SE416397B - MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT - Google Patents

MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT

Info

Publication number
SE416397B
SE416397B SE7714280A SE7714280A SE416397B SE 416397 B SE416397 B SE 416397B SE 7714280 A SE7714280 A SE 7714280A SE 7714280 A SE7714280 A SE 7714280A SE 416397 B SE416397 B SE 416397B
Authority
SE
Sweden
Prior art keywords
parts
weight
acid
hydrogen
dimethylmorpholine
Prior art date
Application number
SE7714280A
Other languages
Swedish (sv)
Other versions
SE7714280L (en
Inventor
N Goets
K-H Koening
B Zeeh
E-H Pommer
Original Assignee
Basf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Ag filed Critical Basf Ag
Publication of SE7714280L publication Critical patent/SE7714280L/en
Publication of SE416397B publication Critical patent/SE416397B/en

Links

Classifications

    • 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
    • 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
    • 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
    • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

15 20 25 30 35 40 u 7714280-o i vilken R betyder en kemiskt enhetlig, minst tvâ förgreningar inne- hållande alkyl- eller alkoxialkylrest med 9 - 20 kolatomer och X1 _ X8 betyder vardera en väteatom eller alkylgrupp med 1 eller 2 kolatomer, samt dessas salter har god fungicid verkan. In which R represents a chemically uniform, at least two branches containing alkyl or alkoxyalkyl radical having 9 to 20 carbon atoms and X 1 to X 8 each represents a hydrogen atom or alkyl group having 1 or 2 carbon atoms, and their salts have good fungicidal action.

Företrädesvis betyder R en kemiskt enhetlig, minst två förgreningar innehållande alkyl- eller alkoxialkylgrupp med 12 - 15 I kolatomer. Man föredrar föreningar, i vilka R betyder en perhydrerad terpenrest.Preferably R represents a chemically uniform, at least two branches containing alkyl or alkoxyalkyl group having 12 to 15 carbon atoms. Compounds in which R represents a perhydrated terpene residue are preferred.

N-alkyl- och N-alkoxialkylmorfolinerna enligt uppfinningen kan användas som fungicider i form av sina fria baser eller som salter med oorganiska syror, t.ex. halogenvätesyror (saltsyra, brom- vätesyra), svavelsyra, salpetersyra och fosforsyra, eller med organisfa syror, t.ex. myrsyra, ättiksyra, smörsyra, akrylsyra, oxalsyra, adi- pinsyra, mjölksyra, vinsyra, citronsyra, triklorättiksyra, stearin- syra, oljesyra, diisopropylditiofosforsyra, dodecylbensolsulfonsyra eller dodekansulfonsyra.The N-alkyl and N-alkoxyalkylmorpholines of the invention can be used as fungicides in the form of their free bases or as salts with inorganic acids, e.g. hydrohalic acids (hydrochloric acid, hydrobromic acid), sulfuric acid, nitric acid and phosphoric acid, or with organic acids, e.g. formic acid, acetic acid, butyric acid, acrylic acid, oxalic acid, adipic acid, lactic acid, tartaric acid, citric acid, trichloroacetic acid, stearic acid, oleic acid, diisopropyl dithiophosphoric acid, dodecylbenzol sulfonic acid or dodecanesulfonic acid.

De enligt uppfinningen avsedda N-alkyl- och N-alkoxia1kyl- morfolinerna kan framställas med kända metoder, t.ex. genom cykli- sering av dialkanolaminer (N-substituerade bis-2-hydroxialkylaminer) med dehydratiserande medel, t.ex. konc. svavelsyra, fosforsyra, halogenvätesyror, borfosfat, aluminiumfosfat eller aluminiumoxid (Houben-Weyl: "Methoden der organischen Chemic" 6/U, 510 - 546) eller genom direkt omsättning av terpenaldehyder eller terpenketoner med motsvarande morfolinförcningar under hydrerande betingelser.The N-alkyl and N-alkoxyalkylmorpholines intended according to the invention can be prepared by known methods, e.g. by cyclization of dialkanolamines (N-substituted bis-2-hydroxyalkylamines) with dehydrating agents, e.g. conc. sulfuric acid, phosphoric acid, hydrohalic acids, boron phosphate, aluminum phosphate or alumina (Houben-Weyl: "Methoden der organischen Chemic" 6 / U, 510 - 546) or by direct reaction of terpenaldehydes or terpene ketones with corresponding morpholine compounds under hydrogenating conditions.

I Morfolíndevivaten enligt uppfinningen har i tridecyl- gruppen förgreningar, som är karakteristiska för terpenföreningar och som är syntetiskt tillgängliga genom användning av terpener, t.ex. terpennldchyderua och -ketonerna uítral, melylcítral, farnesai, geranylaceton, te1rahydrogeranylaceton, pseudojonon, metoxipseudojo- non eller farnesylaceton, som utgångsmaterial. De är kemiskt en- hetliga. De nya föreningarna är därför entydigt skilda från de kända föreningarna.In the morpholine derivatives of the invention, in the tridecyl group, there are branches which are characteristic of terpene compounds and which are synthetically available by the use of terpenes, e.g. terpennldchyderua and the ketones uitral, melylcitral, farnesai, geranylacetone, terahydrogenarylacetone, pseudoionone, methoxypseudoionone or farnesyl acetone, as starting materials. They are chemically uniform. The new compounds are therefore unequivocally different from the known compounds.

K De nya aktiva substanserna lämpar sig för bekämpning av genom svampar orsakade sjukdomar hos kulturväxter, särskilt äkta mjöldaggsvamp, men även andra skadliga svampar. Exempelvis kan man bekämpa Erysiphe graminis på spannmål, Erysiphe cichoracearum på grukväxter Erysiphe polygoni på bönor, Microsphaera querci på ekar och vinrankor, Mycosphearella musicola på bananer samt Corticium salmonicolor och Ganoderma pseudoferreum på gummiträd.K The new active substances are suitable for controlling diseases caused by fungi in cultivated plants, especially true powdery mildew fungi, but also other harmful fungi. For example, you can fight Erysiphe graminis on cereals, Erysiphe cichoracearum on potted plants, Erysiphe polygoni on beans, Microsphaera querci on oaks and vines, Mycosphearella musicola on bananas and Corticium salmonicolor and Ganoderma pseudoferreum on rubber trees.

De fungicida medlen är BySf@miSkï verksamma; de upptas. såväl genom rötterna som genom bladen och transporteras i våxtens vävnader. f 'Medlen används exempelvis genom sprutning, pudring eller övergjutning av de växter som skall skyddas mot svampinfektion. -5 0 Medlen kan på vanligt sätt användas för framställning av sprutvätskor genom tillsättande av fasta fyllmedel till fina - pulver eller under tillsättande av dispergermedel, vätmedel och/el- ler häftmedel till fasta eller vätskeformiga beredningar. Dessutom kan medlen också beredas till lösningar och emulsioner, som kan 10 sprutas enligt aerosolmetoden, om de härför brukliga lösningsmedlen användes.The fungicides are BySf @ miSkï active; they are occupied. both through the roots and through the leaves and is transported in the tissues of the plant. f 'The agents are used, for example, by spraying, powdering or over-casting the plants to be protected against fungal infection. The agents can be used in the usual manner for the preparation of spray liquids by adding solid fillers to fine powders or by adding dispersants, wetting agents and / or adhesives to solid or liquid preparations. In addition, the agents can also be prepared into solutions and emulsions, which can be sprayed according to the aerosol method, if the solvents customary for this are used.

För beredning av direkt sprutbara lösningar, emulsioner, pastor och oljedispersioner kan man b1.a. använda mineraloljefrak- tioner med medelhög till hög kokpunkt, t.ex. fotogen eller diesel- 151. olja, stenkolstjäroljor e.d., oljor av vegetabiliskt eller animaliskt e ursprung, alifatiska, cykloalifatiska och aromatiska kolväten, t.eX. bensen, toluen, xylen, paraffin, tetrahydronaftalen, alkylerade naftalener och dessas derivat, metanol, etanol, propanol, butanol, kloroform, koltetraklorid, cyklohexanol, cyklohexanon, klorbensen 20 och isoforon samt starkt polära lösningsmedel, t.ex. vatten, dimetyl- formamid, dímetylsulfoxid och N-metylpyrrolidon. l _ Vattenhaltiga användningsformer kan beredas av emulsions- rkcncentrat, pastor eller vätbara pulver (sprutpulver) och oljedisper- sioner genom tillsättande av vatten. För framställning av emulsioner, 25 pastor eller oljedispersioner kan substanserna medelst ett vät-, Z binde-, disperger- eller emulgermedel homogent fördelas i vatten, antingen som sådana eller lösta i en olja eller ett lösningsmedel.For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, one can b1.a. use mineral oil fractions with a medium to high boiling point, e.g. kerosene or diesel oil, coal tar oils and the like, oils of vegetable or animal origin, aliphatic, cycloaliphatic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene and isophorone as well as strongly polar solvents, e.g. water, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone. Aqueous use forms can be prepared by emulsion concentrate, pastes or wettable powders (spray powders) and oil dispersions by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances can be homogeneously distributed in water by means of a wetting, z-binding, dispersing or emulsifying agent, either as such or dissolved in an oil or a solvent.

Man kan emellertid också bereda koncentrat, bestående av.aktiv sub- stans, vät-, binde-, disperger- eller emulgermedel samt eventuellt! '30i lösningsmedel eller olja, vilka lämpar sig för förtunning med vatten.However, it is also possible to prepare concentrates, consisting of an active substance, wetting, binding, dispersing or emulsifying agents and, if necessary! '30i solvent or oil, suitable for dilution with water.

Medlen innehåller 0,1 till 95, företrädesvis 0,5 till 90 tviktprocent aktiv substans. För ytskydd av träd eller frukter kan de aktiva substanserna också användas tillsammans med plastdisper- sioner i en mängd av 0,25 till 5 % av dispersionens vikt. Givan 35i ligger mellan 0,25 och S kg aktiv substans per hektar markyta. _ ,»" ~ De aktiva substanserna kan vidare blandas med andra fungí- - cider. I många fall erhåller man därvid en utvidgning av det fungicida .verkningsområdet. Vid vissa av dessa fungicidblandningar erhålles dessutom kombinationseffekter, dvs. kombinationsprdduktensjfungieida 'ajÃ0 _ effekt blir större än de sammanlagda effekterna av de enskilda blandningskomponenterna. j1o 15 '20 30 áåf ?j77142so-o Följande ämnen har visat sig vara särskilt väl lämpadé för kombinationer: och Ditíokarbamater och derivat av dessa, t.ex.The compositions contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active substance. For surface protection of trees or fruits, the active substances can also be used together with plastic dispersions in an amount of 0.25 to 5% of the weight of the dispersion. The yield 35i is between 0.25 and 5 kg of active substance per hectare of land. The active substances can furthermore be mixed with other fungicides. In many cases an expansion of the fungicidal range of action is obtained. In some of these fungicidal mixtures, combination effects are also obtained, ie the combination product effect becomes greater. the following substances have been found to be particularly well suited for combinations: and dithiocarbamates and derivatives thereof, e.g.

Ferridimetylditiokarbamat Zinkdimetylditiokarbamat Manganetylenbisditiokarbamat Zinketylenbisditiokarbamat Tetrametyltiuramdisulfid Manggn-zink-etylendiamin-bis-ditiokarbamat Zink-¶N,N'-propylen-1,2~bis-dítíokarbamat) Ammoniakkomplex av zink-(N,N'-propylen-bis-ditiokarbamat) N,N'-polypvopylen-bis~(tiokarbamoyl)-disulfid, 3,5-dímetyl-1,3,h-2H-tetrahydrotiadíazín-2-tion Nítrofenolderivat, t.ex.Ferridimethyl dithiocarbamate Zinc dimethyl dithiocarbamate Manganese ethylene bisdithiocarbamate Zinc ethylene bisdithiocarbamate Tetramethylthiuram disulfide Manganese zinc-ethylenediamine bis-dithiocarbamate N'-polypropylene-bis- (thiocarbamoyl) -disulfide, 3,5-dimethyl-1,3, h-2H-tetrahydrothiadiazine-2-thione Nitrophenol derivatives, e.g.

Dínitro-(1-metylheptyl)-fenylkrotonat 2-sek-butyl-U,6-dínitrofenyl-3,5-dimetylakrylat 2-sek-butyl-4,6-dínítrofenylísopropylkarhonat Heterocykliska strukturer, t,ex.Dinitro- (1-methylheptyl) -phenylcronate 2-sec-butyl-6,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate Heterocyclic structures, e.g.

N-triklormetyltiotetrahydroftalimid N-triklormetyltioftalimid N-(1,1,2,2-tetrakloretyltio)-tqtrahydroftalimid N,N-dimetyl-N-fenyl-(N~fluordiklormetyltio)-sulfamíd N~metyl-W-fenyl-(N'-fluordiklormetyltio)-N'-metylsulfamid 2-heptadekyl-2-ímidazolin ' 2,4-diklor-6-(o-kloranilino)-s-triazin Dietylftalimidofosforotioat 8-amino-1~fßis-(dimetylamino)-fosfinyi]*3-fenyl~1,2,N-tri- azol 5-etoxi-3-triklormetyl-1,2,U-tiadiazol 2,3-dicyano-1,U-ditiaantrakinon 2-tio-1,3-difio-[hšsïbj - kinoxalin 1-(butylkarbamoyl)-2-behsimidazolkçrbaminsyrametylester 2-metoxikarbonylaminobensimidazol 1-(5-cyanpentylkarbamoyl)-2-bensímidazolkarbaminsyrametyl- ' ester 2-rQdanmety;tiobenstiazol H-(2-klorfenylhydrazono)-3-metyl-5-isoxazolon ~Pyridin-2-tiøl-1-oxíd 10 15 20 25 30 7714280-0 8-hydroxikinolin resp. dess kopparsalter 2,3-dihydro-5-karboxanilido-6-metyl-1,4-oxatiin-4,U-dióxid 2,3-dihydro-5-karboxanilido~6-metyl-1,4-oxatiin 5,5-dimetyl-3-(3,5-díklorfenyl)-2,H-dioxo-1,3-oxazolidin 2-[furyl-(2)]-bensimidazol Piperazin-1,U-diyl-bis-[1-(2,2,2-trikloretylï]-formamid 2-[tiazolyl-(4)¶-benzímidazol 5-butyl-2-dimetylamino-H~hydroxí-6-metylpyrimidin Bis~(p~klorfenyl)-3-pyridinmetanol 1,2-bis-(3~etoxikarbonyl-2-tioureido)-bensol 1,2-bis-(3-metoxíkarbonyl-2-tioureído)-bensol samt diverse fungicider, t.ex.N-Trichloromethylthiotetrahydrophthalimide N-Trichloromethylthiophthalimide N- (1,1,2,2-tetrachlorethylthio) -tetrahydrophthalimide N, N-dimethyl-N-phenyl- (N-fluorodichloromethylthio) -sulfamide N-methyl-N-phenyl fluorodichloromethylthio) -N'-methylsulfamide 2-heptadecyl-2-imidazoline '2,4-dichloro-6- (o-chloroanilino) -s-triazine Diethylphthalimidophosphorothioate 8-amino-1-phosphis- (dimethylamino) -phosphinyl] -3- phenyl-1,2, N-tri-azole 5-ethoxy-3-trichloromethyl-1,2, U-thiadiazole 2,3-dicyano-1, U-dithianethraquinone 2-thio-1,3-difio- [hšsib] - Quinoxaline 1- (butylcarbamoyl) -2-behimimidazolecarbamic acid methyl ester 2-methoxycarbonylaminobenzimidazole 1- (5-cyanopentylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 2-pyranmethyl; thiobenstiazol-5-methyl-5-azone 2-thiol-1-oxide 10 15 20 25 30 7714280-0 8-hydroxyquinoline resp. its copper salts 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,0-dioxide 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine 5,5- dimethyl-3- (3,5-dichlorophenyl) -2,1H-dioxo-1,3-oxazolidine 2- [furyl- (2)] -benzimidazole Piperazine-1,1-diyl-bis- [1- (2, 2,2-Trichloroethyl] -formamide 2- [thiazolyl- (4) 6-benzimidazole 5-butyl-2-dimethylamino-H-hydroxy-6-methylpyrimidine Bis- (p-chlorophenyl) -3-pyridinemethanol 1,2-bis - (3-ethoxycarbonyl-2-thioureido) -benzole 1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzole and various fungicides, e.g.

Dodecylguanidinacetat 3-[Ö-(3,5-dimetyl-2-oxicyklohexyl)-2~hydroxietyl]-glutar- imid 2,5-dimetyl-furan-3-karbonsyreanilid a 2,5-dimetyl-furan-3-karbonsyre-cyklohexylamid 2-jodbensoesyreanilid 3-nitro-isoftalsyre-diisopropylester Hexaklorbensol 2,3-diklor-1,4-naftokinon 2,H~diklor-2,5-dimetoxibensol p-dímetylaminobensoldiazonatriumsulfonat 2-klor-1-nitropropan, Polyklornitrobensoler, 1-fenyltiosemíkarbazíd Bordeauxblandníng _A nickelhaltiga föreningar och svavel.Dodecylguanidine acetate 3- [β- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] -glutarimide 2,5-dimethyl-furan-3-carboxylic acid anilide and 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide 2-iodobenzoic anilide 3-nitro-isophthalic acid diisopropyl ester Hexachlorobenzene 2,3-dichloro-1,4-naphthoquinone 2, H-dichloro-2,5-dimethoxybenzole p-dimethylaminobenzoldiazonodium sulfonate 2-chloro-1-nitropyronitropenyl Bordeaux mixture _A nickel-containing compounds and sulfur.

Blandningen av dessa medel med fungiciderna enligt upp- finningen kan ske i ett viktförhållande mellan 1:10 och 10:1, De kan emellertid eventuellt också tillsättas först omedelbart före användandet (tankblandning). 7 Av de nya morfolinföreningarna må följande nämnas: 17714280-o b Kem. förskjutning Förening Kp OC/Torr av protonerna i morfolín-ringen (6-värden i ppm) 1 CH3CH3CH3 CH3- CH3 N 0 92/0,ü5 *Så \ 3 2 QH3 CH3 C33 ' q-MN 11a/1,s CH3 fíïwn cn3 /N ølfiig 3,97 (2H.m); H 3155 (2Hnd)§ 5 2,72 (2H,c); CH3 C 0\äø*S cnf' /\s 9 0 CH3 H N CH3CH3CH3 C53 03 á g 154/2 'CH3 CH; Q W CH +) 7714280~O Förening Kp OC/Torr Kem. förskjutning ' av pr-oton r ' morfolín-:ígšeå +) (ë-värden 'i ppm) CH: C143 ! CH; , 16_ C113 ¥-( C113 CH), 110/0 02 Cflš LQCH; i ca CH ca ¶ . 3 3 gå 3 oljíg . _ 14% U,l|2 (2H,m); CH: H cfl3* 3,69 (2H,d); CH; _ >"°\1/S . CHB \S e c1a3 / O CH; 8 CHBO CHB CH; CHB CHB N g 130/0,03 C 3 “ficflñ CH; C53 . 11S/0,1 CH 17714280-o ¶ 8 Kem. förskjutning Förening KP OC/TOPP t _ av pro onerna 1 morfolín-ringvn + (8-vürdnn 1 ppm) 10 101/0,01 11 96/0,01 oijig 12 U,26' (2H,m); 3,17 (2H.d); 2,57 (2H|t)§ 7714280-0 Förening Kp oC/Torr Kem. fïrskjutnêng av ro onerna 1 morgolin-ringen+) (ö-vävclen J. ppm) m3 (m: ' I “H3 - ..The mixture of these agents with the fungicides according to the invention can take place in a weight ratio between 1:10 and 10: 1. However, they may also be added first immediately before use (tank mixture). 7 Of the new morpholine compounds the following may be mentioned: 17714280-o b Kem. displacement Compound Kp OC / Torr of the protons in the morpholine ring (6-values in ppm) 1 CH3CH3CH3 CH3- CH3 N 0 92/0, ü5 * So \ 3 2 QH3 CH3 C33 'q-MN 11a / 1, s CH3 fíïwn cn3 / N, δ 3.97 (2H.m); H 3155 (2Hnd) § 5 2.72 (2H, c); CH3 C 0 \ äø * S cnf '/ \ s 9 0 CH3 H N CH3CH3CH3 C53 03 á g 154/2' CH3 CH; Q W CH +) 7714280 ~ O Compound Kp OC / Torr Kem. offset 'of pr-oton r' morpholine-: ígšeå +) (ë-values' in ppm) CH: C143! CH; , 16_ C113 ¥ - (C113 CH), 110/0 02 C fl š LQCH; i ca CH ca ¶. 3 3 gå 3 oljíg. 14% U, 1 | 2 (2H, m); CH: H c fl3 * 3.69 (2H, d); CH; _> "° \ 1 / S. CHB \ S e c1a3 / O CH; 8 CHBO CHB CH; CHB CHB N g 130 / 0.03 C 3“ fi c fl ñ CH; C53. 11S / 0,1 CH 17714280-o ¶ Chemical Displacement Compound KP OC / TOP t _ of the probes 1 morpholine ring ring + (8-vürdnn 1 ppm) 10 101 / 0.01 11 96 / 0.01 oijig 12 U, 26 '(2H, m); 3.17 (2H.d); 2.57 (2H | t) § 7714280-0 Compound Kp oC / Torr Chemical displacement of the ro onons 1 morgolin-ring +) (ö-vävclen J. ppm) m3 (m: ' I “H3 - ..

CH _ 5212118 11,00 (2H,m); s /H _ n 3,20 (2H,m); (m3 CH; 2,1|0 (2H,m); 9 °12H25'@'S°3 CH) C143 CH; C53 CHW/LÅN 0 151/1,5 3 pk CH; cH3 en; C113 cH3 CH; CH N S 196/1 i' LKCH3 CH; CH3 (IH-j (Il-lä (m3 “ms ,~' g “mig Mss <2H.m>; H “s 3,56 (man: 3,41 (1H,d); cflj 2,57 (i-HÜÜ; 7714280-0 Förening KP °c/T°r1~ Kem. förskjutning av grotonerna i mor olín-rin (ö-värden i lgašåf) 17 cH cH cH 3 3 3 - /KA/kfiJW/-fl CH; wo _1o1/o,o1 18 (m3 CHS cH3 115/0 1 cH3 \ < ' C113 _19 ca; 0:13 cHB CH; Wi š 15812 CHB \_< CHB ao _ en; cflš CH, PH; CH 0 111/0,o5 3 \7§ ca CHB 3 25, CH CH CH CH í 3 3 Bråjwxfä CH; N o 1o2/o,o1 cH3 CH 11 '771lr280-0 +) Förening Kp oC/Torr Kem. förskjutning av protonerna i morfolin-ringen (ö-värden i ppm) - N 0 153/0 U CH3 _ \_¿\/ßflš ' , H .3 CH3 cH3 _ CH3 3 N 0 110/0 01 CHB L-k/CHB , N 120/0 01 CH - ' 3 \'¿§«” ca; 5 118/0,1 ca; >-J CH3 CH N o 110/o,o5 z f* CH3 7 on; ca; cH3cfi¿ CH; MWN 0 113/0,05 CH3 >-Å CH3 CH3 -7744280-0 12 Förening Kp OC/Torr Kem. förskjutning av 'protonerna i mórfolin-ringen +) (ö-värden i ppm) __ 3 ø - .. - JVVWHV-(o °131g 11.17 <2H,m); m3 H/ “Q 3,25 <2H,d>; 23 CH; ' 2,60 (2H,c); e °12H25'©'S°3 en; enl eg; WW f °ljåg "'31 ”HW” ¶ m3 H/ 3,30 (2H¿d>; 29 v 2,148 (2H,1:); cn3- (cH2)10- ena- S039 (m3 cH3 m3 C53 ' w f-L-cn Mä]- 0 3 Oljíg 2,[¿0 (qfifln) v ca m3 H | 3 _ ¶ cuš 30 ' e °12H25'©'S°3 ' cH cH cH "'27 (ZHW: Wim oljig 14,05 Ham; / NJ o - 3,40 (2H,1:); C113 3,07 (ï-HÅÛ; 51' CH; _ 2,72 (zmyß) A e . °12H25@'s°3 7714280-0 13 Förening Kp oC/'Forr Kem. förskjutning - av protonerna i morfolín-ringen +) _ (ö-värden i ppm) . CH CH CH CH-f 3 3 3 9 ,_( J _ 11,110 (2n,m); N ° s eo (m m)- 7 1. . I I 9 C113 ° Jlg - 3,3o (1H,a); CH; 3,15 (man: 32 . . 2,50 (IHJ) 9 _ °12H25*<::*S°3 CH CH CH CH /J\:/\V/L\/^\/Jgí/_ I 3|u0 (2Ham)§ CH, H/ fm; 2,60 (zafln) cnñ 33 - °12H25<::>*s°3Q ca cH ca 3 3 3 .. 3 98 (23 m)- Ol, g 1 s :_ fJ*~“*~/L\/^\/%Éu/_<;^\~CH3 ' Jl 3,37 (2H,d); CH; 'H \-k/CH3 ' 2,68 (arm) 511 " u,n2 (1H,m); 3 3cH 3! - 3 e 013 'lg “'08 (IHJ-Og 35 CH; /N O Cl -3,29 (1H,m); 3,08 (1H,m) 7714230-o 1u Pö?ening K§_°C/Torr ~flu Kem:hförskfifitninghM av protonerna i morfolin-ringen +) (6-värden i ppm) C53 333 C53 Cu 0 H,H8 (1H,m); JVVLNMB °1 _ und» 35 CH; 0,” Olfliä _ 3,01 <1H.d>; H CIH 3 2,50 (zum) 3 'en en cH CH _ ' 11.09 (1H.m); WAB /°° , 3,17 (ma), _ 3 olñis 2,140 (mm, Ch; 2,22 (mm cfi3 C113 cnš' *H00 (1H,m)s /L»/^\/l\/^\/lg /“ CH; H/N 06,, °Hï°°° 2,61 (man: 38 _ CH 5 °131g 2,10 (1H,a); 3 _ 1,98 um) +> i H-NMR-spektra upptogs i CDCl3 vid 220 MHz med tetrametylsilan såsom inre standard (6 = O ppm). Jämte 6-värdet är ifrågavarande signals intensitet och multiplicitet angivna inom klammer.CH 2 5212118 11.00 (2H, m); s / H - n 3.20 (2H, m); (m 3 CH; 2.1 | 0 (2H, m); 9 ° 12H 25 '@' S ° 3 CH) C143 CH; C53 CHW / LOAN 0 151 / 1.5 3 pk CH; cH3 and; C113 cH3 CH; CH N S 196/1 i 'LKCH3 CH; CH3 (1H-j (Il-lä (m3 "ms, ~ 'g" mig Mss <2H.m>; H "s 3.56 (man: 3.41 (1H, d); c fl j 2.57 (i -HÜÜ; 7714280-0 Compound KP ° c / T ° r1 ~ Chemical displacement of the grotesons in mor olín-rin (island values in lgašåf) 17 cH cH cH 3 3 3 - / KA / k fi JW / - fl CH; wo _1o1 / o, o1 18 (m3 CHS cH3 115/0 1 cH3 \ <'C113 _19 ca; 0:13 cHB CH; Wi š 15812 CHB \ _ <CHB ao _ en; c fl š CH, PH; CH 0 111/0 , o5 3 \ 7§ ca CHB 3 25, CH CH CH CH í 3 3 Bråjwxfä CH; N o 1o2 / o, o1 cH3 CH 11 '771lr280-0 +) Compound Kp oC / Torr Chemical displacement of the protons in morpholine- ring (ö values in ppm) - N 0 153/0 U CH3 _ \ _¿ \ / ß fl š ', H .3 CH3 cH3 _ CH3 3 N 0 110/0 01 CHB Lk / CHB, N 120/0 01 CH - '3 \' ¿§ «” ca; 5 118 / 0,1 ca;> -J CH3 CH N o 110 / o, o5 zf * CH3 7 on; ca; cH3c fi¿ CH; MWN 0 113 / 0,05 CH3> -Å CH3 CH3 -7744280-0 12 Compound Kp OC / Dry Chemical displacement of the protons in the morpholine ring +) (island values in ppm) __ 3 ø - .. - JVVWHV- (o ° 131g 11.17 < 2H, m); m3 H / .Q 3.25 <2H, d>; 23 CH; 2.60 (2H, c); e ° 12H25 '©' S ° 3 en; enl eg; WW f ° ljåg "'31" HW "¶ m3 H / 3,30 (2 H¿d>; 29 in 2.148 (2H, 1 :); cn3- (cH2) 10- ena- S039 (m3 cH3 m3 C53 'w fL-cn Mä] - 0 3 Oljíg 2, [¿0 (q fifl n) v ca m3 H | 3 _ ¶ cuš 30' e ° 12H25 '© 'S ° 3' cH cH cH "'27 (ZHW: Wim oily 14.05 Ham; / NJ o - 3.40 (2H, 1 :); C113 3.07 (ï-HÅÛ; 51 'CH; _ 2 .72 (zmyß) A e. ° 12H25 @ 's ° 3 7714280-0 13 Compound Kp oC /' Forr Chemical displacement - of the protons in the morpholine ring +) _ (island values in ppm). CH CH CH CH -f 3 3 3 9, _ (J _ 11,110 (2n, m); N ° s eo (mm) - 7 1.. II 9 C113 ° Jlg - 3.3o (1H, a); CH; 3.15 (man: 32.. 2.50 (1HJ) 9 _ ° 12H25 * <:: * S ° 3 CH CH CH CH / J \: / \ V / L \ / ^ \ / Jgí / _ I 3 | u0 ( 2Ham) § CH, H / fm; 2,60 (za fl n) cnñ 33 - ° 12H25 <::> * s ° 3Q ca cH ca 3 3 3 .. 3 98 (23 m) - Ol, g 1 s: _ fJ * ~ “* ~ / L \ / ^ \ /% Éu / _ <; ^ \ ~ CH3 'Jl 3.37 (2H, d); CH;' H \ -k / CH3 '2.68 (arm) 511 "u, n2 (1H, m); 3 3cH 3! - 3 e 013 'lg„ '08 (1HJ-Og 35 CH; / NO Cl -3.29 (1H, m); 3.08 (1H, m) 7714230-o 1u Solution K§_ ° C / Torr ~ fl u Kem: hförskætninghM of the protons in the morpholine ring +) (6-values in ppm) C53 333 C53 Cu 0 H, H8 (1H, m); JVVLNMB ° 1 _ und »35 CH; 0,” Ol fl iä _ 3,01 <1H. d>; H CIH 3 2.50 (zum) 3 'and a cH CH - 11.09 (1H.m); WAB / °°, 3.17 (ma), _ 3 olñis 2,140 (mm, Ch; 2,22 (mm c fi3 C113 cnš '* H00 (1H, m) s / L »/ ^ \ / l \ / ^ \ / lg / “CH; H / N 06 ,, ° Hï °°° 2.61 (man: 38 _ CH 5 ° 131g 2.10 (1H, a); 3 _ 1.98 um) +> i H- NMR spectra were recorded in CDCl 3 at 220 MHz with tetramethylsilane as internal standard (6 = 0 ppm), and in addition to the 6 value, the signal intensity and multiplicity are indicated in parentheses.

De nya föreningarna är lika verksamma som fungicider som de kända N-alkylmorfolinderivaten. Den särskilda fördelen med de nya föreningarna ligger i att de är enhetliga, medan det vid de motsvarande förut kända morfolinderivaten rör sig om isomerbland ningar.The new compounds are as active as fungicides as the known N-alkylmorpholine derivatives. The special advantage of the new compounds is that they are uniform, while the corresponding previously known morpholine derivatives are isomer mixtures.

De aktiva substanserna enligt uppfinningen är föreningar med entydig konstitution, ur vilka det vid användningen alltid uppstår klart definierade sönderfallsprodukter med ständigt lika sammansättning. En annan fördel med ämnena enligt uppfinningen ligger däri, att delstrukturer av de nya föreningarna förekommer som byggstenar i naturen, så att man icke har att befara någon 10 15 20 A25. 30 35 77111280-0 15 nackdel i form av miljöbelastning från dessa nya produkter. Det har helt överraskande visat sig, att man med kemiskt enhetliga pmorfolinföreningar, vilka såsom sidokedja väsentligen uppvisar ett terpenskelett, kan erhålla en lika god fungicid effekt som med nämnda blandning av kända isomera morfoliner.The active substances according to the invention are compounds with an unambiguous constitution, from which, when used, clearly defined decomposition products of always the same composition always arise. Another advantage of the substances according to the invention lies in the fact that substructures of the new compounds occur as building blocks in nature, so that there is no need to fear any A25. 30 35 77111280-0 15 disadvantage in the form of environmental impact from these new products. It has quite surprisingly been found that with chemically uniform pmorpholine compounds, which as a side chain essentially have a terpene skeleton, one can obtain as good a fungicidal effect as with said mixture of known isomeric morpholines.

Z För de följande försöken användes som förut kända aktiva substanser "Tridemorph" (isomerblandning av N-tridecyl-2,6-dimety1- morfoliner) och N-n-dodecyl-2,6-dimetylmorfolin.For the following experiments, previously known active substances "Tridemorph" (isomeric mixture of N-tridecyl-2,6-dimethylmorpholines) and N-n-dodecyl-2,6-dimethylmorpholine were used.

Exempel 1 Bland av i krukor odlade korngroddar besprutades med vattenemulsioner, innehållande 80 viktprocent aktiv substans och 20 viktprocent emulgermedel i torrsubstans, samt bepudrades efter . sprutbeläggningens avtorkning med oidier (sporer) av kornmjöldagg (Erysiphe graminis, var. hordei). Försöksväxterna uppställdes i anslutning därtill i drivhus med en innertemperatur av.mellan 20 och 22°c och vs till ao <2 relativ luftfuktighet. Efter 10 dygn bestämdes omfattningen av den utvecklade mjöldaggssvampen. Resul- taten är sammanställda i efterföljande tabell: Effektivitet med Erysiphe graminis på korn.Example 1 Among peat sprouts grown in pots were sprayed with water emulsions containing 80% by weight of active substance and 20% by weight of emulsifier in dry matter, and powdered after. wiping the spray coating with oidia (spores) of barley flour dew (Erysiphe graminis, var. hordei). The test plants were subsequently set up in greenhouses with an internal temperature of between 20 and 22 ° C and vs to ao <2 relative humidity. After 10 days, the extent of the developed powdery mildew fungus was determined. The results are summarized in the following table: Efficiency with Erysiphe graminis on barley.

Bladangrepp efter besprutning..procentiga _suspensioner resp.emulsíoner av den aktiva substansen: Aktiv substans nr 0,025 0,012 % 0,006 % n-dodehyl-2,6- 1 2 2 dimetylmorfolin "Tridemorph" DB 0 2-3 5 0 1 p -+ 14 0 1 ' -+ 16 0 1 ~+ 18 _ UB 0-1 22 1 1-2 3 23 OB 1 1-2 25 1 1-2 2 za i oB 1 1-2 28 ' 0 2 2 29 0 2 31 0 0-1 _ 32 OB 1 1-2 Kontrollprov (obehandlat) U + = ej provat B = lätta bladangrepp 0 = inga angrepp, skala till 5= totalangrepp ,v 10 20 25 30 t?7142so-o _16 Exemgel 2 Effekt gentemot vätemjöldagg.Leaf infestation after spraying..percent_suspensions or emulsions of the active substance: Active substance no. 0.025 0.012% 0.006% n-dodeahyl-2,6- 1 2 2 dimethylmorpholine "Tridemorph" DB 0 2-3 5 0 1 p - + 14 0 1 '- + 16 0 1 ~ + 18 _ UB 0-1 22 1 1-2 3 23 OB 1 1-2 25 1 1-2 2 za i oB 1 1-2 28' 0 2 2 29 0 2 31 0 0-1 _ 32 OB 1 1-2 Control test (untreated) U + = not tested B = light leaf infestation 0 = no infestation, scale to 5 = total infestation, v 10 20 25 30 t? 7142so-o _16 Exemgel 2 Effect against hydrogen flour dew.

Blad av i krukor odlade plantor ur vetefrön av sorten "Caribo" besprutades droppvått med 0,03- till 0,025-procentiga (viktprocent), vattenhaltiga sprutvätskor, som innehöll 80 % aktiv substans och 20 % ligninsulfonat i-torrsubstans. Efter av- torkning av sprutbeläggningen bepudrades plantorna med cidier (sporer) av vetemjöldagg (Erysiphe graminis var; triticí). Försöka- plantorna uppställdes därefter i drivhus vid temperaturer mellan 20 och 2200 och 65 till 70 % relativ luftfuktighet. Efter 10 dygn bestämdes omfattningen av mjöldaggssvampens angrepp. Resultaten är sammanställda i följandv tabell: Aktivsubstansnr Användningskoncentration n .n 0,05 0,025 0,012 0,006 "Tridemorph" 0/2H 0/2H 0/1H 3 "Tridemorph"-salt med dodekyl- bensensulfonatsyra 0 0 0 1 31 0/1 0 1 32 0. 0 0 1 Kontrollprov U Bladskador: 1 enstaka nekroser 1H " “ och bleka partier 1H lätta bladskador oflibleka partier Exemgel 3 Av föreningen 1 blandades 90 viktdelar med 10 viktdelar N~metyl-u-pyrrolidon och erhöll en lösning, som lämpar sig för användning i form av mycket fina droppar.Leaves of potted plants grown from "Caribo" wheat seeds were sprayed dropwise with 0.03 to 0.025% (weight percent), aqueous spray liquids containing 80% active substance and 20% lignin sulfonate in dry matter. After wiping off the spray coating, the plants were dusted with cider (spores) of wheat flour dew (Erysiphe graminis var; triticí). The test plants were then set up in greenhouses at temperatures between 20 and 2200 and 65 to 70% relative humidity. After 10 days, the extent of the powdery mildew fungus infestation was determined. The results are summarized in the following table: Active substance no. Use concentration n .n 0,05 0,025 0,012 0,006 "Tridemorph" 0 / 2H 0 / 2H 0 / 1H 3 "Tridemorph" salt with dodecylbenzenesulfonate acid 0 0 0 1 31 0/1 0 1 32 0. 0 0 1 Control sample U Leaf damage: 1 single necrosis 1H "" and pale parts 1H light leaf damage and pale parts Example 3 Of compound 1, 90 parts by weight were mixed with 10 parts by weight of N-methyl-u-pyrrolidone to obtain a suitable solution. for use in the form of very fine drops.

Exemgel H Av föreningen 2 löstes 20 viktdelar i en blandning, som bestod av 80 viktdelar Xylol, 10 viktdelar av anlagringsprodukten av 8 till 10 mol etylenoxid till 1 mol oljesyra-N-monoetanolamid, 5 viktdelar kalciumsalt av dodecylbensensulfonsyra och 5 viktdelar av anlagringsprodukten av H0 mol etylenoxid till 1 mol ricinolja.Example H Of compound 2, 20 parts by weight were dissolved in a mixture consisting of 80 parts by weight of Xylol, 10 parts by weight of the storage product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the storage product of H moles of ethylene oxide to 1 mole of castor oil.

Genom införing och finfördelning av denna lösning i 100 000 vikt- delar vatten erhåller man en vattendispersion, som innehåller 0,02 viktprocent av den aktiva substansen. " ,v 10 15 20 25 30 17 7714280-0 Exemgel 5 Av föreningen 3 löstes 20 viktdelar i en blandning, som bestod av 40 viktdelar cyklohexanon, 30 viktdelar isobutanol, 20 viktdelar av anlagringsprodukten av 7 mol etylenoxid till 1 mol isooktylfenol och 10 viktdelar av anlagringsprodukten av H0 mol etylenoxid till 1 mol ricinolja. Genom införande och finfördelning av denna lösning i 100 000 viktdelar vatten erhölls en vatten- dispersion, som innehöll 0,02 viktprocent av den aktiva substansen.By introducing and atomizing this solution in 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.02% by weight of the active substance. Example 5 Of compound 3, 20 parts by weight were dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the storage product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the storage product of HO mol of ethylene oxide to 1 mol of castor oil By introducing and comminuting this solution in 100,000 parts by weight of water, a water dispersion was obtained which contained 0.02% by weight of the active substance.

Exemgel 6 Av föreningen nr 4 löstes 20 viktdelar i en blandning, som bestod av 25 viktdelar cyklohexanol, 65 viktdelar av en mineralolje- fraktion med kokpunkten 210 till 28000 och 10 viktdelar av anlag- ringsprodukten av H0 mol etylenoxid till 1 mol ricinolja. Genom införande och finfördelning av denna lösning i 100 000 viktdelar vatten erhåller man en vattondispersion, som innehåller 0,02 vikt- procent av den aktiva substansen. åkemgel 7 Av föreningen nr 5 blandas 20 víktdelar väl med 3 viktdelar av diisobutylnaftalin-a-sulfonsyrans natriumsalt, 17 viktdelar av natriumsaltet av en ligninsulfonsyra från en sulfitavlut samt 60 vikt- delar pulverformigt kiselsyragel samt males i en hammarkvarn. Genom finfördelning av blandningen i 20 000 viktdelar vatten erhåller .man en sprutvätska, som innehåller 0,1 viktprocent aktiv substans.Example 6 Of compound No. 4, 20 parts by weight were 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 of 210 to 28,000 and 10 parts by weight of the deposition product of HO moles of ethylene oxide to 1 moles of castor oil. By introducing and atomizing this solution in 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.02% by weight of the active substance. Åkemgel 7 Of compound No. 5, 20 parts by weight are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulphite liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By atomizing the mixture in 20,000 parts by weight of water, a spray liquid is obtained, which contains 0.1% by weight of active substance.

Exemgel 8 Av föreningen nr 6 blandas 3 viktdelar väl med 97 viktdelar finpartiklig kaolin. Man erhåller på detta sätt ett bepudringsmedel, som innehåller 3 viktprocent av den aktiva substansen.Example gel 8 Of compound no. 6, 3 parts by weight are mixed well with 97 parts by weight of fine particulate kaolin. In this way a powdering agent is obtained, which contains 3% by weight of the active substance.

Exemgel 9 Av föreningen nr 7 blandas 30 viktdelar väl med en bland- ning av 92 viktdelar pulverformigt kiselsyragel och 8 viktdelar paraffinolja, som sprutades på detta kiselsyragels yta. Man erhåller på ningsförmåga. 10 15 20 25 30 30 -vvwuzso-os 18 Exempel 10-- Av det aktiva ämnet nr 8 blandas H0 viktdelar väl med 10 delar natriumsalt av ett fenolsulfonsyra-karbamidkondensat, 2 delar kiselsyragel och H8 delar vatten. Man erhåller en stabil vattendispersion. Genom förtunning med 100 000 viktdelar vatten erhåller man en vattendispersion, som innehåller 0,04 viktprocent aktiv substans.Example Gel 9 Of Compound No. 7, 30 parts by weight are mixed well with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which was sprayed on the surface of this silica gel. You get on ning ability. Example 15 - Of the active substance No. 8, H0 parts by weight are mixed well with 10 parts of sodium salt of a phenolsulfonic acid urea condensate, 2 parts of silica gel and H8 parts of water. A stable water dispersion is obtained. By diluting with 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.04% by weight of active substance.

Exempel 11 _ Av det aktiva ämnet nr 9 blandas 20 delar väl med 2 delar av dodekylbensolsulfonsyrans kalciumsalt, 8 delar fettalkohol- polyglykoleter, 2 delar natriumsalt av ett fenolsulfonsyra-karbamid- formaldehydkondensat och 68 delar av en paraffinisk mineralolja.Example 11 - Of the active substance No. 9, 20 parts are mixed well with 2 parts of the calcium salt of dodecylbenzol sulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil.

Man erhåller en stabil, oljig dispersion.A stable, oily dispersion is obtained.

Exempel 12 Av tetrahydrogeranylaceton löses 500 delar i 1000 delar metanol och fylles tillsammans med 50 delar metanolfuktigt Raney- nickel i en 3 liters autoklav. Härefter påtryckes 3H0 delar ammoniak.Example 12 500 parts of tetrahydrogeranylacetone are dissolved in 1000 parts of methanol and filled together with 50 parts of methanol-moist Raney nickel in a 3 liter autoclave. Then 3H0 parts of ammonia are applied.

Därpå uppvärmes det hela till 90°C och genom påtryckning av vätgas inställes ett tryck av 100 bar. Genom påföljande tryckökning kompletteras den förbrukade vätgasmängden till vätgasupptagningens slut.The whole is then heated to 90 ° C and a pressure of 100 bar is set by pressing hydrogen. By subsequent pressure increase, the amount of hydrogen consumed is supplemented to the end of the hydrogen uptake.

För uppanbetningen filtreras reaktionsprodukten och destil- leras filtratet.For the addition, the reaction product is filtered and the filtrate is distilled.

Man erhåller H80 delar (omkring 95,5 %) 6,10 dimetyl-2- aminoundekan, Kpoäüs = 65°C.H80 parts are obtained (about 95.5%), 6.10 dimethyl-2-aminoundecane, Kpoäüs = 65 ° C.

H00 delar 6,10-dinetyl-2~amíno-undekan och 4 delar vatten uppvärmes i en 2-liters autoklav med omrörare till 1HO°C. Härefter påtryckes portionsvis 520 delar propylenoxid. Därpå hålles tempe- raturen ytterligare 10 timmar vid 140°C, varefter upparbetning sker. Den destillativa upparbetningen ger 575 delar (omkring 91 % teor. mängd) N,N-di-(2-hydroxi-prop-1-yl)-N-(6,10-dimetyl-undek-2-y1)- amin, xpmm = 168 12111 110%. - Till 530 delar N,H-di-(2-hydroxi-prop-1-yl)-N-(6,10-di- metyleundec-2-yl)-amin sätter man under omrörning H10 delar koncent- rerad svavelsyra och håller blandningen därefter vid 130°C under 5 timmar.H00 parts of 6,10-dinethyl-2-amino-undecane and 4 parts of water are heated in a 2-liter autoclave with stirrer to 1HO ° C. Then 520 parts of propylene oxide are applied portionwise. The temperature is then kept at 140 ° C for a further 10 hours, after which work-up takes place. The distillative work-up gives 575 parts (about 91% of theory, amount) of N, N-di- (2-hydroxy-prop-1-yl) -N- (6,10-dimethyl-undec-2-yl) -amine, xpmm = 168 12111 110%. To 530 parts of N, H-di- (2-hydroxy-prop-1-yl) -N- (6,10-dimethylundec-2-yl) -amine are added with stirring H10 parts of concentrated sulfuric acid and then keep the mixture at 130 ° C for 5 hours.

Claims (1)

1. 0 15 ' 19 771lr280-0 Härefter försätter man reaktíonsblandningen långsamt med 1000 delar 25-procentig (viktprocent) natronlut, varpå den får stå och sjunka samt avskiljer den organiska fasen. Denna deštilleras, 0 varvid man erhåller 470 delar (ca 93 ø av teor. mängd) N-(6',10'- dimetyl~undeo-2'-yl)-2,6-dimetylmorfolin, Kpz = 158OC. Exemgel 13 Man löser UH delar "Farnesal" och 23 delar 2,6-dimetylr morfolin i 70 delar tetrahydrofuran och fyller lösningen tillsammans med 6 delar tetrahydrofuranfuktig Raney-nickel i en 250 ml skak- autoklav. Därefter upphettas till 195°C och pätryckes vätgas till 200 bar. Till slutet av vätgasupptagningen hâlles trycket genom ytter- ligare påtryckning av vätgas vid 200 bar. Härefter filtreras reaktíonsprodukten och filtratet destil- Å leras. Man erhåller härvid 57 delar (ca 87,5 1 av teoretisk mängd) N-(3', 7', 11'-trimetyl-dodoc-1'-yl)-2,6-dimetylmorfolin, = 1 O . Kp1,5 61 C PATENTKRAV Morfolinderivat med fungicid verkan enligt formeln k ä n n e t e c k n a t av att R betecknar en kemiskt enhetlig, två eller flera förgreningar innehållande alkyl- eller alkoxialkylrest med 9 till 20 kolatomer, och att X1 t.o.m. X8 betecknar en väteatom eller en alkylrest med 1 eller 2 kolatomer, sant denns salter. ANFÖRDÅ PUBLIKATIONER:1. 0 15 '19 771lr280-0 Then the reaction mixture is slowly added with 1000 parts of 25% (by weight) sodium hydroxide solution, after which it is allowed to stand and sink and the organic phase is separated. This is distilled to give 470 parts (about 93 ø of theory amount) of N- (6 ', 10'-dimethyl-undeo-2'-yl) -2,6-dimethylmorpholine, Kpz = 158 ° C. Example gel 13 Dissolve UH parts of "Farnesal" and 23 parts of 2,6-dimethylmorpholine in 70 parts of tetrahydrofuran and fill the solution together with 6 parts of tetrahydrofuran-moist Raney nickel in a 250 ml shake autoclave. Then heat to 195 ° C and pressurize hydrogen to 200 bar. Until the end of the hydrogen uptake, the pressure is maintained by further applying hydrogen at 200 bar. The reaction product is then filtered and the filtrate is distilled. 57 parts are obtained (about 87.5 l of theoretical amount) of N- (3 ', 7', 11'-trimethyl-dodoc-1'-yl) -2,6-dimethylmorpholine, = 10. Kp1,5 61 C PATENT REQUIREMENTS Morpholine derivatives with fungicidal action according to the formula are characterized in that R represents a chemically uniform, two or more branches containing alkyl or alkoxyalkyl radical having 9 to 20 carbon atoms, and that X1 t.o.m. X8 represents a hydrogen atom or an alkyl radical having 1 or 2 carbon atoms, true its salts. BEFORE PUBLICATIONS:
SE7714280A 1976-12-18 1977-12-15 MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT SE416397B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19762657476 DE2657476A1 (en) 1976-12-18 1976-12-18 MORPHOLINE DERIVATIVES

Publications (2)

Publication Number Publication Date
SE7714280L SE7714280L (en) 1978-06-19
SE416397B true SE416397B (en) 1980-12-22

Family

ID=5995881

Family Applications (1)

Application Number Title Priority Date Filing Date
SE7714280A SE416397B (en) 1976-12-18 1977-12-15 MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT

Country Status (8)

Country Link
BE (1) BE862002A (en)
CS (1) CS195345B2 (en)
DE (1) DE2657476A1 (en)
DK (1) DK151015C (en)
FR (1) FR2374316A1 (en)
GB (1) GB1591144A (en)
NL (1) NL187809C (en)
SE (1) SE416397B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2921221A1 (en) * 1979-05-25 1980-12-11 Basf Ag TRANS-3- (4'-TERT.-BUTYL-CYCLOHEXYL-1 ') - 2-METHYL-1- (3'-METHYLPIPERIDINO, 3', 5'-DIMETHYLPIPERIDINO AND 2 ', 6'-DIMETHYLMORPHOLINO) -PROPAN, METHOD FOR THEIR PREPARATION AND ANTIMYCOTIC AGENTS CONTAINING THEM
WO1999065318A2 (en) * 1998-06-18 1999-12-23 Merck Patent Gmbh Geminally substituted amines
DE19827166A1 (en) * 1998-06-18 1999-12-23 Merck Patent Gmbh Process for the catalytic disubstitution of carboxamides with at least one Grignard reagent
DE19827161A1 (en) * 1998-06-18 1999-12-23 Merck Patent Gmbh Process for the catalytic, symmetrical disubstitution of carboxamides with Grignard reagents
SI1373232T1 (en) 2001-03-16 2006-04-30 Basf Ag Method for producing n-substituted 2,6-dialkyl morpholines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1216311B (en) * 1960-11-28 1966-05-12 Jefferson Chem Co Inc Process for the preparation of N-alkylmorpholines
BE614214A (en) * 1961-02-22
US3418895A (en) * 1967-06-20 1968-12-31 Charles G. Palmer Control system for article stackers
FR1535615A (en) * 1967-06-26 1968-08-09 Ct Europ De Rech S Mauvernay Process for obtaining tetrahydro-1, 4-oxazines substituted in 2, 4 and in 2, 2, 4
DE2461513A1 (en) * 1974-12-27 1976-07-08 Basf Ag MORPHOLINE DERIVATIVES

Also Published As

Publication number Publication date
DE2657476A1 (en) 1978-06-22
CS195345B2 (en) 1980-01-31
BE862002A (en) 1978-06-19
NL7713682A (en) 1978-06-20
DK561677A (en) 1978-06-19
FR2374316A1 (en) 1978-07-13
GB1591144A (en) 1981-06-17
SE7714280L (en) 1978-06-19
FR2374316B1 (en) 1982-11-19
DK151015B (en) 1987-10-12
DE2657476C2 (en) 1988-10-06
NL187809B (en) 1991-08-16
DK151015C (en) 1988-06-06
NL187809C (en) 1992-01-16

Similar Documents

Publication Publication Date Title
SE441527B (en) FUNGICIDICALLY EFFECTIVE MORPHOLINE DERIVATIVES
EP0000940B1 (en) Gamma-azolyl alcohols and their use as plant growth regulators
EP0251082A2 (en) Substituted acrylic acid esters and fungicides containing these compounds
EP0000333B1 (en) Cyclic amine derivatives and fungicides containing them
EP0021345A1 (en) Alpha-azolylglycol derivatives, their preparation, plant growth regulating agents containing them, and their use
CS208669B2 (en) Fungicide means
CS199223B2 (en) Fungicide
CH635481A5 (en) FUNGICIDE AGENT.
SE416397B (en) MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT
CH629079A5 (en) Fungicide
DE2926096A1 (en) FUNGICIDE BETA -TRIAZOLYL ETHER, THEIR PRODUCTION AND USE
EP0000112B1 (en) Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides
EP0102578B1 (en) 2-aryl-2-azolyl-methyl-1,3-dioxepines
EP0002671A1 (en) Triazolylglycol ethers, process for their preparation and their use as fungicides
EP0161455B1 (en) Beta-naphthylalkyl amines
CH622510A5 (en)
DE3110767A1 (en) FIGHTING MUSHROOMS WITH 1,2-OXAZOLYLALKYLPHOSPHATES
EP0056125B1 (en) Alkene-o,n-acetals, method for their preparation, fungicides containing them and their application as fungicides
EP0031962B1 (en) Fungicidal azolyl-silyl-glycol ethers, their preparation, their use to combat fungi and composition therefor
EP0019153A1 (en) Carbinol ethers, process for their preparation and fungicides containing them
DE2609105A1 (en) AMMONIUM AND SULPHONIUM SALTS
EP0093274B1 (en) Organosilyl compounds and their use as fungicides
EP0056461B1 (en) N-3&#39;(p-tertiary-butylphenyl)-2&#39;-methyl-propyl-1-piperidine derivatives, fungicides containing them and their use as fungicides
EP0008731B1 (en) N-sulfenyl formanilides, their preparation and their use as fungicides
DE3805117A1 (en) Novel azolylmethylsilanes

Legal Events

Date Code Title Description
NAL Patent in force

Ref document number: 7714280-0

Format of ref document f/p: F

NUG Patent has lapsed

Ref document number: 7714280-0

Format of ref document f/p: F