chloride solution, whereupon the solution heats up to almost boiling. Upon cooling, 12 g of hydrochloride cr~stallizes out (active ingredient 19). The melting point o~ the recrystallized cis cyclohexane derivative is 240C.
A sample of the salt decomposed with KOH revealed on gas chromato-graphic analysis that the compound is trans-free cis.
e) Crystallization of the pure trans compound via the HCl salt 20 g of the trans product enriched to more than 90% is taken up in 30 g of ethanolic hydrogen chloride solution. Upon cooling, 13 ~ of the hydrochloride of the pure trans compound (m.p.: 202C) arystallizes out tactive ingredient 20). The free base, obtained by decomposing a sample of the salt, re~eals on gas chromatographic analysis that the compound is cis-free trans. NMR analysis con-firms the gas chromatography findings.
3. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')--2-methyl-1-~2',6l-cis-dimethylmorpholyl)-propane a~ 3-(p-tert-butylphenyl)-2-methyl-1-(2',6'-cis-dimethylmorpholyl)--propane is manufactured as described in Manufacturing Process 1 by reaction of 3~(p-tert-butylphenyl)-2-methylpropanal with 2,6-3 -cis-dimethylmorpholine and formic acid. The aromatic amine is llZZ~2~:
purified by distillation (it distils over at 170-175C/3.Ombars.
b) Hydrogenation to the cyclohexane compound 500 g of dioxane is added to 720 g of the morpholine derivative described above. 0.5 g of ruthenium oxide hydrate is added as hydrogenation catalyst. Hydrogenation is carried out in a 2.6 liter rotating autoclave at a hydrogen pressure of 120 bars and a tem-perature of 140C. Over a period of 24 hours, a total of 130 bars of hydrogen is pressured in.
c) Fractional distillation 623 K Of the cis-trans isomer mixture (60% cis, 40% trans) obtained is fractionated at a pressure of 3.0 mbars in an 80 cm column packed with silver wire coils. The reflux ratio is set at 1:5. The cis compound distils over at 144-145C/3.0 mm. The cis compound in the firs~ 3 fractions, each of about 70 g, was enriched to more than 90%. The last 3 fractions (71 g, 54 g and 38 g) contain the enriched (more than 85~) trans compound.
d) Crystallization of the pure cis and trans HC1 salt The pure hydrochloride of the cis compound may be obtained by the method described in Manufacturing Processes 1 and 2, with ethanolic hydrogen chloride solution; m.p.: 161C (active ingredient 23~.
The pure trans compound forms a hydrochloride having a melting point Of 199C (active ingredient 24), Gas chromatogl~aphic analysis of the 2 free bases prepared from the 2 salts by reaction with KOH reveals that the bases are pure.
The cis cyclohexane derivative thus prepurified contains less than 0.5g Qf trans product; the trans compound contains less than 1%
of cis compound. NMR analysis confirms the gas chromatography findings.
3 The remaining active ingredients are prepared in the same way.
- 8 -,, `` 112~S22 Active R b.p./m.p. C.
ingredient no.
1 pyrrolidine cis base b-P16 177 pyrrolidine trans basè b-p4 = 130 3 pyrrolidine cis HCl salt m.p. = 170 4 pyrrolidine trans HCl salt m.p. - 208 piperidine cis base b Plo 180 6 piperidine trans base b.p3 = 135 7 4-methylpiperidine cis base b-P20= 2o5-2o6 8 4-methylpi.peridine trans base b.p3 ~ 146-147
ingredient no.
1 pyrrolidine cis base b-P16 177 pyrrolidine trans basè b-p4 = 130 3 pyrrolidine cis HCl salt m.p. = 170 4 pyrrolidine trans HCl salt m.p. - 208 piperidine cis base b Plo 180 6 piperidine trans base b.p3 = 135 7 4-methylpiperidine cis base b-P20= 2o5-2o6 8 4-methylpi.peridine trans base b.p3 ~ 146-147
9 hexamethylenimine cis base b Po,2 151 hexamethylenimine . trans base b Po,2 153 11 3,5-dimethyl-4- cis base b.p3 = 144 -piperidone 12 3,5-dimethyl-4- trans base b p ~148 -piperidone 13 4-ethylpiperidine cis base b.p3 = 157 14 4-ethylpiperldine trans base b.p4 ~ 159 4-ethylpiperidine cis HCl salt m.p. = 214 16 4-ethylpiperidine trans HCl salt m.p. = 240 17 3,5-dimethylpiperidine cis base b P18' 195 18 3,5-dimethylpiperidine trans base b P18 199 19 3,5-dimethylpiperidine cis HCl salt m.p. ~ 240 :
3,5-dimethylpiperidine trans HCl salt ;m.p. = 202 21 cis-2,6-dimethyl- cis base b.p3 - 145 morpholine 22 cis-2,6-dimethyl- trans base b.p3 D 148 :~
morpholine -23 cis-2,6-dimethyl- cis HCl salt m.p. ~ 161 -morpholine 24 cis-2,6-dimethyl- trans HCl salt m.p. = 199 dimethylmorpholine 1'1~2~S%~
O.Z. 0050/033880 The fungicides are particularly suitable for combating plant diseases, e.g., Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in grapes, Erysiphe polygoni in beans, Sphaerotheca pannosa in roses, Microsphaera querci in oaks, Botrytis cinerea in straw-berries and grapes, Micosphaerella musicola in bananas, Puccinia species in cereals, Uromyces appendiculatus and U. phaseoli in beans, Hemileia vastatrix in coffee, and Rhizoctonia solani. The active ingredients have a systemic action; they are taken up not only through the roots but also via the foliage, and translocated in the plant ti~sue.
When the new active ingredients are used to treat plants against fungus infections, application rates are from 0.025 to 5 kg of active ingredient per hectare. For the surface protection of trees or fruit, the active ingredients may also be used in conàunction with plastics dispersions in amounts of from 0.25 to 5%, based on the weight of the dispersion.
The fungicides generally contain from 0.1 to 95, and prèfer-ably from 0.5 to 90, wt% o~ acti~e ingredient.
The active ingredients may also be mixed with other, prior art, ~ungicides. In many cases, the spectrum of fungicidal action is increased; with a number of these fungicidal compositions in the weight ratio range of from 1:10 to 10:1, synergistic effects also occur, i.e., the ~ungicidal action of the combination product is greater than the effect of the individual components added together.
Examples of fungicides which may ~e combined with the com-pounds according to the invention are: dithiocarbamates and their derivatives, e.g.~ zinc dimethyldithiocarbamate, manganese 3 N,N-ethylene-bis-dithiocarbamate, manganese zinc N,N-ethylenediamine-- ~2Z~iZ%
O.Z. 0050/033880 -bis-dithiocarbamate, zinc N,N-ethylene-bis dithiocarbamate, tetramethylthiuram disulfide, the ammonia complex of zinc N,N--ethylene-bis-dithiocarbamate and N,N'-polyethylene-bis-(thio-carbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis-dithiocarbamate and N,Nt-polypropylene-bis-(thiocarbamoyl)-disulfide; heterocyclic compounds, e.g. N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthio-phthalimide, N-(1,1,2,2-tetrachloroethylthio)--tetrahydrophthalimide, methyl 1-(butyl-carbamoyl)-2-benzimidazole carbamate, 2-methyloxycarbonylamino-benzimidazole, 2,3-dihydro-5--carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-dihydro-5--carboxanilino-6-methyl-1,4-oxathiine, 5-butyl-2-dimethylamino-4--hydroxy-6-methyl-pyrimidine, 1,2-bis-(3-ethoxycarbonyl-2-thio-ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and various other fungicides, e.g., dodecylguanidine acetate, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-di-methylfuran-3-carboxylic acid cyclohexylamide, 2,5-dimethylfuran--3-carboxylic acid-N-methoxy-cyclohexylamide, 2-bromo-benzoic acid anilide, 2-iodo-benzoic acid anilide, diisopropyl 3-nitroiso-phthalate, 1-(1,2,4-triazol-1'-yl-~1-(4'-chlorophenoxy)]-3,3-di-methylbutan-2-one, 1-(1,2,4-triazol-1'-yl)-[1-(4'-chlorophenoxy)~--3,3-dimethylbutan-2-ol, 1-(1-imidazolyl)-2-allyloxy-2-(2,4-di- -chlorophenyl)-e~hane, piperazine-1,4-diyl-bis-1-(2,2,2-trichloro-ethyl)-formamide, 2,4,5,6-tetrachloro-isophthalonitrile, ~nd 1,2-dimethyl-3,5-diphenyl-pyrazolinium methyl sulfate.
Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, 3 or granules by spraying, atomizing, dusting, broadcasting or ~122S2~
o . z . ooso/033880 watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.
- For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cycli~ and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as di~ethylformamide, dimethyl-sulfoxide, N methylpyrrolidone, water, etc. are sùitable.
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing age~ts, adherents or emulsifiers. Concentrates which are su~table for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acidsg alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline 3 earth metal salts of fatty acids, salts of sul~ated hexadecanols, ~L12Z52Z
o. z. ooso/033880 heptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol~ ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetalg sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin~
Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, mag-nesium oxide, ground plastics, fertilizers such as ammonium -sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
There may be added to the compositions or individual active ingredients oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other effective compounds.
5~2 O.Z. 0050/033880 EXPERIMENT
Action on wheat mildew Leaves of pot-grown wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions consisting of 80% (by weight) of active ingredient and 20% of emulsifier, and dusted, after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminus var. tritici). The plants are then placed in a ~reenhouse at 20 to 22C and 75 to 80% relative humidity. The extent of mildew spread is determined after 10 days.
lO Active ingredient Leaf attack after spraying with liquor containing active ingredient in amounts Or _ o.oo6% 0.003%_ 0.0015~ O.OQ07%
9 (cis ~orm) 0 2 3 3
3,5-dimethylpiperidine trans HCl salt ;m.p. = 202 21 cis-2,6-dimethyl- cis base b.p3 - 145 morpholine 22 cis-2,6-dimethyl- trans base b.p3 D 148 :~
morpholine -23 cis-2,6-dimethyl- cis HCl salt m.p. ~ 161 -morpholine 24 cis-2,6-dimethyl- trans HCl salt m.p. = 199 dimethylmorpholine 1'1~2~S%~
O.Z. 0050/033880 The fungicides are particularly suitable for combating plant diseases, e.g., Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in grapes, Erysiphe polygoni in beans, Sphaerotheca pannosa in roses, Microsphaera querci in oaks, Botrytis cinerea in straw-berries and grapes, Micosphaerella musicola in bananas, Puccinia species in cereals, Uromyces appendiculatus and U. phaseoli in beans, Hemileia vastatrix in coffee, and Rhizoctonia solani. The active ingredients have a systemic action; they are taken up not only through the roots but also via the foliage, and translocated in the plant ti~sue.
When the new active ingredients are used to treat plants against fungus infections, application rates are from 0.025 to 5 kg of active ingredient per hectare. For the surface protection of trees or fruit, the active ingredients may also be used in conàunction with plastics dispersions in amounts of from 0.25 to 5%, based on the weight of the dispersion.
The fungicides generally contain from 0.1 to 95, and prèfer-ably from 0.5 to 90, wt% o~ acti~e ingredient.
The active ingredients may also be mixed with other, prior art, ~ungicides. In many cases, the spectrum of fungicidal action is increased; with a number of these fungicidal compositions in the weight ratio range of from 1:10 to 10:1, synergistic effects also occur, i.e., the ~ungicidal action of the combination product is greater than the effect of the individual components added together.
Examples of fungicides which may ~e combined with the com-pounds according to the invention are: dithiocarbamates and their derivatives, e.g.~ zinc dimethyldithiocarbamate, manganese 3 N,N-ethylene-bis-dithiocarbamate, manganese zinc N,N-ethylenediamine-- ~2Z~iZ%
O.Z. 0050/033880 -bis-dithiocarbamate, zinc N,N-ethylene-bis dithiocarbamate, tetramethylthiuram disulfide, the ammonia complex of zinc N,N--ethylene-bis-dithiocarbamate and N,N'-polyethylene-bis-(thio-carbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis-dithiocarbamate and N,Nt-polypropylene-bis-(thiocarbamoyl)-disulfide; heterocyclic compounds, e.g. N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthio-phthalimide, N-(1,1,2,2-tetrachloroethylthio)--tetrahydrophthalimide, methyl 1-(butyl-carbamoyl)-2-benzimidazole carbamate, 2-methyloxycarbonylamino-benzimidazole, 2,3-dihydro-5--carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-dihydro-5--carboxanilino-6-methyl-1,4-oxathiine, 5-butyl-2-dimethylamino-4--hydroxy-6-methyl-pyrimidine, 1,2-bis-(3-ethoxycarbonyl-2-thio-ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and various other fungicides, e.g., dodecylguanidine acetate, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-di-methylfuran-3-carboxylic acid cyclohexylamide, 2,5-dimethylfuran--3-carboxylic acid-N-methoxy-cyclohexylamide, 2-bromo-benzoic acid anilide, 2-iodo-benzoic acid anilide, diisopropyl 3-nitroiso-phthalate, 1-(1,2,4-triazol-1'-yl-~1-(4'-chlorophenoxy)]-3,3-di-methylbutan-2-one, 1-(1,2,4-triazol-1'-yl)-[1-(4'-chlorophenoxy)~--3,3-dimethylbutan-2-ol, 1-(1-imidazolyl)-2-allyloxy-2-(2,4-di- -chlorophenyl)-e~hane, piperazine-1,4-diyl-bis-1-(2,2,2-trichloro-ethyl)-formamide, 2,4,5,6-tetrachloro-isophthalonitrile, ~nd 1,2-dimethyl-3,5-diphenyl-pyrazolinium methyl sulfate.
Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, 3 or granules by spraying, atomizing, dusting, broadcasting or ~122S2~
o . z . ooso/033880 watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.
- For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cycli~ and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as di~ethylformamide, dimethyl-sulfoxide, N methylpyrrolidone, water, etc. are sùitable.
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing age~ts, adherents or emulsifiers. Concentrates which are su~table for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acidsg alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline 3 earth metal salts of fatty acids, salts of sul~ated hexadecanols, ~L12Z52Z
o. z. ooso/033880 heptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol~ ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetalg sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin~
Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, mag-nesium oxide, ground plastics, fertilizers such as ammonium -sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
There may be added to the compositions or individual active ingredients oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other effective compounds.
5~2 O.Z. 0050/033880 EXPERIMENT
Action on wheat mildew Leaves of pot-grown wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions consisting of 80% (by weight) of active ingredient and 20% of emulsifier, and dusted, after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminus var. tritici). The plants are then placed in a ~reenhouse at 20 to 22C and 75 to 80% relative humidity. The extent of mildew spread is determined after 10 days.
lO Active ingredient Leaf attack after spraying with liquor containing active ingredient in amounts Or _ o.oo6% 0.003%_ 0.0015~ O.OQ07%
9 (cis ~orm) 0 2 3 3
10 (trans form) 0 0 0 0 23 (cis form) 0 2 2-3 2-3 24 (trans form) 0 0 0 0 ~ontrol (untreated) 5 0 = no attack, graduated down to 5 = total attack Action on leaf rust of wheat Leaves of pot-grown wheat plants are artificially infected with spores of leaf rust (Puccinia recondita), and the plants are placed for 48 hours in a steam-saturated chamber at from 20 to 25C. The plants are then sprayed with aqueous liquors containing, as a solution or emulsion in the water, a mixture made up of 80 of active ingredient and 2Q% of sodium lignin sulfonate, and are set up in a greenhouse at from 20 to 22C and 75 to 80% relative humidity. The extent of fungus spread is assessed after 10 days.
3o ~zz`szz O.Z. 0050/033880 Active Leaf attack aftar spraying with liquor con-ingredient taining active ingredient in amaunts of 0.012% 0. oo6 %o . 003% o. 0015%
5 (cis form) 2-3 2-3 2-3 4 6 (trans form~ 0 0 0 3
3o ~zz`szz O.Z. 0050/033880 Active Leaf attack aftar spraying with liquor con-ingredient taining active ingredient in amaunts of 0.012% 0. oo6 %o . 003% o. 0015%
5 (cis form) 2-3 2-3 2-3 4 6 (trans form~ 0 0 0 3
11 (cis form) 2 2-3 4 4-5
12 (trans form) 0 0 0 2 21 (cis form) 2 3 3 4 22 (trans form) 0 0 0 0 23 (cis form) 3 5 5 5 10 ` 24 (trans form) 0 0 2 Control (untreated) 5 .
0 = no attack, graduated down to 5 - total attack EXAMPLE
90 parts by weight of compound 10 is mixed with 10 parts by weight of N-methyl-C~-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
EXA~LE 2 20 parts by weight of compound 6 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight o~ the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
20 parts by weight of compound 12 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone3 30 parts by 3 weight of isobutanol, 20 parts by weight of the adduct of 7 moles ~2522 O.Z. 0050/033880 of ethylene oxide with 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100~000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
20 parts by weight of compound 22 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100l000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
20 parts by weight ~f compound 6 is well mixed with 3 parts by weight of the sodium salt o~ diisobutylnaphthalene-C~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sul~onic 2~ acid obtained from a sulrite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uni-formly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1~ by weight of the active ingredient.
EXAMPLE
3 parts by weight of compound 12 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3~ by weight of the active ingredient.
30 parts by weight of compound 22 is inti~ately mixed with ~Z;~ 2 o. z. ooso/033880 a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
40 parts by weight of coMpound 6 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water.
- Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% of active ingredient.
EXA~PLE 9 20 parts of compound 4 is intimately mixed with 12 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ethèr, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
0 = no attack, graduated down to 5 - total attack EXAMPLE
90 parts by weight of compound 10 is mixed with 10 parts by weight of N-methyl-C~-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
EXA~LE 2 20 parts by weight of compound 6 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight o~ the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
20 parts by weight of compound 12 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone3 30 parts by 3 weight of isobutanol, 20 parts by weight of the adduct of 7 moles ~2522 O.Z. 0050/033880 of ethylene oxide with 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100~000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
20 parts by weight of compound 22 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100l000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
20 parts by weight ~f compound 6 is well mixed with 3 parts by weight of the sodium salt o~ diisobutylnaphthalene-C~-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sul~onic 2~ acid obtained from a sulrite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uni-formly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1~ by weight of the active ingredient.
EXAMPLE
3 parts by weight of compound 12 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3~ by weight of the active ingredient.
30 parts by weight of compound 22 is inti~ately mixed with ~Z;~ 2 o. z. ooso/033880 a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
40 parts by weight of coMpound 6 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water.
- Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% of active ingredient.
EXA~PLE 9 20 parts of compound 4 is intimately mixed with 12 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ethèr, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
Claims (2)
1. A fungicide for crop protection comprising a solid or liquid carrier and a trans compound of the formula , where R denotes the radical of a saturated, 5-, 6- or 7-membered nitrogenous heterocyclic radical which is attached at the nitrogen, is unsubstituted or mono- or polysubstituted by methyl, and may bear, in the 4-position to the nitrogen atom, an oxygen atom or a C=O radical instead of the methylene radical, or a salt thereof.
2. A process for combating fungi in the crop protection field, wherein the fungi or the plants to be protected against fungus attack are treated with a trans compound of the formula , where R denotes the radical of a saturated, 5-, 6- or 7-membered nitrogenous heterocyclic radical which is attached at the nitrogen, is unsubstituted or mono- or polysubstituted by methyl, and may bear, in the 4-position to the nitrogen atom, an oxygen atom or a C=O radical instead of the methylene radical, or a salt thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2921131.2 | 1979-05-25 | ||
| DE19792921131 DE2921131A1 (en) | 1979-05-25 | 1979-05-25 | FUNGICIDE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122522A true CA1122522A (en) | 1982-04-27 |
Family
ID=6071615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA351,346A Expired CA1122522A (en) | 1979-05-25 | 1980-05-06 | Fungicide containing a 3-cyclohexane-1-aminopropane derivative, its manufacture, and its use for combating fungi |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0019769B1 (en) |
| AT (1) | ATE990T1 (en) |
| CA (1) | CA1122522A (en) |
| CS (1) | CS211371B2 (en) |
| DD (1) | DD150839A5 (en) |
| DE (2) | DE2921131A1 (en) |
| DK (1) | DK158760C (en) |
| HU (1) | HU182669B (en) |
| IL (1) | IL59946A (en) |
| PL (1) | PL121967B2 (en) |
| SU (1) | SU923346A3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3121349A1 (en) * | 1981-05-29 | 1982-12-16 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXEN DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
| DE3309720A1 (en) * | 1983-03-18 | 1984-09-20 | Basf Ag, 6700 Ludwigshafen | FUNGICIDE AGENT, CONTAINING TRANS-3- (4-TERT.-ALKYLCYCLOHEXYL-1) -2-METHYL-1-DIALKYLAMINOPROPANE AND THEIR USE FOR CONTROLLING FUNGI |
| DE3624648A1 (en) * | 1986-07-22 | 1988-01-28 | Bayer Ag | DECAHYDRONAPHTH-2-YL ALKYLAMINE |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT354187B (en) * | 1976-11-22 | 1979-12-27 | Hoffmann La Roche | FUNGICIDE AGENT |
| DE2720612A1 (en) * | 1977-05-07 | 1978-11-16 | Basf Ag | 3,5-DIMETHYL-PIPERIDIN-4-ONE |
-
1979
- 1979-05-25 DE DE19792921131 patent/DE2921131A1/en not_active Withdrawn
-
1980
- 1980-04-29 IL IL59946A patent/IL59946A/en not_active IP Right Cessation
- 1980-05-06 CA CA351,346A patent/CA1122522A/en not_active Expired
- 1980-05-08 EP EP80102514A patent/EP0019769B1/en not_active Expired
- 1980-05-08 AT AT80102514T patent/ATE990T1/en active
- 1980-05-08 DE DE8080102514T patent/DE3060408D1/en not_active Expired
- 1980-05-19 SU SU802921953A patent/SU923346A3/en active
- 1980-05-21 DD DD80221274A patent/DD150839A5/en not_active IP Right Cessation
- 1980-05-23 HU HU801308A patent/HU182669B/en not_active IP Right Cessation
- 1980-05-23 DK DK226180A patent/DK158760C/en not_active IP Right Cessation
- 1980-05-23 PL PL1980224433A patent/PL121967B2/en unknown
- 1980-05-23 CS CS803654A patent/CS211371B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS211371B2 (en) | 1982-02-26 |
| DK158760C (en) | 1990-12-03 |
| DD150839A5 (en) | 1981-09-23 |
| IL59946A (en) | 1983-03-31 |
| DK158760B (en) | 1990-07-16 |
| PL121967B2 (en) | 1982-06-30 |
| SU923346A3 (en) | 1982-04-23 |
| HU182669B (en) | 1984-02-28 |
| PL224433A2 (en) | 1981-02-13 |
| DE3060408D1 (en) | 1982-07-01 |
| DK226180A (en) | 1980-11-26 |
| DE2921131A1 (en) | 1980-12-04 |
| ATE990T1 (en) | 1982-05-15 |
| IL59946A0 (en) | 1980-06-30 |
| EP0019769B1 (en) | 1982-05-12 |
| EP0019769A1 (en) | 1980-12-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |