PL90691B1 - Heterocyclic compounds and fungidical compositions[au6271173a] - Google Patents

Heterocyclic compounds and fungidical compositions[au6271173a] Download PDF

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PL90691B1
PL90691B1 PL1974168031A PL16803174A PL90691B1 PL 90691 B1 PL90691 B1 PL 90691B1 PL 1974168031 A PL1974168031 A PL 1974168031A PL 16803174 A PL16803174 A PL 16803174A PL 90691 B1 PL90691 B1 PL 90691B1
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methyl
compound
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nitro
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Rohm And Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

1422430 3-Thioallophonic acid derivatives ROHM & HAAS CO 5 Dec 1973 [22 Jan 1973 (2)] 56309/73 Heading C2C Novel compounds have the Formula I wherein X is R<SP>1</SP>O- or R<SP>1</SP>S-, R<SP>1</SP> being: (a) alkyl, straight or branched, of 1 to 12 carbon atoms, (b) alkyl or 1 to 12 carbon atoms substituted with halo, preferably chloro, or methoxy groups, (c) alkenyl of 2 to 12 carbon atoms, (d) alkynyl of 3 to 12 carbon atoms, (e) phenyl, (f) phenyl substituted with halo (preferably chloro) methyl, methoxy or nitro, (g) benzyl or (h) benzyl substituted in the ring with halo (preferably chloro) methyl, methoxy or nitro; Y is a heterocyclic radical having 5 or 6 cyclic atoms and having as a hetero atom O, S or N or any combination of two of these wherein the total number of hetero atoms is up to three and the acetoxymethyl, chloro, methyl or nitro substituted derivatives of these; R is hydrogen or methyl; Z is halo (preferably chloro) methyl, methoxy or nitro and n is 0 to 3. The compounds of Formula I are prepared by (A) reacting a compound of formula R-CO-Y with a compound of formula or (B) reacting a compound of formula with a compound of formula the use of a base being necessary in (A) or (B) when reactions of acid-sensitive aldehydes or their Schiff bases are involved. In particular, compounds of Formula VII wherein W is hydrogen, acetoxymethyl, chloro, methyl or nitro, are obtained by reacting a compound of formula with a compound of formula, X-CO-NCS in the presence of an inert solvent and 0À5-20 mole per cent based on the heterocyclic reactant of a tertiary amine whose dissociation constant at 25‹ C. is in the range of 5 Î 10<SP>-3</SP> to 5 Î 10<SP>-5</SP> (e.g. trimethylamine, triethylamine, tripropylamine, triisobutylamine, methyldiethylamine, tetramethylethylenediamine, N,N-dimethylethanolamine and dimethylaniline). Examples prepare compounds of Formula I wherein Y is 2-furyl optionally 5-substituted by CH 3 -, CH 3 CO.OCH 2 - or NO 2 groups, 2- thienyl optionally 5-substituted by chlorine, 2-pyrryl, 2-(N-methyl)pyrryl, 5-isothiazolyl or 2-pyridyl. Other specified heterocyclic radicals Y are thiazolyl, imidazolyl, isoxazolyl, oxadiazolyl, oxazolyl, pyrimidyl, thiadiazolyl, triazinyl and triazolyl. The compounds of Formula I (and VII) are fungicides and show anthelmintic activity. [GB1422430A]

Description

Przedmiotem wynalazku jest srodek grzybobój¬ czy, zawierajacy jako substancje aktywna .nowe pochodne kwasu 3-tioallofanowego.W literaturze niewiele jest informacji dotycza¬ cych pokrewnych zwiazków. Zainteresowanie bu¬ dza srodki grzybobójcze znane pod nazwa Topsin, takie jak l,2-bis(3-metoksy) lub etoksy(karbonylo- -2-tioureido)benzen. Zwiazki takie opisano na przyklad w belgijskim opisie patentowym nr 722 080. Biologicznie czynne zwiazki o wzorze ogól¬ nym 3, w którym Z oznacza miedzy innymi grupe benzylidenoaminowa lub jej pochodna chlorowa, metoksylowa lub nitrowa sa znane np. z brytyj¬ skiego opisu patentowego nr 1 214 415.W srodku grzybobójczym wedlug wynalazku substancje aktywna stanowia nowe pochodne kwa¬ su 3-tioallofanowego o wzorze ogólnym 1, w któ¬ rym X oznacza grupe lUO— lub I^S—, w której R1 oznacza grupe alkilowa o lancuchu prostym lub rozgalezionym o 1—12 atomach wegla ewentu¬ alnie podstawiona podstawnikami takimi jak atom chlorowca, korzystnie chloru lub grupa metoksy¬ lowa, grupe alkenyIowa o 2—12 atomach wegla, grupe alkinylowa o 3—12. atomach wegla, grupe fenylowa ewentualnie podstawiona atomem chlo¬ rowca, korzystnie chloru, grupa metylowa, grupa metoksylowa lub grupa nitrowa; grupe benzylo¬ wa ewentualnie podstawiona atomem chlorowca, korzystnie chloru, grupa metylowa, grupa meto¬ ksylowa lub grupa nitrowa, Y oznacza 5- lub 6- i '¦czlonowa grupe heterocykliczna, z heteroatomami takimi jak tlen, siarka lub azot lub dowolna kombinacja dwu z tych atomów, przy czym cal¬ kowita liczba heteroatomów jest nie wieksza niz 3, ewentualnie podstawiona grupa acetoksymetylo- wa, atomem chloru, grupa metylowa lub grupa nitrowa, R oznacza atom wodoru lub grupe me¬ tylowa^ Z oznacza atom chlorowca, korzystnie chloru grupe metylowa, grupe metoksylowa lub grupe nitrowa a n oznacza liczbe calkowita 0—3; Typowymi heterocyklicznymi grupami Y sa: fu- rylowa, imidazolilowa, izotiazolilowa, izoksazolilo- wa, N-metylopirylowa, oksadiazolilowa, tiazolilowa, tienylowa, triazynylowa i triazolilowa. Do grup korzystnych naleza: 2-furylowa, 5-izotiazolilowa, 1-metylopiryIowa, 2-pirydylowa, 2-pirylowa, 4-tia- zolilowa i 2-tienylowa.Sposród korzystnych zwiazków najkorzystniejsze sa te, w których Y oznacza grupe 2-furylowa lub 2-tienylowa, a R oznacza atom wodoru. W przy¬ padku, gdy Y oznacza grupe 2-furylowa, zwiazki te przedstawia wzór ogólny 2.Z grup weglowodorowych, R1 korzystne sa grupy alkilowe, a zwlaszcza nizsze gru¬ py alkilowe o 1—6 atomach wegla, zwlaszcza metylowa lub etylowa, dopuszczalne sa jednak in¬ ne grupy np. oktylowa, decylowa lub dodecylowa.Zwiazki stosowane jako substancja aktywna w srodku wedlug wynalazku mozna, na ogól, otrzy¬ mywac sposobami stosowanymi do otrzymywania 9069190691 analogicznych zwiazków znanych, zwlaszcza przez dzialanie na pochodna fenylenbdwuaminy o wzo¬ rze ogólnym 4, w którym T oznacza ugrupowanie —HNCNHC—X lub = C—Y zwiazkiem o wzo- ii ir i S O R rze 5, gdy T oznacza ugrupowanie —HNCNHC—X, II II S O a zwiazkiem o wzorze 6, gdy T oznacza ugrupo¬ wanie = C—Y. Symbole Z, X, Y, R i n maja ta- I R kie znaczenie, jak podano dla zwiazku o wzorze 1.Tak wiec zwiazki o wzorze ogólnym 1, mozna otrzymywac dzialajac zwiazkiem o wzorze ogól¬ nym 5 na zwiazek o wzorze ogólnym 7, lub dzia¬ lajac zwiazkiem o wzorze ogólnym 6 na zwiazek o wzorze ogólnym 8. W przypadku wytwarzania furfurylidenów, druga z tych reakcji korzystnie przeprowadza sie w obecnosci trzeciorzedowych amin.Ponizej podano szczególy obu dróg postepowa¬ nia, w obu przypadkach wychodzac z o-fenyleno- dwuiminy.W pierwszym przypadku na o-fenylenodwuimine dziala sie estrem kwasu izotiocyjanowego, otrzy¬ mujac 4-(2-aminofenylo)-3-tioallofanian, na który z kolei dziala sie aldehydem lub ketonem, otrzy¬ mujac odpowiednia zasade Schiffa, np. 4-(2-mety- lenoaminofenylo)-3-tioallofanian. Przebieg reakcji przedstawiono na schemacie 1. Wszystkie symbole maja znaczenie podane powyzej.Izotiocyjaniany o wzorze ogólnym 6 mozna lat¬ wo otrzymac sposobami opisanymi w literaturze.Jeden z tych sposobów polega na dzialaniu na ester kwasu chloromrówkowego tiocyjanianem amonu lub potasu w obecnosci obojetnego rozpuszczalnika, takiego jak aceton, 2-metoksyetanol, octan etylu, octan butylu lub toluen w podwyzszonej tempera¬ turze, np. 25—100°C. W przypadku uzycia tiocyja- nianu potasu, reakcje mozna przedstawic schema¬ tem 2.Izotiocyjanian oczyszcza sie przez destylacje, lecz w procesie tym czesto nastepuje znaczny rozklad termiczny lub polimeryzacja. Z tej przyczyny ko¬ rzystne jest uzycie, w dalszej reakcji z amina su¬ rowego izotiocyjanianu zidentyfikowanego na pod¬ stawie widma w podczerwieni.W reakcji o-fenylenodwuiminy z izotiocyjania- nem o wzorze ogólnym 6 zazwyczaj stosuje sie oba skladniki- w ilosciach stechimetrycznych. Reakcje prowadzi sie w obecnosci obojetnego rozpuszczal¬ nika, takiego jak eter, 2-metoksy-etanol, octan etylu, octan butylu lub toluen. Reakcja zwykle zachodzi latwo i przeprowadza sie ja w tempera¬ turze —20°C i powyzej. 4-(2-aminofenylo)-3-tioal- lofaniany o wzorze 7 zwykle wykrystalizowuja z mieszaniny reakcyjnej i sa oczyszczane znanymi sposobami, takimi jak rekrystalizacja. Nalezy uni¬ kac nadmiernego ogrzewania tych zwiazków, po¬ niewaz moze to prowadzic do tworzenia benzimi- dazolu jak przedstawiono na schemacie 3.Na 4-(2-aminofenylo)-3-tioallofaniany dziala sie nastepnie heterocyklicznym aldehydem lub keto¬ nem w obecnosci obojetnego rozpuszczalnika, ta- 40 45 50 kiego jak weglowodór aromatyczny i katalitycz¬ nych ilosci kwasu, takiego jak kwas p-toluenosul- fonowy. Reakcje przeprowadza sie najczesciej w temperaturze wrzenia rozpuszczalnika, lecz czesto w temperaturze 50—150°C. Trudnosci moga wy¬ niknac w przypadku aldehydów nie odpornych na dzialanie kwasów, takich jak furfural. Dla tych przypadków opracowano sposoby zmodyfikowane.Schematem 4 przedstawiono typowa reakcje z al¬ dehydem (2-tiofeno)-mrówkowym lub ketonem 2- -tienylometylowym.O-fenylenodwuaminy i heterocykliczne aldehydy oraz ketony sa w wiekszosci produktami dostep¬ nymi w handlu. Inne heterocykliczne aldehydy i ketony metylowe mozna otrzymac sposobami opi¬ sanymi w literaturze. Przykladowo, mozna do he¬ terocyklicznego pierscienia wprowadzic funkcje al¬ dehydowa przez formylowanie tlenkiem wegla, cy¬ janowodorem lub N-metyloformanilidem, przez dzialanie na pochodna chlorowcometylowa heksa- metylenoczteroamina, przez dzialanie etoksymety- loanilina z odczynnikiem Grignarda, przez hydro¬ lize pochodnej dwuchlorowcometylowej lub przez redukcje pochodnej acylohalogenkowej.W ponizszej tablicy 1 przedstawiono typowe zwiazki o wzorze 7 stosowane do wytwarzania zwiazków wedlug niniejszego wynalazku.Tablica 1 Zwiazki o wzorze 7, w których: zn= H H 4-CH3 -N02 4-(lub 5-)Cl 4-(lub 5-)CH3 4- 4-(lub 5-)N02 X= OCH3 OC2H5 OCH3 OC2H5 OCH3 OCH3 OCH3 OCH3 Temperatura rozkladu °C lub odnosnik literaturowy Patent Brytyjski 1214 415 Patent Brytyjski 1214 415 Patent Brytyjski 1214 415 Patent Brytyjski 1214 415 183—185 168—170 184—185 211—212 | 65 W drugim przypadku na o-fenylenodwuimine dzia?a sie równowazna iloscia heterocyklicznego aldehydu lub ketonu, otrzymujac o-(metylenoami- no)-aniline (zasade Schiffa), na która dziala sie nastepnie estrem hydrokarbyloksy-karbonyloizotio- cyjanianowym otrzymujac zwiazek o wzorze 1.Przebieg reakcji przedstawia schemat 5.Reakcje o-fenylenodwuminy ze zwiazkiem kar- bonylowym przeprowadza sie zwykle w obecnosci obojetnego rozpuszczalnika, takiego jak benzen lub toluen, najczesciej w temperaturze wrzenia rozpuszczalnika, lecz czesto w zakresie 50—150°C.Reakcje mozna pobudzac usuwaniem powstajacej wody. Jako rozpuszczalnik mozna stosowac alko-5 hol, lecz w tym przypadku nalezy ja przeprowa¬ dzac w temperaturze ponizej 0°C. Otrzymane za¬ sady Schiffa sa w wiekszosci zwiazkami znanymi.Reakcje zwiazków o wzorze 3 z izotiocyjanianem przeprowadza sie zwykle w obecnosci obojetnego rozpuszczalnika, takiego jak eter, 2-metoksyetanol, octan etylu, octan butylu lub toluen. Reakcja za¬ chodzi latwo w temperaturze pokojowej i w zakre¬ sie —20 do 100°C.Niektóre z wyzej opisanych zwiazków przejscio¬ wych mozna otrzymywac innymi znanymi sposo¬ bami. Na przyklad, na 2-aminonitrobenzen mozna dzialac izotiocyjanianem o wzorze 6, otrzymujac zwiazek o wzorze 9, który nastepnie redukuje sie, np. za pomoca polaczonych metalu i kwasu, do zwiazku o wzorze 7.W korzystnym wariancie tego sposobu otrzymu¬ je sie furfurylideny w obecnosci aminy trzeciorze¬ dowej. Tak wiec zwiazki o wzorze ogólnym 10, w którym Z i X maja znaczenie wyzej podane, a W oznacza atom wodoru, grupe acetoksymety-v Iowa, atom chloru, grupe metylowa lub grupe ni¬ trowa, otrzymuje sie dzialajac na zwiazek o wzo¬ rze ogólnym 11 izotiocyjanianem o wzorze 6, w obecnosci organicznej zasady typu trzeciorzedowej aminy. Symbole W, X, Z we wzorze 11 maja zna¬ czenie wyzej podane.O-furfurylidenoaminoaniliny o wzorze 11 sa omówione w literaturze, np. w Chemical Abstracts 61, 828Ób i 14860f i(1964) oraz 67, 11629m (1967).Otrzymuje sie je dzialajac na o-fenylenodwuami- ne równowazna iloscia furfuralu, ewentualnie w obecnosci trzeciorzedowej aminy. Przebieg reakcji przedstawia schemat 6. Symbole W, Z i n maja znaczenie wyzej podane, Reakcje przeprowadza Sie zwykle w obecnosci obojetnego rozpuszczalni¬ ka, takiego jak benzen lub toluen, najczesciej w temperaturze wrzenia rozpuszczalnika, iecz czesto w temperaturze 50—150ÓC. Jako rozpuszczalnik mozna stosowac alkohol, lecz w takim przypadku reakcje przeprowadza sie w temperaturze 0°C lub nizszej. Reakcje mozna pobudzac usuwaniem powstajacej wody. Jako czynnik stabilizujacy stosuje sie czasami trzeciorzedowa zasade, taka jak trójetyloamina lub dwumetyloanilina, lecz nie jest to konieczne.Sposród trzeciorzedowych amin znajduja zasto¬ sowanie takie, które w 25°C maja stala dysocja- cji rzedu 5 X lO-3 do 5 X 10~5. Typowymi takimi aminami sa: trójmetyloamina, trójetyloamina, trój- propyloamina, trójizobutyloamina, metylodwuety- loamina, czterometyloetylenodwuimina, N,N-dwu- metyloetanoloamina i dwumetyloanilina. Korzyst¬ nymi trzeciorzedowymi aminami sa trójetyloamina i trójpropyloamina. Amine stosuje sie zwykle w ilpsci 0,5—20% molowych. Przykladowo trójetylo- amine która ma ciezar czasteczkowy 101, stosuje sie tw ilosci 0,5—2,0 g na mol reagentów. Ilosc zwykle stosowana zawiera sie w granicach 5—15% molowych. Amine mozna dodawac badz do o-fur- furylidenoaminoaniliriy badz tez do estru hydro- karbyloksykarbonyloizotiocyjanianowego lub tez rozdzielic miedzy oba te reagenty.Reakcje o-furfurylidenoaminoaniliny o wzorze 11 z izotiocyjanianem o wzorze 6 w obecnosci 90691 6 trzeciorzedowej aminy (R3N) prowadzi sie zwykle w obojetnym rozpuszczalniku takim jak eter, 2-me¬ toksyetanol, octan etylu, octan butylu lub toluen.Reagenty stosuje sie w ilosciach równomolowych, lecz czesto stosuje sie izotiocyjanian w nadmiarze do 100%, korzystnie w nadmiarze 20—40%. Re¬ akcja przebiega latwo w temperaturze powyzej —20°C. 4-[2-(furfurylidenoamino)-fenylo]-3-tioallo- faniany o wzorze 10 zwykle krystalizuja z miesza- niny reakcyjnej i sa oczyszczane zwyklymi sposo¬ bami, np. w drodze rekrystalizacji. Nalezy unikac nadmiernego ogrzewania tych zwiazków, poniewaz moze to prowadzic do tworzenia benzimidazolL Przebieg reakcji przedstawia schemat 7.Ponizej podano kilka przykladów wytwarzania zwiazków stanowiacych substancje czynna w srod¬ ku grzybobójczym wedlug wynalazku.Przyklad I. Otrzymywanie 4-[2-(furfurylide- noamino)fenylo]-3-tioallofaniami metylu.Sposób 1. 11 g (0,040 mola) 4n(2-aminofenylo)-3- -tioallofanianu metylu w 200 ml benzenu dodano ,75 g (0,06 mola) furfuralu i katalitycznych ilosci kwasu p-toluenosulfonowego. Mieszanine reakcyj¬ na utrzymywano w ciagu 4 godzin w temperatu- rze wrzenia, oddzielajac z mieszaniny azeotropo- wej 0,9 ml wody. Nastepnie oziebiano mieszanine reakcyjna, otrzymujac cialo stale o barwie zóltej, które po wysuszeniu topnialo z rozkladem w tem¬ peraturze 150—152°C. Wydajnosc 4-[2-(furfurylide- noamino)fenylo]-3-tioallofanianu metylu wyniosla 8,1 g (55% teoretycznej).Sposób 2. Do zawiesiny 52,4 g tiocyjanianu po¬ tasu (0,565 mola) w 162 g octanu butylu, miesza-* nej w temperaturze 50—55dC szybkó dodano 52,4 g chloromrówczanu metylu (0,565 mola). Zachodzi¬ la lekko egzotermiczna reakcja. Mieszanine reak¬ cyjna utrzymywano w temperaturze 60°C w ciagu 4 godzin, w którym to czasie wydzielilo sie 2,6 li¬ tra dwutlenku wegla. Otrzymana mieszanine izo- *° tiocyjanianu metoksykarbonylowego oziebiano do temperatury 10ÓC i zachowano do dalszej reakcji.Do 39,2 g o-fenylenodwuiminy (0,362 mola) ewentualnym dodatkiem 2,2 g N,N-dwumetyloani- liny) dodano 37,0 g furfuralu (0,385 mola) w 119 g 45 toluenu. Mieszanine reakcyjna podgrzewano do temperatury 35°C, w ciagu 0,5 godziny. Roztwór odparowano nastepnie' pod cisnieniem 50 mm, zbierajac 93 g destylatu toluen-woda. Pozostala o-(2-furfurylidenoamino)aniline oziebiono do tem- 50 peratury pokojowej i dodano 3,0 g trójetyloaminy.Do utrzymywanej w temperaturze 0°C zawie¬ siny izotiocyjanianu metoksykarbonylowego doda¬ no 7 g trójetyloaminy, a nastepnie powoli o-(2-fur- furylidenoamino)aniliny, utrzymujac temperature 55 ponizej 35°C. Calosc mieszano w ciagu godziny, oziebiano do temperatury 10°C i odsaczono wytra¬ cony osad. Po przemyciu 100 ml zimnego toluenu oraz 300 ml wody i wysuszeniu otrzymano 100 g 4-[2^(furfurylidenoamino)fenylo]-3-tioallofaniami s° metylu o barwie zóltej, o temperaturze topnienia 155—156°C. Stanowi to 90% wydajnosci teoretycz¬ nej.W brytyjskim opisie patentowym nr 1214 415 podano w przykladzie XI sposób otrzymywania 65 l-benzylidenoamino-2-(3-metoksykarbonylo-2-tio-l u*eido)-benzenu. W sposobie tym dzialano izotio- cyjanianem metoksykarbonylowym na 2-benzylide- noaminoaniline w acetonie, w temperaturze od —5°C do pokojowej. Postepujac wedlug tego spo¬ sobu nie zdolano wyizolowac, wychodzac z o-(2- furfurylidenoamino)aniliny, 4-[2H(furfurylidenoami- nb)fenylo]-3-tioallofanianu. Równiez nie otrzymy¬ wano tego produktu, gdy nie dodawano trójetylo- aniliny. Zastosowanie zasady jest konieczne, gdy w reakcji biora udzial czule na dzialanie kwasów aldehydy lub ich zasady Schiffa. Udane byly na¬ tomiast próby otrzymywania 4-[2-(furfurylideno- amino)fenylo]-3-tioallofanianów korzystnym ogól¬ nym sposobem 2.Sposób 3. Do 60 g o-fenylodwuaminy (0,56 mo¬ la) w 500 ml toluenu dodano w temperaturze °C, 5 g N,N-dwumetyloaniliny (0,04 mola) i 56 g furfuralu (0,58 mola). Pod cisnieniem 50 mm w temperaturze 35°C, oddestylowano toluen i wode, otrzymujac 150,3 g stezonego roztworu toluenowe- go. Do powyzszego roztworu dodano 4 g trójetylo- aminy (0,04 mola) i ochlodzono go do temperatury pokojowej (roztwór D).Do 81 g tiocyjanianu potasu (0,835 mola) zawie¬ szonego w 300 ml octanu butylu dodano szybko, w temperaturze 60°C 81 g chloromrówczanu mety¬ lu (0,86 mola). Otrzymana mieszanine barwy zól¬ tej mieszano w ciagu 2 godzin, utrzymujac tem¬ perature 60°C Produkt oziebiono do temperatury °C i dodano 2 g trójetylóaminy (0,02 mola).Do powyzszego roztworu izotiocyjanianu meto- ksykarbonylowego dodano roztworu D, w tempera¬ turze ponizej 35°C i calosc mieszano w ciagu go¬ dziny, a nastepnie oziebiano do temperatury 10°C, co powodowalo wytracenie osadu, który odsaczano, wytrzasnieto z 600 ml wody i osuszono, otrzymu¬ jac 151,5 g produktu o temperaturze topnienia 154—155°C. Analiza elementarna: wartosci znale¬ zione 54,6% C, 4,2% H, 14,0% N, wartosci obliczo¬ ne dla Ci4Hl3N303S 55,3% C, 4,4% H, 13,8% N.Wydajnosc produktu jest 4-[2-(furfurylidenoami- no)fenylo]-3-tioallofanianu metylu wyniosla 90%.Struktura zostala potwierdzona przez analize wi¬ dma w podczerwieni. Produkt zawieral niewielka domieszke chlorku potasu.Sposób 4. Do 30,0 g o-fenylenodwuiminy (0,278 mola) w 325 ml toluenu dodano, w temperaturze 60°C 28,0 g furfuralu (0,292 mola). Mieszanine to- luen-woda oddestylowano w temperaturze 60°C, pod cisnieniem 130 mm, do otrzymania w kolbie 55 'g pozostalosci, do której dodano 2 g trójety¬ lóaminy (0,02 mola) (roztwór E).Do 40,5 g tiocyjanianu potasu (0,417 mola) za¬ wieszonego w 150 ml etylu dodano szybko, w tem¬ peraturze 45°C, 40,5 g chloromrówczanu metylu (0,429 mola). Calosc mieszano w ciagu 2 godzin w temperaturze 45°C, a nastepnie oziebiano do temperatury 10°C.Do otrzymanej zawiesiny izotiocyjanianu meto- ksykarbonylowego dodano 4 g trójetylóami¬ ny (0,04 mola), a nastepnie w ciagu 15 minut, roztwór E, nie przekraczajac temperatury 35°C.Calosc mieszano w ciagu godziny i przesaczono, przemyto osad 300 ml wody i osuszono, otrzy¬ mujac 57,3 g produktu o temperaturze topnienia 90^1 i 40 45 50 55 60 65 154—155°C. Analiza elementarna: wartosci znale¬ zione: 55,3% C, 4,3% H, 13,7% N, wartosci obliczo¬ ne dla C14H13N303S 55,4% C, 4,3% H, 13,85% N.Wydajnosc 4-[2-furfurylidenoamino/fenylo]-3-tioal- lofaniamu metylu wyniosla 68%.W tablicy 2 podano struktury pokrewnych 4-[2- -furfurylidenoamino)fenylo]-3-tioallofanianów o- trzymanych sposobami 3 i 4.W tablicy 5 przedstawiono temperatury topnienia lub rozkladu i dane analityczne dotyczace tych zwiazków.Tablica 2 Otrzymane zwiazki o wzorze ogólnym 10 Zwia- <¦ zek I II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI X OCH3 OC2H5 SC2H5 OC4H9-n OC8H17-n OC6H5 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH2CCl3 OCH2CH= =CH2 OCH2C6H5 W H H H H H H CH3 CH30(0)0CH2 H H H H N02 H H H Zn H H H H H H H H 4 (lub 5) -Cl 4 (lub 5) -CH8 4 (lub 5) -OCH3 4,5-Cl2 H H H H Przyklad II. Otrzymywanie 4-[2- noamino)fenylo]-3-tio-tioloallofanianu etylu tj. zwiazku III z tablicy 2.Do zawiesiny 20 g tiocyjanianu potasu (0,206 mo¬ la) w 125 ml 2-metoksyetanolu, utrzymywanej w temperaturze pokojowej, dodano 25 g (0,2 mola) S-etylowego chlorotiolomrówczanu. Calosc miesza¬ no w ciagu 3 godzin i odpedzono rozpuszczalnik.Do pozostalosci dodano 3 g trójetylóaminy i o-(2- -furfurylidenoamino)aniliny (0,185 mola) zawiera¬ jacej okolo 3 g trójetylóaminy, sposobem opisanym w przykladzie I. Po izolacji, przeprowadzonej spo¬ sobem opisanym w przykladzie I, otrzymano 24,5 g produktu o barwie zóltej. Po rekrystalizacji z benzenu otrzymano 14,3 g igiel barwy zóltej, top¬ niejacych z rozkladem w temperaturze 157—158°C.Wydajnosc 4-[2-(furfurylidenoamino/fenylo]-3-tio- tiodoalilofanianu etylu wyniosla 23%!.Przyklad III. Otrzymywanie 4-{2-(tienylide- noamino) fenylo]-3-tioallofanianu metylu to jest zwiazku XVII z tablicy 3.Mieszanine reakcyjna skladajaca sie z 4,5 g 4-<2- -aminofenylo)-3-tioallofanianu metylu (0,02 mola), 2,24 g tiofeno-2-karboksyaldehydu (0^02 mola) i 10090691 ml benzenu mieszano w ciagu 2 godzin w tempe¬ raturze wrzenia, a z azeotropowego destylatu od¬ prowadzano wode. Z oziebionej mieszaniny reak¬ cyjnej odsaczono 3,5 g produktu o temperaturze topnienia 175°C z rozkladem. Wydajnosc 4-[2-(tie- nylidenoamino)fenylo]-3-tioallofanianu metylu wy¬ niosla 55%.W tablicy 3 podano struktury otrzymanych zwiazków. W tablicy 5 podano ich wlasnosci.Tablica 3 Otrzymane zwiazki o wzorze ogólnym 13 Zwia¬ zek XVII XVIII XIX XX XXI XXII XXIII R H H H H H H CH3 X OCH3 OC2H5 OCH3 OCH3 OCH3 OCH3 OCH3 W H H Cl H H H H Z H H H 4 (lub 5) -Cl 4 (lub 5) -Cl 4 (lub 5) -N02 H Przyklad IV. Otrzymywanie 4-[2-tienylideno- amino)-4(lub 5)-chlorofenylo]-3-tioallofanianu me-. tylu to jest zwiazku XX z tablicy 3.Do 10 g 4-chloro-o-fenylidenodwuaminy (0,07 mo¬ la) w 175 ml eteru dodano 8 g izotiocyjanianu me- toksykarbonylowego (0,068 mola) w temperaturze ponizej 25°C. Zawiesine przesaczono, suszono po¬ zostalosc otrzymujac 12,3 g zólto zabarwionej sub¬ stancji o temperaturze topnienia 184—185°C z roz¬ kladem. Z drugiego rzutu (6,1 g) otrzymano, po przekrystalizowaniu, 4,3 g substancji o temperatu¬ rze topnienia 183—185°C. Laczna wydajnosc z obu rzutów 4-(2-amino-4/lub 5)-chlorpfenylo)-3-tioallo- fanianu metylu wyniosla 92%.Do 6 g 4-(2-amino-4(lub 5)-chlorofenylo)-3-tioal- lofanianu metylu (0,023 mola) w 250 ml benzenu dodano 2,8 g 2-tiofenokarboksyaldehydu (0,025 mo¬ la), zawierajacego okolo 0,2 g kwasu p-toluenosul- fonowego. Mieszanine reakcyjna utrzymywano w temperaturze wrzenia w ciagu 6 godzin, azeotro- powo odpedzajac wydzielajaca sie wode. Pozosta-. losc po odpedzeniu rozpuszczalnika, o barwie po- maranczowo-brazowej roztarto z eterem, otrzy¬ mujac 4 g substancji o barwie pomaranczowo-zól- tej, topniejacej z rozkladem w temperaturze L73— —175°C. Poniewaz, jak wykazala analiza, produkt byl mieszanina, poddano go dzialaniu 3 g alde¬ hydu 2-tiofenokarboksylowego. W wyzej opisany sposób wyizolowano 3,3 g produktu o barwie po- maranczowozóltej, topniejacego z rozkladem w tem¬ peraturze 183^l°C. 'Wydajnosc 4-[2-(tienylidenoa- mino)-4-(lub 5) -chlorofenylo]-3-tioallofanianu me¬ tylu wyniosla 41%.Przyklad V. Otrzymywanie 4-{2n(tienylideno- amino)-4(lub 5) chlorofenylo]-3-tioallofanianu me¬ tylu to jest zwiazku XXI z tablicy 3.Do mieszaniny 9,5 g 4-chloro-o-fenylenodwuami- ny (0,067 mola) w 250 ml benzenu dodano 7,5 g 40 45 55 ® 2-tiofenokarboksyaldehydu (0,067 mola). Mieszani¬ ne utrzymywano w ciagu 3 godzin w temperaturze wrzenia, nastepnie zatezano do polowy objetosci, dodano 25 ml heksanu i ochlodzono, w wyniku czego otrzymano olej. Olej, który oddzielano i zatezano byl mieszanina, która poddano reakcji z dalsza porcja 2,5 g 2-tiofenokarboksyaldehydu, w ciagu 2 godzin, w temperaturze wrzenia, nastep¬ nie oziebiono, co powodowalo wytracenie osadu.Po odsaczeniu i wysuszeniu jego ilosc wyniosla 4,1 g. Z przesaczu oddzielono 3,2 g oleistego osadu.Obie porcje polaczono i przekrystalizowano z mie¬ szaniny heksanu z eterem (50 :50), otrzymujac 5,2 g substancji o temperaturze topnienia 69—70°C. Wy¬ dajnosc 2-tienylidenoamino-4(lub 5)-chloroaniliny wyniosla 33%.Do 4 g 2-tienylidenoamino-4(lub 5)chloroaniliny (0,017 mola) w 120 ml eteru dodano 2 g izotiocy¬ janianu metoksykarbonylowego (0,017 mola) i ca¬ losc mieszano w ciagu godziny w temperaturze po¬ kojowej. Wytracony osad o barwie zóltej odsaczo¬ no, przemyto eterem i suszono, otrzymujac 1,8 g substancji o temperaturze topnienia 143—144° z rozkladem. Wydajnosc 4-[2-(tienylidenoamino)- -4(lub 5)-chlorofenylo]-3-tioallofanianu metylu wy¬ niosla 30%.Przyklad VI. Otrzymywanie 4-[2-(a-metylo-2- -tienylidenoamino)fenylo]-3-tioallofanianu metylu to jest zwiazku XXIII z tablicy 3.Mieszanine reakcyjna, skladajaca sie z 15 g o-fenylenodwuiminy (0,139 mola) 19 g 2-acetylo- tiofenu (0,151 mola) i 200 ml benzenu ogrzewano w ciagu 56 godzin w temperaturze wrzenia, od¬ dzielajac wydzielajaca sie w reakcji wode. Roz¬ puszczalnik odparowano, otrzymujac pozostalosc barwy zóltej, która roztarto z heksanem i prze¬ krystalizowano z mieszaniny benzenu z heksanem (1 :1), otrzymujac 15,4 g 2-(a-metylo-2-tienylideno- amino)aniliny.Do roztworu 5 g 2-(a-metylo-2-tienylidenoamino)- aniliny (0,0232 mola) w 175 ml eteru wkraplano 3 g izotiocyjanianu metoksykarbonylowego (0,0256 mola), w temperaturze 24—28°C. Z zólto zabarwio¬ nego roztworu odpedzano rozpuszczalnik, otrzy¬ mujac oleisty osad, który roztarto z zimnym ete¬ rem otrzymujac, po odsaczeniu, 2 g substancji o temperaturze topnienia 126—127°C z rozkladem.Wydajnosc 4-[2-(a-metylo-2-tienylidenoamino)feny- lo]-3-tioallofanianu metylu wyniosla 26%.Przyklad VII. Otrzymywanie 4-[2n(2^pirolilo- metylenoamino)fenylo]-3-tioallofanianu metylu to jest zwiazku XXIV.Roztwór 15 g o-fenylenodwuaminy (0,139 mola) w 45 ml metanolu ochladzano do temperatury —10°C, a nastepnie dodano do niego, w tempera¬ turze nie przekraczajacej —5°C, roztwór 13,2 g pirolo-2-karboksyaldehydu (0,139 mola) w 45 ml metanolu. Calosc mieszano w ciagu 0,5 godziny w temperaturze ponizej —5°C. Zólto zabarwiony osad odsaczono, otrzymujac 10,5 g produktu o tempera¬ turze topnienia 106—108°C. Po pewnym czasie wy¬ tracono z roztworu dalsze 12,4 g osadu o tempe¬ raturze topnienia 106—108°C. Polaczone osady sta¬ nowily 89% wydajnosci 2H(2-piroUlometylenoami- no)aniliny,90691 li Do roztworu 5 g 2-(2-pirolilometylenoamino)ani¬ liny (0,027 mcla) w 175 ml roztworu dodano 3,7 g izotiocyjanianu metoksykarbonylowego (0,315 mo¬ la) i calosc mieszano w ciagu godziny. Wytracony osad odsaczono i suszono, otrzymujac 5,1 g sub- 5 stancji bsrwy pomaranczowozóltej, o temperaturze topnienia 178—179°C z rozkladem. Wydajnosc 4-[2- (2-pirolometylenoamino)fenylo-3-tioallofanianu me¬ tylu wyniosla 63%.Przyklad VIII. Otrzymywanie 4-[2-(l-metylo- ao -2-pirolometylenoamino)fenylo]-3-ticallofaniami me¬ tylu, to jest zwiazku XXV.Mieszanine 10 g o-fenylenodwuiminy (0,0926 mo¬ la) 10,1 g N-metylopirclo-2-karboksyaldehydu (0,0926 mola) i 175 ml benzenu ogrzewano w cia- 15 gu godziny w temperaturze wrzenia, oddzielajac wode, nastepnie odpedzano rozpuszczalnik, otrzy¬ mujac ciemno zabarwiona, oleista pozostalosc, któ¬ ra dwukrotnie roztarto z porcjami po 100 ml go¬ racego heksanu. Ekstrakty heksanowe oziebiano, w otrzymujac 10,2 g oleju zóltej barwy, który roz¬ puszczono w 100 ml eteru. Ilosc ta odpowiadala¬ by, gdyby substancja byla czysta, 0,05 mola 2-(l- -metylo-2-pirolilometyloamino)aniliny. 70 ml po¬ wyzszego roztworu (0,035 mola) zadano 5 g izotio- 25 cyjanianu metoksykarbonylowego (0,43 mola), otrzymujac 4,1 g ciala stalego o temperaturze top¬ nienia 155—157°C, stanowiacego mieszanine poza¬ danego produktu i 4-(2-aminofenylo)-3-tioallofania- nu metylu. 3,8 g tego produktu zawieszono w 175 30 ml benzenu zawierajacego 0,1 g kwasu p-tolueno- sulfonowego i poddano dalszej reakcji z 3 g N- -metylcpirolo-2-kairboksyaldehydu (0,095 mola), og¬ rzewajac ja w ciagu 3 godzin w temperaturze wrzenia. Mieszanine reakcyjna nastepnie ogrzewa- 35 no w ciagu 0,5 godziny z weglem aktywnym, prze¬ saczono, a z przesaczu odpedzono rozpuszczalnik, otrzymujac oleista pozostalosc. Po roztarciu z ete¬ rem otrzymano 2,4 g produktu o temperaturze to¬ pnienia 171—172°C z rozkladem. Wydajnosc 4-[2- 40 -(l-metylo-2-pirolilometylenoamino)fenylo]-3-tioal- lofanianu metylu wyniosla 22%.Przyklad IX. Otrzymywanie 4-[2-(5-izotiozo- lilo-metyleno-amino)fenylo]-3-tioallof aniami metylu to jest zwiazkuXXVI. 45 Mieszanine reakcyjna, skladajaca sie z 9,4 g o- -fenylenodwuaminy (0,0867 mola) i 9,8 g 5-izotia- zolokarboksyaldehydu (0,0867 mola) i 80 ml ben¬ zenu ogrzewano w ciagu 2 godzin w temperatu¬ rze wrzenia, oddzielajac wode reakcyjna. Po od- 50 pedzeniu rozpuszczalnika otrzymano jako pozo¬ stalosc olej barwy czerwonopomaranczowej. Po roz¬ tarciu ze 100 ml zimnej mieszaniny eteru z hek¬ sanem (1:1) otrzymano 9,1 g ciala stalego o bar¬ wie czerwonopomaranczowej. Analiza widma w 55 podczerwieni potwierdzila, ze otrzymano 2-(5-izo- tiazolilometylenoamino)aniline. Wydajnosc wyniosla 52%.Do roztworu 5 g 2-(5-izotiazolilometylenoamino)- aniliny (0,0246 mola) w 100 ml eteru dodano 3,5 g ™ izotocyjanianu metoksykarbonylowego (0,03 mola) i calosc mieszano w ciagu godziny. Wytracono osad barwy czerwonopomaranczowej, który odsaczono i suszono,, otrzymujac 3,5 g substancji o tempera¬ turze topnienia 176—177°C z rozkladem. Wydajnosc 65 12 4-[-2-(5-izotiazolilometylenoamino)fenylo]-3-tioallo- fanianu metylu wyniosla 46%.Przyklad X. Otrzymywanie 4-[2-(2-pirydylo- metylenoamino)fenylo]-3-tioallofanianu metylu to jest zwiazku XXVII.Mieszanine reakcyjna, skladajaca sie z 7,1 g 4-(2- -aminofenylo)-3-tioallofaniami metylu (0,0316 mo¬ la), 3,7 g 2-pirydynokarboksyaldehydu (0,0346 mo¬ la), 0,2 g kwasu p-toluenosulfonowego i 250 ml benzenu ogrzewano w ciagu 3 godzin w tempera¬ turze wrzenia. Po oziebieniu wytracono staly pro¬ dukt uboczny barwy brazowej, którego ilosc po odsaczeniu wyniosla 3,2 g. Przesacz zadano 150 ml heksanu, otrzymujac 4,3 g produktu o barwie pur¬ purowej, topniejacego w temperaturze 144—5°C, z rozkladem. Wydajnosc 4-[2-(2-pirydylometyleno- amino)fenylo]-3-tioallofaniami metylu wyniosla 43%.W tablicy 4 przedstawiono otrzymane zwiazki wedlug grupy Y.W tablicy 5 podano dane fizykochemiczne tych zwiazków z tablic 2, 3 i 4.Tablica 4 Otrzymane zwiazki o wzorze ogólnym 14 Zwiazek I XVII XXIV xxv XXVI 1 xxvii ' Y fvryl tienyl pirolil N-metylopirolil -izotiazolil pirydyl 4-(2-metylenoaminofenylo)-3-tioallofaniany sa znakomitymi srodkami grzybobójczymi. Nadaja sie one szczególnie do zwalczania fitopatologenicznych grzybów z grup Ascomycetes i Fungi Imperfecti.Rodzajami grzybów, które mozna zwalczac srodka¬ mi wedlug wynalazku sa przykladowo: Acanthor- hynchus; Acanthostigma, Acremonium; Acrostalag- mus; Acrospora; Aspergillus, np. A. Oryzae, A. repens i A. terreus; Botryosphaeria; Botryospor- ium; Botrytis, np. B. cinerea; Calonectria; Calos- phaeria; Cenangium; Cephalosporium; Cephalothe- cium; Ceratostomella; Cercospora, np. C. apii; Cerco- sporella Claviceps; Cleistothecopsis; Coccomyces; Cryptosporella; Dasyschypha; Diaporthe; Didyma- ria; Didymellina; Didymosphoeria; Dothidella; En- dothia, Epichloe; Erysiphe, np. E. graminie i E. polygoni; Fabraca; Fusidium; Gibberella; Gloespo- rium, np. G. aridium, G. fagi, G. musarum i G. auercinum; Glomerella, np. G. cingulata i G. gos- sypii; Gnomonia; Guignardia; Herpotrichia; Hya- lodema; Hypoderma; Hypodermella; Hypoxylon; Keithia; Leptosphaeria; Lophodermium; Meliola; Microsphaera; Monilia; Monilinia, np. M. fructio- cola; Mycogone; Mycosphaerella; Nectria, np. N. episphaeria; Neofabraea; Neopeckia; Nummullaria; Oidiopsis; Oidium; Oospora; Ophiobolus; Penici- lium, np. P. diversum, P. funiculosum, P. italicum, P, oxalicum i P. yemaculosum; Phabdocline; Pha-13 90691 Tablica 5 14 Zwiazek 1 I II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI XVII XVIII XIX XX XXI XXII XXIII XXIV xxv XXVI XXVII Tempera¬ tura top¬ nienia °C 2 155—6 *). 113—115 *) 157—158 *) 122—124 *) 84—85*) 172—173 *) 127—128 *) 149—150 *) 188—189 *) 168—169 *) 163—164 *) 202—203 *) 206—208 *) 166—167 *) 108—110*) 161—162 *) 163—165 *) 136—137 *) 149_151 *) 183—184 *) 143—144 *) 203—204 *) 126—127 *) 178—179 *) 171—172*) 176—177 *) 144—145 *) Wzór sumaryczny 3 C14H13N3O3S Ci5H15N303S C15H15N3O2S2 Ci7Hi9N303S C21H27N3O3S C19H15N303S C15H15N3O3S C17H17N305S C14H12CIN3O2S Ci5H15N303S C15H15N304S Ci4Hi8Cl2N303S Ci4H12N405S C^H^ClgNgOgS C16H15N303S C20H17N3O3S C14H13N302S2 Ci5H15N302S2 C14H12CIN3O2S2 C14H12C1N302S2 C^H^ClNgC^Sg C14H12N404S2 C15H15N302S2 C14H14N402S Cl5Hi6N402S Cl3H12N402S2 Ci5H14N402S C 4 55,5 56,9 54,0 59,2 62,4 62,5 56,8 54,4 49,6 56,8 54,0 45,5 48,2 42,8 58,3 62,0 52,7 54,1 47,7 47,6 47,7 46,2 54,0 55,7 57,0 48,7 57,3 (55,3) (57,2) (54,0) (58,9) (62,8) (62,7) '(57,4) (54,3) (49,6) (57,0) (54,4) (45,6) <48,6) (43,0) <58,3) (63,1) (52,4) (53,1) (47,5) (47,6) (47,6) (45,7) (54,0) (56,2) (57,2) (48,9) (57,0) A naliza elementarna**) H 4,3 4,8 4,5 ,6 6,6 4,1 4,8 4,5 3,6 4,8 4,6 2,1 3,5 2,9 ,2 4.5 4,1 4,5 3,4 3,4 3,4 3,3 4,5 4,7 ,1 3,8 4,5 (4,4) (4,8) •(4,7) (5,9) (6,3) (4,2) (4,8) (4,6) (3,5) (4,9) (4,7) (2,7) (3,4) (3,0) (4,6) (4,5) (4,2) (4,4) (3,5) (3,5) (3,1) (3,6) (4,5) (4,4) (5,0) (3,9) (4,5) N 6 13,9 (13,8) 13,3 (13,1) 12,6 (12,7) 12,2 (12,1) ,4 (10,5) 11,5 (11,8) 13,2 (13,3) 11,2 (11,2) 12,5 (12,2) 13,3 (13,1) 12,6 (12,5) 11,4 (11) 16,1 (16,0) ,0 (9,8) 12,9 (12,8) ,7 <11,11 13,2 (13,2) 12,6 (12,8) 11,9 (11,8) 11,9 (11,4) 11,9 (H,7) ,4 (15,5) 12,6 (12,5) 18,5 (19,0) 17,8 (17,4) 17,5 (17,4) 17,9 (17,8) O 7 ,9 (16,0) ,1 (15,2) 9.6 (10,1) 13,9 (14,1) 12,2 (12,0) 13,1 (13,3) ,2 (15,6) 21,3 (21,6) 14,3 (14,6) ,2 (15,1) 19,2 (19,3) 13,2 (13,2) 23,0 i(22,9) 11,4 (11,4) ,0 (14,6) 13,0 (12,7) 9,6 (10,0) 9,1 (9,3) 9,0 (9,9) 9,0 (9,7) 17,6 (17,7) 9,6 (9,9) ,6 (10,6) ,0 (10,6) ,0 (9,8) ,2 (10,1) S "®~~' ,6 (10,5) ,1 (9,8) 1 19,2 (19,3) 9,3 (9,4) 8,1 (8,0) 8,2.; (8,2) ,1 (10,0) 8,6 (8,5) 9,5 (9,5) ,l (9,8) 9,6 (9,6) 8,6 (8,8) 9,2 (8,9) 7,6 (7,9) 8,9 (8,7) (8,5) 19,2 (19,3) 18,1 (18,0) 18,1 (18,9) 18,1 (17,7) 19,3 (19,4) ,6 (10,5) ,0 (10,0) ,0 (19,8) ,2 (10,5) 1 *) z rozkladem **) Liczba w nawiasie oznacza wartosc teoretyczna, obliczona ze wzoru sumarycznego cidiella; Phyllactinia; Phyllachora; Physalospora; Piricularia, np. P. oryzae; Plectodiscella; Pleosphae- rulina; Pleospora; Plowrighttia; Podosphaera, Pseu- dopeziza; Pyrenophora; Quvlaria; Ramularia; Rhy- tisma; Rosellinia;Rhizina; Sclerotinia, np. S. sclero- tiorum; Septocylindrium; Sphaerotheca, np. S. fuli- ginea; Sphoerulina; Sterigmatocystus; Taphrina; Thielavia; Titea; Trochila; Tricholadia; Trichospho- eria; Uncinula; Ustilaginoidea; Valsa; Venturia; Verticilium, np. V. albo-atrum.Powyzsze 4-(2-metylenoaminofenylo)-3-trioallofa- niany wykazuja wysoka grzybobójcza aktywnosc ukladowa, tzn. chronia rosline przed atakiem grzy¬ bów zarówno- od strony zewnetrznej, jak i od strony wewnetrznej. Rozwazania na temat mecha¬ nizmu dzialania ukladowych srodków grzybobój¬ czych mozna znalezc w World Review of Pest Control 2 (3), 1963, gdzie podano przyklady tego typu dzialania w przypadku fenylotiosemikarbazy- dów. Rozwój ukladowy srodków grzybobójczych w dziesiecioleciu poprzedzajacym powyzszy artykul mozna znalezc w PANS 18 (1), 1972. W powyz¬ szym artykule omówiono wlasciwosci ukladowych 55 65 srodków grzybobójczych, miedzy innymi benzimi- dazoli i pokrewnych struktur, takich jak niektóre 3-tioallofaniany.Srodki grzybobójcze wedlug wynalazku moga byc stosowane na nasiona, listowie lub glebe. Jako ukladowe srodki grzybobójcze sa one szczególnie efektywne przy nanoszeniu na glebe.Wstepna ocene wlasciwosci grzybobójczych zwiaz¬ ków stosowanych jako substancja aktywna w srod¬ ku wedlug wynalazku przeprowadzono zraszajac rosliny roztworem o stezeniu zwiazku 300 czesci na milion w ilosci okolo 14,25 m3/ha. Roztwór lub zawiesine do opryskiwan sporzadzono przez rozpu¬ szczenie odwazonej ilosci zwiazku w mieszaninie 50 :50 acetonu z woda i dodanie do roztworu ta¬ kiej samej ilosci wody.Ogólny sposób przeprowadzania testów grzybo¬ bójczych polegal na opryskaniu rosliny w donicz¬ ce, w stadium rozwoju, w którym byla ona podat¬ na na odpowiednia chorobe grzybowa. W tym ce¬ lu umieszczano doniczke z- roslina na ruchomej tasmie, opryskiwano i pozwalno obeschnac. Na¬ stepnie rosline inokulowano odpowiednimi zaród-90691 16 Tablica 6 Choroby roslin oceniane w badaniu wstepnym 1 Choroba grzybowa (inoculum/zarodniki ml) 1) Botrytis cinerea (150 000) 2) Erysiphe polygoni (10—25 000) 3) Piricularia oryzae (10—25 000) 4) Phytophtora infestans (50—60 000) ) Plasmopora viticola (150 000) 6) Helminthosphorium teres (10—15 000) 7) Cercospora apii (25 000) 8) Puccinia recondita (60 000) Roslina (wiek) fasola <10 dni) Vicia faba fasola (2 tygodnie) Phaseolus vulgaris ryz (2 tygodnie) Oryza sativa pomidory (3 tygodnie) Lycopersicum esculentum sadzonki winorosli (stadium 3—4 liscieniowe) Vitis vinifera owies (6 dni) Hordeum vulgare seler (rozsada 6—8 tygodni) Apium graveolens pszenica (6 dni) Triticum vulgare Czas inkubacji i temperatura 3 dni (27—28°C) dni (temperatura otoczenia) 1 dzien * + 5—8 dni (27—28°C) 1,5—2 dni (13°C) 2—3 dni (2l°C) 2 dni (21°C) * 4 dni (temperatura otoczenia) 1 dzien (21°C) * 1 dzien (27°C) * 3—4 dni i(24°C) 1 dzien (27°C) * 14—18 dni (temperatura otoczenia) 1 dzien (21°C) * 6—8 dni (temperatura otoczenia) *) wysoka wilgotnosc Tablica 7 Stopien ograniczenia rozwoju choroby przy stezeniu 300 czesci na milion Zwiazek I II III IV V VI VII VIII IX X XI XII XIII XIV XVII XVIII XIX XX XXI XXII XXIII XXIV xxv XXVI XXVII B. cinerea A A A A E A A A D A B E B A A B A B D C B B A B B E. polygoni A A 4 A B A A A A A A C A A A A A A A E A A A A A P. oryzae A E A B E B A B E B B E A A B B B E E E C B C A C A infestans E B E E — E E E E E E E E E E E E E E E E E E E E P. viticola E — — — — — — — — — — — — — E — — — — — E E E H. teres E E E E E E E E E E E E B E E E E E E E E E E E E C. apii A — — — — — — — — — — — — — — — — . — — — — — ^ .^ — P. recondita D B C D E E B C D D D E E C D D C B D E A D A ¦ D C17 nikami grzybów i inkubowano do rozwoju sym¬ ptomów choroby, po czym oceniano stopien ogra¬ niczenia rozwoju choroby. Stosowano nastepujaca skale ocen: A = zahamowanie 97—100% B = zahamowanie 90—96% C = zahamowanie 70—89% D = zahamowanie 50—70% E = brak aktywnosci, zahamowanie ponizej 50%.Rosliny i choroby grzybowe poddane badaniom podano w tablicy 6. Wstepna ocene wlasciwosci grzybobójczych zwiazków przedstawiono w tabli¬ cy 7.Traktujac niektóre z powyzszych przykladów jako typowe, przeprowadzono badania dalsze i spe¬ cjalne, w sposób nizej opisany.Przyklad XI. Badanie A — dawka/efekt 1. Plesn proszkowa fasoli (Erysiphe polygoni).Odwazona ilosc potencjalnego srodka grzybobój¬ czego rozpuszczono w acetonie i rozcienczono zde- mineralizowana woda, zawierajaca 0,05 ml emul¬ gatora — modyfikowanej zywicy alkilogliceryno- ftalowej w 100 ml wody. Stezenie doprowadzono do 25 czesci na milion a roztwór podstawowy roz¬ cienczono nastepnie przez podwajanie objetosci, 90691 18 otrzymujac szereg rozcienczen do 1,5 czesci na mi¬ lion. Roztworami o róznych stezeniach spryskano kielkujace nasiona fasoli, w ilosci dajacej calko¬ wite zmoczenie rosliny. Dla kazdego stezenia pró¬ by przeprowadzano dwukrotnie. Rosliny obsycha¬ ly w ciagu 20 godzin, a nastepnie byly inokulowa- ne zawiesina zarodników Erysiphe polygoni, zawie¬ rajaca 2 X 104 zarodników w ml. Inokulowane i kontrolne rosliny utrzymywano w ciagu 10 go¬ dzin w cieplarni w temperaturze 24—27°C Poli¬ czono ilosc plam plesni, a stopien zahamowania chorobowego obliczono z wzoru: Stopien zahamowania choroby = liczba plam na roslinach kontrolnych liczba plam na roslinach traktowanych liczba plam na roslinach kontrolnych X100 Wyniki przedstawiono w tablicy 8. 2. Plesn proszkowa ogórków (Sphaerotheca fu- liginea).Kielkujace nasiona ogórków, o dwóch dobrze roz¬ winietych lisciach i malym lisciu trzecim opryska¬ no az do calkowitego zmoczenia, roztworami 4-[2- - lu (przyklad I) o róznych stezeniach. Rosliny ob¬ sychaly w ciagu kilku godzin, po czym inokulowa- Tablica 8 Dawka/efekt na badanej fasoli Zwiazek I II III IV VI VII VIII IX X XI XII XVII XVIII XIX XX XXI XXII XXIII XXIV xxv XXVI XXVII % zahamowania choroby przy stezeniach czesci na milion 100 99,5 97,9 91,7 0 100 100 98,8 87,3 100 91,6 100 100 100 95,2 94,8 91,6 100 100 100 100 99,0 12,5 98,4 95,3 98,4 63,0 0 100 100 86,8 75,9 94,9 85,0 98,8 98,0 100 96,2 87,5 0 100 100 100 100 98,5 6,2 94,6 86,6 83,1 29,7 0 100 98,4 68,8 ,3 96,8 82,1 95,7 79,3 100 86,7 62,6 0 100 100 98,1 98,8 95,0 3,1 96,1 36,6 85,5 34,0 0 95,5 92,1 0 39,8 49,3 0 92,7 78,1 96,2 80,5 0 0 96,8 94,3 96,2 97,7 79,8 1,5 95,7 0 — — — — — 0 — — — 91,5 0 -~ — — — — — — 89,7 53,719 90691 no je zawiesina zarodników Sphaerotheca fulginea, zawierajaca okolo 2 X 104 zarodników w ml. Ro¬ sliny natychmiast umieszczono w cieplarni w tem¬ peraturze 24—27°C i po uplywie 11 dni obliczono e/o zahamowania rozwoju choroby. Otrzymano na¬ stepujace wyniki: °/o zahamowania rozwoju choroby przy stezeniu czesci na milion Zwiazek wedlug 50 25 12,5 6,3 3,1 1,6 przykladu I 100 100 99,6 97,9 94,3 72^5 ' Przyklad XII. Badanie B. Szczatkowa akty¬ wnosc po deszczu.Po opryskaniu chemicznym niektóre z roslin te¬ stowych poddano dzialaniu symulowanego deszczu ,4 mm, a nastepnie inokulowano je zarodnikami fitopatogennych grzybów. Wyniki przedstawiono w tablicy 9.Przyklad XIII. Badania ukladowe. C. Wchla¬ nianie przez korzenie. 1. Zaraza ryzu (Piricularia oryzae).W plastikowych doniczkach wyhodowano sa¬ dzonki ryzu do wysokosci 2,5—8 cm. Zwiazek XVII rozpuszczono w mieszaninie: aceton: metanol: woda (1 :1 i 2), dobierajac stezenie tak, ze 15 ml roztwo¬ ru zawieralo okreslona, w czesciach na milion, dawke, stosowana do podlewania rosliny poprzez 2. Plesn proszkowa ogórków (Sphaerotheca fuli¬ ginea) Rosliny ogórka, posiadajace 2 dobrze rozwinie¬ te liscie, rosnace w 8 cm plastikowych donicz¬ kach, podlewano 15 ml roztworu zawierajacego rózne stezenia, wyrazone w czesciach na milion, Zwiazek XVII czesci na milion w wodzie do ¦¦ podlewania 150 300 °/o zahamowania rozwoju choroby 91,7 98,0 zwiazku XVII. Rosliny opryskano nastepnie zawie¬ sina zarodników S. fuliginea, zawierajaca 2 X 104 zarodników w ml. Inokulowane rosliny natych¬ miast umieszczano w cieplarni, w temperaturze 29—32°C i okresowo obserwowano rozwój choroby.Otrzymano nastepujace wyniki: W celu dalszej oceny trwalosci czynnosci ukla¬ dowej, rosliny ogórka uzyte w badaniach odpor¬ nosci na dzialanie deszczu, opisanej w czesci B, tablica 9, poddano okresowej obserwacji rozwoju Tablica 9 Badanie wplywu deszczu na skutecznosc ochrony zwiazkiem XVII (1,2 g/litr) Choroba Botrytis cinerea na fasoli Erysiphe polygoni na fasoli Piricularia oryzae na ryzu Sphaerotheca fuliginea na ogórkach Cercospora apii na selerach Puccina recondita na pszenicy -*) B A C B A ' C 1/16 deszcz + **) E B E A A B — B A C B A B i/8 deszcz + C B E A A A — A.A B B — — 1/4 deszcz + B A E.A - — — A A B B — — 1/2 deszcz + A A C A — — *) bez deszczu **) z deszczem glebe. Opryskane rosliny ryzu byly utrzymywane 60 w typowych warunkach cieplarnianych, w tempe¬ raturze okolo 27°C, w ciagu 8 dni. Inokulowano je zarodnikami P. Oryzae, a procentowe zahamowa¬ nie rozwoju choroby odczytywano po uplywie 6 dni. Otrzymano nastepujacewyniki; •* S. fuliginea. Poczyniono nastepujace obserwacje: Zwiazki stanowiace substancje aktywna w srod¬ ku wedlug wynalazku przy niskich dawkach za¬ pewniaja dobra ochrone przed choroba w czasie przekraczajacym 5 tygodni po opryskaniu listowia lub gleby.90691 21 22 Zwiazek XVII Czesci na milion w wodzie do podlewania 125 250 500 °/o zahamowania choroby po 6 tygodniach pod¬ lewania E E A Zwia¬ zek XVII Tygod¬ ni po oprys¬ kaniu - rosliny 3 4 Minimalne efektywne ste¬ zenie (czesci na milion), da¬ jace 50% zahamowanie roz¬ woju plesni bez deszczu 150 150 300 z deszczem ponizej 75 600 600 3. Plesn proszkowa pszenicy (Erysiphe graminis). a. Podlewanie gleby Rosliny pszenicy w wieku 5—7 dni, rosnace w plastikowych doniczkach, przycieto do wysokosci 38—50 mm i podlano 15 ml wodnego roztworu zwiazku XVII, typowego przedstawiciela zwiazków stosowanych w srodku wedlug wynalazku. Rosliny umieszczono nastepnie na przeciag 2 dni w cie¬ plarni w temperaturze 24°C, po czym inokulowano, rozpylajac na nie zarodniki z roslin pszenicy za¬ kazonej E. graminis. Ocene rozwoju choroby prze¬ prowadzono po uplywie 6 dni. Otrzymano naste¬ pujace wyniki: Zwiazek XVII kontrola Ograniczenie rozwoju choroby 1 przy stezeniu czesci na milion C (E) C b. Obróbka nasion Nasiona pszenicy potraktowano róznymi dawka¬ mi zwiazku XVII, wytrzasajac 40 g nasion z 1 ml acetonu, 0,5 ml wody i zwiazkiem grzybobójczym w ilosci odpowiadajacej 31, 62, 124 i 248 g/100 kg.Zaimpregnowane ziarno umieszczono w doniczkach z ziemia, wielkosci 8 cm, powtarzajac kazda próbe w czterech seriach. Doniczki umieszczono w cie¬ plarni, w temperaturze 21—24°C. Po wyhodowaniu roslin do wysokosci okolo 50 mm inokulowano je zawiesina zarodników E, graminis, zawierajaca oko¬ lo 30 000 zarodników w mL Rosliny wysuszono i ponownie umieszczono w cieplarni w temperaturze 21—24GC. Po uplywie 17 dni dokonano oceny roz¬ woju choroby, Otrzymano nastepujace wyniki; 50 55 Zabieg Zwiazek I ' Zwiazek XVII kontrola Opryskanie lis¬ ci stezenie czesci na milion " 12,5 6,3 12,5 6,3 °/o wyte¬ pienia 100 100 100 100 100 100 0 40 Przyklad XV. Badanie E. Ochrona sklado¬ wanych owoców przed zgnilizna, taka jak nekta¬ ryna brazowa (Monilinia fructicola) przez zanu¬ rzenie po zebraniu.Dla oceny skutecznosci ochrony owoców przez zanurzenie w roztworze po zebraniu, czesciowo dojrzale brzoskwinie uszkadzano, a nastepnie na¬ tychmiast zanurzano w roztworze badanego zwiaz¬ ku o stezeniu 300 lub 600 czesci na milion w mie¬ szaninie aceton : metanol : woda (1:1:2). Owoce suszono w temperaturze pokojowej, a nastepnie inokulowano zawiesina zarodników Monilinia fruc¬ ticola 30 X 103. Owoce nastepnie przechowywano w temperaturze 24 i 14°C, az do wystapienia bra¬ zowej zgnilizny na owocach kontrolnych. Otrzy¬ mano nastepujace wyniki: Zwiazek I kontrola Stezenie roz¬ tworu czesci do zanurza¬ nia na milion 300 600 % choroby Wyniki obserwa¬ cji po zaszczepie¬ niu °C/tygodni /1 1,4 1,6 4,0 14/1 0 0 4,0 14/2 0 0 23,0 W Przyklad XVI. Badanie F. Porównanie ze zwiazkami znanymi.Przeprowadzono kilka badan porównawczych zwiazku I i zwiazków opisanych w brytyjskim opi¬ sie patentowym nr 1 214 415. Ponizej przedstawio¬ no kilka reprezentatywnych wyników: 1. Ochrona przed zaraza ryzu (Piricularia ory- zae).Sadzonki ryzu opryskano badanym zwiazkiem w roztworze o zmiennym stezeniu, wyrazonym w czesciach na milion, po czym inokulowano je za¬ rodnikami P. oryzae w sposób wyzej opisany.Przeprowadzono bezposrednie porównanie z efek¬ tywnoscia nastepujacych zwiazków z brytyjskiego opisu patentowego nr 1214 415:23 90691 24 zwiazek Nazwa l-benzylidenoamino-2j(3-metoksykarbo nylo-2-tioureido)-benzen l-(4-chlorobenzylidenoamino)-2-(3-me- toksykarbonylo-2-tioureido)benzen lH(4-metoksybenzylidenoamino)-2-(3- -metoksykarbonylo-2-tioureido)benzen l-(3-nitrobenzylidenoamino)-2-(3-eto- ksykarbonylo-2-tioureido)benzen Otrzymano nastepujace wyniki: B D Zabieg Zwiazek I zwiazek A zwiazek B zwiazek C zwiazek D • kontrola Ograniczenie rozwoju choroby przy stezeniu czesci na milion 1200 A C C A B (E) 600 A D D B C 300 A E D B D 150 A E E D E 75 B E E E E 37,5 B E E E E 2. Okreslenie strefy zahamowania dla róznych organizmów grzybowych. ml agaru z dekstroza ziemniaczana rozlano na plastikowa plytke srednicy 9 cm. Sporzadzono roztwory potencjalnych srodków grzybobójczych o zmienych stezeniach. Roztworami wysycano kraz¬ ki antybiotyczne o srednicy 6,35 mm, które na¬ stepnie umieszczano na plytkach z agarem, w srod¬ ku plytek. Na przeciwleglych stronach, na krawe¬ dziach plytek umieszczano strzepki grzybni róz- nych grzybów. Plytki utrzymywano nastepnie w warunkach sprzyjajacych rozwojowi odpowiednich organizmów. Po uplywie 3—6 dni mierzono strefy zahamowania wzrostu grzybni. Stosowano naste¬ pujace oceny stopnia zahamowania wzrostu: + +'+ silny + + umiarkowany + slaby —brak Przeprowadzono porównanie ze zwiazkami z bry¬ tyjskiego patentu 1 214 415 (zwiazki A—D). Wyniki przedstawiono w tablicy 11.Przyklad XVII. Badanie G. Wplyw srodka grzybobójczego na fermentacje soku winogronowe¬ go Jest pozadane, by srodek grzybobójczy, stosowa¬ ny do opryskiwania winorosli nie mial wplywu na szybkosc fermentacji soku winogronowego przy produkcji wina.Przeprowadzono badania porównawcze tych wla¬ sciwosci zwiazku XVII i dobrze znanego srodka grzybobójczego N-trójchlorometylotioftalamidu. W badaniach tych media fermentacyjne, skladajace sie z 3785 ml soku winogronowego i 454 g glukozy rozdzielono na 200 ml próbki, które rozlano do naczyn zawierajacych wystarczajaca ilosc bada¬ nych zwiazków, rozpuszczonych w mieszaninie aceton : metanol : woda (1:1: 2).Stezenie srodka grzybobójczego wynosilo 5 i 20 czesci na milion. Do kazdej próbki dodano zawie¬ sine drozdzy (Saccromyces cerevisiae) zawierajaca 3 X 107 komórek w ml i zakorbowano naczynia korkiem z rurka szklana i plastikowa. Wolny ko¬ niec plastikowej rurki zanurzono w odwróconym naczyniu o pojemnosci 125 ml, wypelnionym woda.Tablica 11 Zahamowanie wzrostu grzybów Badany zwiazek zwiazek I zwiazek A zwiazek B zwiazek C zwiazek D czesci na milion na krazku antybiotycz¬ nym 1000 500 250 125 1000 500 250 125 1000 500 250 1000 500 250 1000 500 250 Aspergillus terreus +H- + +i+ + + + + +:, +;++ ++ — — —' — — + + + + + + — Fusarium roseum „Culmorum" + + + — — — + — — — . — — — — — — + ! — 1 Sclerotinia sclerotiorum +.+ + + + + + + + — + + + + + + +: — — — — ++¦, + — — —.— Zythia pinastria +¦+¦+ + + ++ + + + + + +¦ + ' + — — — — : ' ' — |90691 26 Okreslano czas potrzebny do wywiazania 125 ml dwutlenku wegla. Otrzymano nastepujace wyniki: Tablica 11 Srodek grzybobójczy Zwiazek XVII N-trójchlorometylotio- ftalamid kontrola Czesci na mi¬ lion — Czas wywia¬ zywania 125 ml C02 godzin 24 24 120 120 24 Zwiazki stosowane jako skladnik aktywny w srodku wedlug wynalazku nigdy nie wykazywaly fitotoksycznosci przy opryskiwaniu roslin dawka¬ mi dajacymi doskonala ochrone przed fitopatogen- nymi grzybami.Zwiazki te nigdy nie wykazywaly wlasciwosci owadobójczych i w zwiazku z tym nie szkodza owadom drapieznym. Wykazuja one aktywnosc przeciwrobaczycowa. Przykladowo wykazano, ze silnie oddzialywuja na Aspicularis tetraptera i Sy- phacia obvelata. 4-i(2-metylenoaminofenylo)-3-tioallofaniany sa uzyteczne jako grzybobójcze srodki do pielegnacji roslin i moga byc stosowane do opryskiwania na¬ sion, gleby lub listowia.Ogólnie walka z fitopatogennymi grzybami po¬ lega na potraktowaniu hodowanych roslin, w miej¬ scu hodowli, grzybobójczo aktywna dawka co naj¬ mniej jednego z powyzszych zwiazków.W zastosowaniach grzybobójczych powyzsze 3- -tioallofaniany moga byc stosowane w postaci roz¬ tworów lub w innych postaciach.Mozna mieszac jeden lub wieksza liczbe zwiaz¬ ków o wzorze 1 z jednym lub wieksza liczba no¬ sników stosowanych zwykle w preparatach grzy¬ bobójczych.Zwiazki o wzorze 1 zazwyczaj rozpuszcza sie w stanowiacym nosnik rozcienczalniku lub przygo¬ towuje w sposób umozliwiajacy ich rozpylanie ja¬ ko preparatów grzybobójczych. Przykladowo, mo¬ zna tioallofaniany przygotowac jako zwilzalne proszki, koncentraty emulsji, proszki, granulki, aerozole itp. W takich postaciach zwiazki stosowa¬ ne w srodku wedlug wynalazku sa rozcienczane cieklym lub stalym nosnikiem, do którego dodaje sie, jezeli to jest pozadane, srodki powierzchniowo czynne.Korzystne jest, zwlaszcza w przypadku prepa¬ ratów do opryskiwania listowia, by preparaty za¬ wieraly takie dodatki, jak emulgatory, srodki zwil¬ zajace, rozpraszajace, zwiekszajace przyczepnosc itp., zwykle stosowane w praktyce. Zwykle stoso¬ wane dodatki tego rodzaju mozna znalezc w pu¬ blikacji John W McCutcheon, Inc. Detergenty and Emulsifiers 1971 AnnuaL Ogólnie, rozpuszczalnosc zwiazków o wzorce 1 jest ograniczona, rozpuszczaja sie one jednak w takich rozpuszczalnikach jak dwumetyloformamid, pirydyna lub dwumetylosulfotlenek, a roztwory te mozna rozcienczac woda. Stezenie roztworu moze wynosic 2—50%, korzystnie 5—25%.W celu sporzadzenia koncentratu emulsji, dany zwiazek rozpuszcza sie w odpowiednim rozpusz¬ czalniku organicznym lub w mieszaninie rozpusz¬ czalników, z dodatkiem emulgatora, umozliwiaja¬ cego rozproszenie srodka grzybobójczego w wodzie.Stezenie aktywnego czynnika w koncentracie emulsji wynosi zwykle 10—25%, a w pewnych przypadkach moze dochodzic do 75%.Zwilzalne proszki do opryskiwan sporzadza sie mieszajac zwiazek z drobnoziarnistym cialem, sta¬ lym, takim jak glinki, nieorganiczne krzemiany i weglany, krzemionka oraz z czynnikiem zwilzaja¬ cym, zwiekszajacym przyczepnosc i/lub czynnikiem rozpraszajacym. Stezenie aktywnego czynnika wy¬ nosi w takich preparatach zwykle 20—98%, ko¬ rzystnie 40—75%. Typowy zwilzalny proszek spo¬ rzadza sie mieszajac 50 czesci zwiazku I, 45 czesci syntetycznego, wytraconego uwodnionego dwutlen¬ ku krzemu o nazwie handlowej Hi-SilR i 5 czesci lignosiarczanu sodu (MarasperseR N-22). W innym preparacie w miejsce Hi-Sil uzyto glinki typu ka¬ olinowej (Barden), a w jeszcze innym 25% Hi-Sil zastapiono syntetycznym glinokrzemianem sodu o nazwie handlowej Zeolex R 7.Proszki sporzadza sie mieszajac 3-tioallofaniany z drobnoziarnistym obojetnym cialem stalym, or¬ ganicznym lub nieorganicznym. Odpowiednimi do tego celu materialami sa maczki roslinne, krze¬ mionka, krzemiany, weglany i glinki. Jednym ze sposobów otrzymywania proszków jest rozciencze¬ nie zwilzalnego proszku drobnoziarnistym nosni- nikiem. Zwykle sporzadza sie koncentraty prosz¬ kowe o 20—80% zawartosci aktywnego skladnika,' które nastepnie rozciencza sie do stezenia 1—10%.Zawierajace 3-tioallofaniany srodki grzybobójcze mozna rozpylac zwyklymi sposobami, np. stosujac jako czynnik rozpraszajacy" wode lub powietrze.Rozcienczenie i szybkosc rozpylania sa zalezne od typu urzadzenia, sposobu rozpraszania i zwalcza¬ nej choroby. Aktywny czynnik stosuje sie zwykle w ilosci 0,125^30 kg/ha.W przypadku impregnacji nasion, czynnik akty¬ wny stosuje sie zwykle w ilosci 3—600 g/100 kg.W przypadku nanoszenia na glebe stosuje sie go 0,125—68 kg/ha, a w przypadku opryskiwania ro¬ slin 0,4—12,5 kg/ha.Zwiazki o wzorze 1 moga byc stosowane lacznie ze znanymi srodkami grzybobójczymi: takimi jak: — dwutiokarbaminiany i ich pochodne, takie jak dwumetylodwutiokarbaminian zelazowy (fer- bam), dwumetylodwutiokarbaminian cynku (ziram), etylenobisdwutiokarbaminian manganowy (maneb) i jego zwiazek koordynacyjny z jonem cynku (mancozeb), etylenobisdwutiokarbaminian cynku (zineb), propylenobisdwutiokarbaminian cynku (propineb) metylenodwutiokarbaminian sodu (met- ham) dwusiarczek czterometylotiuramu (thiram), kompleks zinebu i dwusiarczku polietylenotiuramu, 3,5-dwumetylo-l,3,5-2H-czterowodorotiadwuazy- no-2-tion (dazomet) i mieszaniny tych zwiazków ze soba oraz z solami miedzi; — pochodne nitrofenolu, takie jak krotonian 40 45 50 55 6090691 27 dwunitro-(l-metyloheptylo)fenylu (dinocap), 3,3- -dwumetyloakrylan 2-IIrz.-butylo-4,6-dwunitrofe- nyloizopropyIowy; — Zwiazki heterocykliczne, takie jak N-trójchlo- rometylotioczterowodoroftalamid (captan), N-trój- chlorometylotioftalamid (folpet), octan 2-heptadecy- lo-2-imidazolinowy (glyodin), 2-oktyloizotiazolon-3, 2,4-dwuchloro-6H(o-chloroanilino)-s-triazyna, ftali- midofosforotionian dwuetylowy, 4-butylo-l,2,4-tria- zol, 5-amino-l-[dwu(dwumetyloamino)fosfinylo]-3- -fenylo-l,2,4-triazol, 5^etoksy-3-trójchIorometylo- -1,2,4-tiadiazol, 2,3-dwucyjano-l,4-dwutiaantrachi- non (ditianon), 2-tio-l,3-dwutio[4,5-b]chinoksalina (thioqunox), karbaminian metylo-1-(butylokarba- mylo)-2-benzimidazolowy (benomyl), 2-(4'-tiazoli- lo)benzimidazol(thiabendazole), 4H(2-chlorofenylohy- drazóno)-3-metylo-5-izoksazolon, 1-tlenek pirydy- no-2-tiolu, kwas 8-hydroksychinolinowy i jego sole metaliczne, 4,4-dwutlenek 2,3-dwuwodoro-5-karbo- ksyanilido-6-metyloksatyny, 2,3-dwuwodoro-5-kar- boksyanilido-6-metylo-l,4-oksatyna, a-(fenylo)-a- -(2,4-dwuchlorofenylo)-5-pirymidynylo-metanol (triarimol), cis-N-[l,l,2,2-czterochloroetylo/tio]-4- cyklohekseno-l,2-dwukarboksyimid, 3-[2-(3,5-dwu- metylo-2-hydroksycykloheksylo-2-hydroksy]gluta- rimid (cykloheksimid), kwas dehydrooctowy, N- -(l,l,2,2-czterochlorotio)-3a,4,7,7a-czterowodorofta- lamid (captafol), 5-butylo-2-etyloamino-4-hydroksy- -6-metylopirymidyna (ethirimol) octan 4-cyklodo- decylo-2,6-dwumetylowy i morfolina (dodemorph), 6-metylo-2-keto-l,3-dwutiolo-4,5-b)-chinoksalina (auinomethionate); rózne chlorowcowane srodki grzybobójcze, takie jak czterochloro-p-benzochinon (chloranil), 2,3-dwu- chloro-l,4-naftochinon, (dichlone), 1,4-dwuchloro- -2,5-dwumetoksyi)enzen (chloroneb), k*was 3,5,6-trój- chioro-o-anizynowy (tricamba), 2,4,5,6-czterochlo- roizonaftalonitryl (TCPN), 2,6-dwuchloro-4-nitro- anilina (dicloran), 2-chloro-l-nitro-propan, poli- chlorobenzeny, takie jak pieciochloronitrobenzen (PCNB) i czterofluorodwuchloroaceton; — antybiotyki grzybobójcze, takie jak gryzeoful- wina, kasugamycyna i streptomycyna; — srodki grzybobójcze na bazie miedzi, takie jak tlenek miedziawy, zasadowy chlorek miedzio¬ wy, zasadowy weglan miedzi, naftenian miedzi i mieszanina Bordeux; — rózne inne srodki grzybobójcze, takie jak 28 dwufenyl, octan dodecyanoguanidyny (dodine), octan fenylomiedzi, N-etylortecio-l,2,3,6-czterowo- doro-3,6-endometano-3,4,5,6,7,7-szesciochloroftala- mid, mleczan fenylorteciomonetarioloamonowy, siarczan p-dwumetyloaminobenzenodiazosodowy, izotiocyjanian metylu, l-tiocyjano-2,4-dwunitroben- zen, 1-fenylotiosemikarbazyd, zwiazki zawierajace nikiel, cyjanamid wapnia, wapno siarczane, siar¬ ka i l,2-dwu(3-metoksykarbonylo-2-tioureido)ben- io zen PLThe subject of the invention is a fungicide containing as active substance new derivatives of 3-thioallophanic acid. There is little information in the literature on related compounds. Of interest are the fungicides known under Topsin, such as 1,2-bis (3-methoxy) or ethoxy (carbonyl-2-thioureido) benzene. Such compounds are described, for example, in Belgian Patent Specification No. 722,080. Biologically active compounds of the general formula 3, in which Z is, inter alia, a benzylidene amino group or a chlorine, methoxy or nitro derivative thereof, are known, for example, from British Patent Specification No. In the fungicide according to the invention, the active substance consists of the new derivatives of 3-thioallophanic acid of the general formula I, in which X represents the group IUO- or I-S-, in which R1 is a straight-chain alkyl group or branched with 1 to 12 carbon atoms, optionally substituted with substituents such as halogen, preferably chlorine or methoxy, alkenyl group with 2 to 12 carbon atoms, alkynyl group with 3 to 12. carbon atoms, a phenyl group optionally substituted with a halogen atom, preferably a chlorine atom, a methyl group, a methoxy group or a nitro group; a benzyl group optionally substituted with a halogen atom, preferably a chlorine atom, a methyl group, a methoxyl group or a nitro group, Y is a 5- or 6- and a tethered heterocyclic group, with heteroatoms such as oxygen, sulfur or nitrogen, or any combination of two of these atoms, where the total number of heteroatoms is no more than 3, optionally substituted acetoxymethyl group, chlorine atom, methyl group or nitro group, R is hydrogen or methyl group, Z is halogen, preferably chlorine a methyl group, a methoxy group or a nitro group is an integer from 0-3; Typical heterocyclic Y groups are: furyl, imidazolyl, isothiazolyl, isoxazolyl, N-methylpyryl, oxadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl. Preferred groups include 2-furyl, 5-isothiazolyl, 1-methylpyrl, 2-pyridyl, 2-pyrryl, 4-thiazolyl and 2-thienyl. Of the preferred compounds, the most preferred are those where Y is 2-furyl or 2-thienyl and R is hydrogen. In the case where Y is a 2-furyl group, these compounds are represented by the general formula 2. From the hydrocarbyl groups, R1 are preferred alkyl groups, especially lower alkyl groups with 1 to 6 carbon atoms, especially methyl or ethyl, acceptable however, there are other groups, e.g. octyl, decyl or dodecyl. The compounds used as the active ingredient in the composition according to the invention can, in general, be obtained by the methods used for the preparation of 9,069,190,691 analogous known compounds, in particular by treating the phenylene diamine derivative of the formula general 4, in which T is the group -HNCNHC-X or = C-Y with a compound of formula i and SOR 5, when T is a group -HNCNHC-X, II II SO and a compound of formula 6 when T is a group Wanie = C — Y. The symbols Z, X, Y, R and n have the same meaning as given for the compound of formula 1. Thus compounds of general formula I can be prepared by treating a compound of general formula 5 on a compound of general formula 7, or by treating a compound of general formula VI on a compound of general formula 8. For the preparation of furfurilidens, the latter reaction is preferably carried out in the presence of tertiary amines. Details of both routes are given below, both starting with o-phenylene In the first case, the o-phenylenedimine is treated with an isothiocyanic acid ester to give 4- (2-aminophenyl) -3-thioallophanate, which in turn is treated with an aldehyde or a ketone, obtaining the appropriate Schiff's principle, e.g. - (2-methylenaminophenyl) -3-thioallophanate. The course of the reaction is shown in Scheme 1. All symbols have the meaning given above. The isothiocyanates of general formula 6 can easily be obtained by methods described in the literature. One of these methods consists in treating the ester of chloroformic acid with ammonium or potassium thiocyanate in the presence of an inert solvent such as such as acetone, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene at elevated temperatures, for example 25-100 ° C. In the case of using potassium thiocyanate, the reactions can be represented by the scheme 2. The isothiocyanate is purified by distillation, but this process often involves significant thermal decomposition or polymerization. For this reason, it is preferable to use, in the subsequent reaction with the amine, the crude isothiocyanate identified on the basis of the infrared spectrum. In the reaction of o-phenylenediamine with an isothiocyanate of the general formula VI, both components are generally used in stoichimetric amounts. The reactions are carried out in the presence of an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. The reaction is usually easy and is carried out at temperatures of -20 ° C and above. The 4- (2-aminophenyl) -3-thioallophanates of formula 7 usually crystallize out of the reaction mixture and are purified by known methods such as recrystallization. Excessive heating of these compounds should be avoided as this may lead to the formation of benzimidazole as shown in Scheme 3. 4- (2-Aminophenyl) -3-thioallophanates are then treated with a heterocyclic aldehyde or ketone in the presence of an inert a solvent such as an aromatic hydrocarbon; and catalytic amounts of an acid such as p-toluenesulfonic acid. The reactions are usually performed at the reflux temperature of the solvent, but often at 50-150 ° C. Difficulties may arise with non-acid resistant aldehydes such as furfural. Modified methods have been developed for these cases. Scheme 4 shows a typical reaction with (2-thiophene) formic aldehyde or 2-thienylmethyl ketone. O-phenylenediamines and heterocyclic aldehydes and ketones are mostly commercially available products. Other heterocyclic aldehydes and methyl ketones can be obtained by methods described in the literature. For example, an aldehyde function can be introduced into a heterocyclic ring by formylation with carbon monoxide, hydrogen cyanide or N-methylformanilide, by treatment of the halomethyl derivative hexamethylene tetraamine, by the action of ethoxymethyldetylin with a Grignard reagent, via a hydroglorethyl derivative or by reduction of an acylhalide derivative. Table 1 below shows typical compounds of formula 7 used to prepare the compounds of the present invention. Table 1 Compounds of formula 7 in which: n = HH 4-CH 3 -NO 2 4- (or 5-) Cl 4- (or 5-) CH3 4- 4- (or 5-) N02 X = OCH3 OC2H5 OCH3 OC2H5 OCH3 OCH3 OCH3 OCH3 Decomposition temperature ° C or reference British patent 1214 415 British patent 1214 415 British patent 1214 415 British patent 1214 415 183-185 168-170 184-185 211-212 | 65 In the second case, o-phenylenedimine is treated with an equivalent amount of a heterocyclic aldehyde or ketone to give o- (methyleneamino) -aniline (Schiff's base), which is then treated with a hydrocarbyloxy-carbonylisothiocyanate ester to give the compound of formula 1 The course of the reaction is shown in Scheme 5. Reactions of o-phenyleneddumin with a carbonyl compound are usually carried out in the presence of an inert solvent such as benzene or toluene, usually at the boiling point of the solvent, but often in the range 50-150 ° C. Reactions can be stimulated by removal rising water. Alcohol may be used as the solvent, but in this case it should be carried out at a temperature below 0 ° C. The obtained Schiff bases are mostly known compounds. The reactions of the compounds of formula III with isothiocyanate are usually carried out in the presence of an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. The reaction takes place easily at room temperature and in the range of -20 to 100 ° C. Some of the above-described transients may be obtained by other known methods. For example, 2-aminonitrobenzene can be treated with an isothiocyanate of formula VI to give a compound of formula 9 which is then reduced, for example by a combined metal and acid, to a compound of formula 7. In a preferred variant of this process, furfurilidenes are obtained. in the presence of a tertiary amine. Thus, compounds of general formula 10, in which Z and X are as defined above, and W is a hydrogen atom, an Iowa acetoxymethyl group, a chlorine atom, a methyl group or a nitro group, can be obtained by treating a compound of the formula a general isothiocyanate of formula 6 in the presence of an organic tertiary amine base. The symbols W, X, Z in Formula 11 have the meanings given above. O-furfurylideneaminoanilines of Formula 11 are discussed in the literature, e.g. in Chemical Abstracts 61, 828B, and 14860f i (1964) and 67, 11629m (1967). they are treated by treating the o-phenylenediamines with an equal amount of furfural, possibly in the presence of a tertiary amine. The course of the reaction is shown in Scheme 6. The symbols W, Z and n have the meanings given above. The reactions are usually carried out in the presence of an inert solvent such as benzene or toluene, usually at the boiling point of the solvent, and often at a temperature of 50-150 ° C. An alcohol can be used as a solvent, but in this case the reactions are performed at or below 0 ° C. Reactions can be stimulated by removing the water formed. A tertiary base, such as triethylamine or dimethylaniline, is sometimes used as the stabilizing agent, but this is not necessary. Among the tertiary amines, those which have a dissociation constant of 5 X 10 -3 to 5 X 10 at 25 ° C are used. ~ 5. Typical of such amines are: trimethylamine, triethylamine, trimethylamine, triisobutylamine, methyldiethylamine, tetramethylethylenedimine, N, N-dimethylethanolamine, and dimethylaniline. The preferred tertiary amines are triethylamine and tripropylamine. Amine is usually used in an amount of 0.5-20 mole percent. For example, triethylamine, which has a molecular weight of 101, is used in amounts of 0.5-2.0 g per mole of reactants. The amount normally used is in the range 5-15 mole percent. The amine can be added to or to the o-furfurylideneaminoaniline or to the hydrocarbyloxycarbonylisothiocyanate ester or to be separated between the two reactants. The reaction of o-furfurylideneaminoaniline of formula 11 with isothiocyanate of formula 6 (usually in the tertiary number of 90691) an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. Reagents are used in equimolar amounts, but isothiocyanate is often used in an excess of up to 100%, preferably in an excess of 20-40%. The reaction proceeds readily at temperatures above -20 ° C. The 4- [2- (furfurylideneamino) phenyl] -3-thioallophanates of the formula (10) usually crystallize from the reaction mixture and are purified by conventional methods, for example by recrystallization. Excessive heating of these compounds should be avoided, as this may lead to the formation of benzimidazole. The course of the reaction is shown in Scheme 7. Below are some examples of the preparation of active compounds in the fungicide according to the invention. Example I. Preparation of 4- [2- (furfurylideamine) ) phenyl] -3-methyl thioallophane. Method 1 11 g (0.040 mol) of methyl 4n (2-aminophenyl) -3-thioallophanate in 200 ml of benzene were added, 75 g (0.06 mol) of furfural and catalytic amounts of p -toluenesulfonic acid. The reaction mixture was boiled for 4 hours, while 0.9 ml of water was separated from the azeotrope. The reaction mixture was then cooled to give a yellow solid which, on drying, melted decomposing at 150 ° -152 ° C. The yield of methyl 4- [2- (furfurylidenamino) phenyl] -3-thioallophanate was 8.1 g (55% of theory). Process 2. For a suspension of 52.4 g of potassium thiocyanate (0.565 mol) in 162 g of acetate butyl, while stirring at 50 ° -55 ° C, 52.4 g of methyl chloroformate (0.565 mol) was rapidly added. There was a slightly exothermic reaction. The reaction mixture was held at 60 ° C. for 4 hours, during which time 2.6 liters of carbon dioxide were evolved. The obtained mixture of methoxycarbonyl iso * thiocyanate was cooled to 10 ° C and kept for further reaction. To 39.2 g of o-phenylenedimine (0.362 mol), optionally by addition of 2.2 g of N, N-dimethylaniline) 37.0 g of furfural were added. (0.385 mol) in 119 g of toluene. The reaction mixture was heated to 35 ° C for 0.5 hour. The solution was then evaporated at 50 mm, collecting 93 g of toluene-water distillate. The remaining o- (2-furfurylideneamino) aniline was cooled to room temperature, and 3.0 g of triethylamine was added. To the suspension of methoxycarbonyl isothiocyanate kept at 0 ° C., 7 g of triethiylamine was added, followed slowly by -fur-furylideneamino) aniline, keeping the temperature 55 below 35 ° C. The mixture was stirred for an hour, cooled to 10 ° C., and the precipitate was filtered off. After washing with 100 ml of cold toluene and 300 ml of water and drying, there was obtained 100 g of s-methyl 4- [2- (furfurylideneamino) phenyl] -3-thioallophane, mp 155-156 ° C. This is 90% of theoretical yield. In British Patent Specification No. 1,214,415, Example 11 shows the preparation of 65 l-benzylideneamino-2- (3-methoxycarbonyl-2-thiol-l [mu] eido) benzene. In this process, 2-benzylideaminoaniline was treated with methoxycarbonyl isothiocyanate in acetone at a temperature of -5 ° C to room temperature. By following this method it was not possible to isolate, starting from o- (2-furfurylideneamino) aniline, 4- [2H (furfurylideneamine) phenyl] -3-thioallophanate. Also, this product was not obtained if triethylaniline was not added. The use of a base is necessary if aldehydes or their Schiff bases are sensitive to acids in the reaction. Successful attempts have been made to prepare 4- [2- (furfurylideneamino) phenyl] -3-thioallophanates by the preferred general method 2. Method 3. Up to 60 g of o-phenyldiamine (0.56 mol) in 500 ml. Toluene was added at ° C, 5 g of N, N-dimethylaniline (0.04 mol) and 56 g of furfural (0.58 mol). At a pressure of 50 mm at 35 ° C, toluene and water were distilled off to obtain 150.3 g of a concentrated toluene solution. 4 g of triethylamine (0.04 mol) was added to the above solution and it was cooled to room temperature (solution D). To 81 g of potassium thiocyanate (0.835 mol), suspended in 300 ml of butyl acetate, was added quickly at 60 ° C. C 81 g of methyl chloroformate (0.86 mol). The resulting yellow mixture was stirred for 2 hours, keeping the temperature at 60 ° C. The product was cooled to ° C. and 2 g of triethylamine (0.02 mol) was added. To the above solution of methoxycarbonyl isothiocyanate was added solution D at The temperature was below 35 ° C and was stirred for an hour, then cooled to 10 ° C, which resulted in the precipitation of a precipitate, which was filtered off, shaken with 600 ml of water and dried to obtain 151.5 g of product at mp 154-155 ° C. Elemental analysis: found values 54.6% C, 4.2% H, 14.0% N, values calculated for Ci4H13N303S 55.3% C, 4.4% H, 13.8% N. Yield the product is methyl 4- [2- (furfurylideneamino) phenyl] -3-thioallophanate was 90%. The structure was confirmed by infrared light analysis. The product contained a slight admixture of potassium chloride. Method 4. To 30.0 g of o-phenylenedimine (0.278 mol) in 325 ml of toluene was added 28.0 g of furfural (0.292 mol) at 60 ° C. The toluene-water mixture was distilled at 60 ° C and 130 mm pressure until a residue of 55 'was obtained in a flask, to which was added 2 g of triethylamine (0.02 mole) (solution E). g. potassium thiocyanate (0.417 mole) suspended in 150 ml. of ethyl was added quickly at 45 ° C. 40.5 g. methyl chloroformate (0.429 mole). The whole was stirred for 2 hours at 45 ° C, and then cooled to 10 ° C. To the obtained methoxycarbonyl isothiocyanate suspension was added 4 g of triethylaminamine (0.04 mol), and then within 15 minutes, solution E temperature not exceeding 35 ° C. The mixture was stirred for an hour and filtered, washed with 300 ml of water and dried to give 57.3 g of product, m.p. 90 ° C and 40 45 50 55 60 65 154-155 ° C. . Elemental analysis: found values: 55.3% C, 4.3% H, 13.7% N, calculated values for C14H13N303S 55.4% C, 4.3% H, 13.85% N. The yield of methyl 4- [2-furfurylideneamino / phenyl] -3-thioalylophanam was 68%. Table 2 shows the structures of the related 4- [2-furfurylideneamino) phenyl] -3-thioallophanates obtained by methods 3 and 4. Table 5 shows the melting or decomposition points and analytical data for these compounds. Table 2 Obtained compounds of general formula 10 Compound I II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI X OCH3 OC2H5 SC2H5 OC4H9-n OC8H17-n OC6H5 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH2CCl3 OCH2CH = = CH2 OCH2C6H5 WHHHHHH CH3 CH3 CH30 (0) OCH2 HHHH NO2 HHH Zn HHHHHHHH 4 (or 5) -CH4 (or 5) 5) -Cl8 (or 5) -Cl8 (or 4,5-Cl2 HHHH Example II. Preparation of ethyl 4- [2-aminoamino) phenyl] -3-thio-thiolallophanate, i.e. compound III of Table 2: To a suspension of 20 g of potassium thiocyanate (0.206 mol) in 125 ml of 2-methoxyethanol, kept at room temperature, was added 25 g (0.2 mol) of S-ethyl chlorothiolformate. The mixture was stirred for 3 hours and the solvent was stripped off. To the residue were added 3 g of triethylamine and o- (2 -furfurylideneamine) aniline (0.185 mol) containing about 3 g of triethylamine, as described in Example I. by the method described in Example 1, 24.5 g of a yellow product were obtained. After recrystallization from benzene, 14.3 g of yellow needles were obtained, melting decomposed at 157-158 ° C. The yield of ethyl 4- [2- (furfurylideneamino / phenyl] -3-thio-thiodoallylphanate was 23%! III. Preparation of methyl 4- {2- (thienylideamino) phenyl] -3-thioallophanate, ie compound XVII of Table 3 Reaction mixture consisting of 4.5 g of methyl 4- < 2-aminophenyl) -3-thioallophanate (0.02 mole), 2.24 g of thiophene-2-carboxaldehyde (0.02 mole) and 10090691 ml of benzene were stirred for 2 hours at boiling point, and the azeotropic distillate was drained from water. From the cooled reaction mixture, 3.5 g of product, m.p. 175 ° C., were filtered off. The yield of methyl 4- [2- (thienylideneamino) phenyl] -3-thioallophanate was 55%. Table 3 shows the structures of the compounds obtained. Their properties are given in Table 5. Table 3 Compounds of general formula 13 obtained Compound XVII XVIII XIX XX XXI XXII XXIII RHHHHHH CH3 X OCH3 OC2H5 OCH3 OCH3 OCH3 OCH3 OCH3 WHH Cl HHHHZHHH 4 (or 5) -Cl 4 (or 5) -Cl 4 (or 5) -NO 2 H Example IV. Preparation of methanol 4- [2-thienylidene-amino) -4 (or 5) -chlorophenyl] -3-thioallophanate. This is compound XX of Table 3. To 10 g of 4-chloro-o-phenylidene diamine (0.07 mol) in 175 ml of ether was added 8 g of methoxycarbonyl isothiocyanate (0.068 mol) at a temperature below 25 ° C. The slurry was filtered, and the residue was dried to obtain 12.3 g of a yellow colored substance, mp 184-185 ° C with decomposition. The second crop (6.1 g) yielded, after recrystallization, 4.3 g of a substance having a melting point of 183 ° -185 ° C. The total yield from both crops of methyl 4- (2-amino-4 / or 5) -chlorphenyl) -3-thioallophanate was 92%. Up to 6 g of 4- (2-amino-4 (or 5) -chlorophenyl) - Methyl 3-thioalphanate (0.023 mol) in 250 ml of benzene was added 2.8 g of 2-thiophenecarboxaldehyde (0.025 mol), containing about 0.2 g of p-toluenesulfonic acid. The reaction mixture was heated to reflux for 6 hours, while the water which evaporated was azeotropically chased off. Remain-. The stripped solvent, orange-brown color, was triturated with ether to give 4 g of an orange-yellow substance, melting decomposed at L73—175 ° C. Since the analysis showed that the product was a mixture, it was treated with 3 g of 2-thiophenecarboxylic aldehyde. 3.3 g of an orange-yellow product which melts with decomposition at 183 ° C. Was isolated as described above. The yield of methyl 4- [2- (thienylideneamino) -4- (or 5) -chlorophenyl] -3-thioallophanate was 41%. Example 5 Preparation of 4- {2n (thienylidene amino) -4 (or 5) Methyl chlorophenyl] -3-thioallophanate, ie the compound XXI of Table 3. To a mixture of 9.5 g of 4-chloro-o-phenylenediamine (0.067 mol) in 250 ml of benzene was added 7.5 g of 40 45 55 ® 2-thiophenecarboxaldehyde (0.067 mol). The mixtures were heated to reflux for 3 hours, then concentrated to half volume, added 25 ml of hexane and cooled to give an oil. The oil which was separated and concentrated was a mixture which was reacted with a further 2.5 g of 2-thiophenecarboxaldehyde for 2 hours at reflux temperature, then cooled, causing precipitation. After filtration and drying, the amount was 4 , 1 g. 3.2 g of an oily precipitate were separated from the filtrate. Both portions were combined and recrystallized from a mixture of hexane and ether (50:50) to give 5.2 g of a material, mp 69-70 ° C. The yield of 2-thienylideneamino-4 (or 5) -chloroaniline was 33%. To 4 g of 2-thienylidene-4 (or 5) chloroaniline (0.017 mol) in 120 ml of ether were added 2 g of methoxycarbonyl isothiocyanate (0.017 mol). and the mixture was stirred for an hour at room temperature. The yellow precipitate was filtered off, washed with ether and dried to give 1.8 g of a substance, mp 143-144 ° with decomposition. The yield of methyl 4- [2- (thienylideneamino) -4 (or 5) -chlorophenyl] -3-thioallophanate was 30%. Preparation of methyl 4- [2- (α-methyl-2-thienylideneamino) phenyl] -3-thioallophanate i.e. compound XXIII of Table 3 Reaction mixture consisting of 15 g of o-phenylenedimine (0.139 mol) 19 g of 2- acetylthiophene (0.151 mole) and 200 ml of benzene were heated to reflux for 56 hours, separating the water which evolved from the reaction. The solvent was evaporated to a yellow residue, which was triturated with hexane and recrystallized from benzene / hexane (1: 1) to give 15.4 g of 2- (α-methyl-2-thienylidene-amino) aniline. A solution of 5 g of 2- (α-methyl-2-thienylideneamino) aniline (0.0232 mol) in 175 ml of ether was added dropwise 3 g of methoxycarbonyl isothiocyanate (0.0256 mol) at 24-28 ° C. The yellow-colored solution was stripped of the solvent to give an oily precipitate which was triturated with cold ether to obtain, after filtration, 2 g of substance, mp 126-127 ° C decomposed. Yield 4- [2- (a- methyl 2-thienylideneamino) phenyl] -3-thioallophanate was 26%. Example VII. Preparation of methyl 4- [2n (2-pyrrolylmethyleneamino) phenyl] -3-thioallophanate, i.e. compound XXIV. A solution of 15 g of o-phenylenediamine (0.139 mol) in 45 ml of methanol was cooled to -10 ° C and then added to at a temperature not exceeding -5 ° C, a solution of 13.2 g of pyrrole-2-carboxaldehyde (0.139 mol) in 45 ml of methanol. The mixture was stirred for 0.5 hours at a temperature below -5 ° C. The yellow colored precipitate was filtered off, yielding 10.5 g of product, mp 106-108 ° C. After some time a further 12.4 g of a solid, mp 106-108 ° C, was lost from the solution. The combined precipitates accounted for 89% of the yield of 2H (2-pyrrolylmethyleneamino) aniline, 90691 l. To a solution of 5 g of 2- (2-pyrrolylmethyleneamino) aniline (0.027 ml) in 175 ml of the solution was added 3.7 g of methoxycarbonyl isothiocyanate ( 0.315 mol) and was stirred for one hour. The precipitate was filtered off and dried to give 5.1 g of orange-yellow solid, mp 178-179 ° C with decomposition. The yield of methyl 4- [2- (2-pyrrolomethyleneamino) phenyl-3-thioallophanate was 63%. Example VIII. Preparation of 4- [2- (1-methyl-ao -2-pyrrolomethyleneamino) phenyl] -3-thicallophanic methyl, i.e. compound XXV. Mixture of 10 g of o-phenylenedimine (0.0926 mol) 10.1 g N-methylpyrrole-2-carboxaldehyde (0.0926 mole) and 175 ml of benzene were heated for 15 hours at reflux temperature, the water was separated off, and the solvent was then drained off to give a dark colored, oily residue which was triturated twice with 100 ml. of dark hexane. The hexane extracts were cooled to give 10.2 g of a yellow oil which was dissolved in 100 ml of ether. This amount would correspond, if the material was pure, to 0.05 moles of 2- (1-methyl-2-pyrrolylmethylamino) aniline. 70 ml of the above solution (0.035 mol) were treated with 5 g of methoxycarbonyl isothiocyanate (0.43 mol) to give 4.1 g of a solid, mp 155-157 ° C, a mixture of the extrinsic product and Methyl 4- (2-aminophenyl) -3-thioallophanate. 3.8 g of this product was suspended in 175 ml of benzene containing 0.1 g of p-toluenesulfonic acid and further reacted with 3 g of N-methylpyrrole-2-carboxaldehyde (0.095 mole), heating it for 3 hours at boiling point. The reaction mixture was then heated for 0.5 hour with activated carbon, filtered, and the filtrate stripped of the solvent, leaving an oily residue. After trituration with ether, 2.4 g of product were obtained, mp 171-172 ° C. with decomposition. The yield of methyl 4- [2- 40 - (1-methyl-2-pyrrolylmethyleneamino) phenyl] -3-thioalphanate was 22%. Example IX. Preparation of methyl 4- [2- (5-isothiozolyl-methylene-amino) phenyl] -3-thioallophanates ie compound XXVI. 45 A reaction mixture consisting of 9.4 g of o-phenylenediamine (0.0867 mol) and 9.8 g of 5-isothiazolecarboxaldehyde (0.0867 mol) and 80 ml of benzene was heated for 2 hours at Boiling point, separating the water of reaction. After stripping off the solvent, a red-orange oil was obtained as a residue. After trituration with 100 ml of a cold mixture of ether and hexane (1: 1), 9.1 g of a red-orange solid was obtained. Infrared spectrum analysis confirmed that 2- (5-isothiazolylmethyleneamino) aniline was obtained. The yield was 52%. To a solution of 5 g of 2- (5-isothiazolylmethyleneamino) aniline (0.0246 mol) in 100 ml of ether was added 3.5 g of methoxycarbonyl isotocyanate (0.03 mol) and the mixture was stirred for an hour. A red-orange precipitate was precipitated, filtered off and dried to give 3.5 g of a substance, mp 176-177 ° C, with decomposition. The yield of 65 12 methyl 4 - [- 2- (5-isothiazolylmethyleneamino) phenyl] -3-thioallophanate was 46%. Example X. Preparation of methyl 4- [2- (2-pyridylmethyleneamino) phenyl] -3-thioallophanoate that is compound XXVII. A reaction mixture consisting of 7.1 g of methyl 4- (2-aminophenyl) -3-thioallophane (0.0316 mol), 3.7 g of 2-pyridinecarboxaldehyde (0.0346 mol) 1a), 0.2 g of p-toluenesulfonic acid and 250 ml of benzene were heated under reflux for 3 hours. After cooling, a brown solid by-product was precipitated, the amount of which was 3.2 g after draining. The filtrate was treated with 150 ml of hexane, yielding 4.3 g of a purine product, melting at 144-5 ° C, with a decomposition . The yield of methyl 4- [2- (2-pyridylmethylene-amino) phenyl] -3-thioallophane was 43%. Table 4 shows the obtained compounds according to the Y group. Table 5 shows the physicochemical data of these compounds from Tables 2, 3 and 4. Compounds of general formula 14 obtained. Compound I XVII XXIV xxv XXVI 1 xxvii 'Y fvryl thienyl pyrrolyl N-methylpyrrolyl-isothiazolyl pyridyl 4- (2-methyleneaminophenyl) -3-thioallophanates are excellent fungicides. They are particularly suitable for controlling phytopathological fungi of the groups Ascomycetes and Fungi Imperfecti. The types of fungi which can be controlled according to the invention are, for example: Acanthorhynchus; Acanthostigma, Acremonium; Acrostalag- mous; Acrospora; Aspergillus, e.g., A. Oryzae, A. repens, and A. terreus; Botryosphaeria; Botryosporium; Botrytis, e.g. B. cinerea; Calonectria; Calos-phaeria; Cenangium; Cephalosporium; Cephalothelium; Ceratostomella; Cercospora, e.g. C. apii; Cercosporella Claviceps; Cleistothecopsis; Coccomyces; Cryptosporella; Dasyschypha; Diaporthe; Didymaria; Didimellina; Didymosphoeria; Dothidella; Endothia, Epichloe; Erysiphe, e.g., E. gramine and E. polygoni; Fabraca; Fusidium; Gibberella; Gloesporium, eg G. aridium, G. phagi, G. musarum and G. auercinum; Glomerella, eg G. cingulata and G. gosypii; Gnomony; Guignardia; Herpotrichia; Hya-lodema; Hypoderma; Hypodermella; Hypoxylon; Keithia; Leptosphaeria; Lophodermium; Meliola; Microsphaera; Monilia; Monilinia, e.g. M. fructocola; Mycogone; Mycosphaerella; Nectria, e.g. N. episphaeria; Neofabraea; Neopeckia; Nummullaria; Oidiopsis; Oidium; Oospora; Ophiobolus; Penicilliums, e.g. P. diversum, P. funiculosum, P. italicum, P, oxalicum and P. yemaculosum; Phabdocline; Pha-13 90691 Table 5 14 Compound 1 I II III IV V VI VII VIII IX XI XII XIII XIV XV XVI XVII XVIII XIX XXI XXII XXIII XXIV xxv XXVI XXVII Melting point ° C 2 155-6 *) . 113—115 *) 157—158 *) 122—124 *) 84—85 *) 172—173 *) 127—128 *) 149—150 *) 188—189 *) 168—169 *) 163—164 *) 202—203 *) 206—208 *) 166—167 *) 108—110 *) 161—162 *) 163—165 *) 136—137 *) 149_151 *) 183—184 *) 143—144 *) 203— * 204) 126-127 *) * 178-179) 171-172 *) * 176-177) 144-145 *) 3 Empirical formula C14H13N3O3S C15H15N3O2S2 Ci5H15N303S Ci7Hi9N303S C21H27N3O3S C15H15N3O3S C19H15N303S C17H17N305S C15H15N304S C14H12CIN3O2S Ci5H15N303S Ci4Hi8Cl2N303S Ci4H12N405S C ^ H ^ ClgNgOgS C16H15N303S C20H17N3O3S C14H13N302S2 C15H15N302S2 C14H12CIN3O2S2 C14H12C1N302S2 C ^ H ^ ClNgC ^ Sg C14H12N404S2 C15H15N302S2 C14H14N402S Cl5Hi6N402S 56.96N402.5 55.62.56N402.5 56.9 56.3 54.0 45.5 48.2 42.8 58.3 62.0 52.7 54.1 47.7 47.6 47.7 46.2 54.0 55.7 57.0 48.7 57, 3 (55.3) (57.2) (54.0) (58.9) (62.8) (62.7) '(57.4) (54.3) (49.6) (57, 0) (54.4) (45.6) <48.6) (43.0) <58.3) (63.1) (52.4) (53.1) (47.5) (47, 6) (47.6) (45.7) (54.0) (56.2) (57.2) (48.9) (57.0) A elemental analysis **) H 4.3 4.8 4.5, 6 6.6 4.1 4.8 4.5 3.6 4.8 4.6 2.1 3.5 2.9, 2 4.5 4.1 4.5 3.4 3.4 3.4 3.3 4.5 4.7, 1 3.8 4.5 (4.4) (4.8) • (4.7) (5.9) (6.3) ( 4.2) (4.8) (4.6) (3.5) (4.9) (4.7) (2.7) (3.4) (3.0) (4.6) ( 4.5) (4.2) (4.4) (3.5) (3.5) (3.1) (3.6) (4.5) (4.4) (5.0) ( 3.9) (4.5) N 6 13.9 (13.8) 13.3 (13.1) 12.6 (12.7) 12.2 (12.1), 4 (10.5) 11.5 (11.8) 13.2 (13.3) 11.2 (11.2) 12.5 (12.2) 13.3 (13.1) 12.6 (12.5) 11, 4 (11) 16.1 (16.0), 0 (9.8) 12.9 (12.8), 7 <11.11 13.2 (13.2) 12.6 (12.8) 11 . 9 (11.8) 11.9 (11.4) 11.9 (H, 7), 4 (15.5) 12.6 (12.5) 18.5 (19.0) 17.8 ( 17.4) 17.5 (17.4) 17.9 (17.8) O 7.9 (16.0), 1 (15.2) 9.6 (10.1) 13.9 (14.1) 12.2 (12.0) 13.1 (13.3), 2 (15.6) 21.3 (21.6) 14.3 (14.6), 2 (15.1) 19.2 ( 19.3) 13.2 (13.2) 23.0 and (22.9) 11.4 (11.4), 0 (14.6) 13.0 (12.7) 9.6 (10, 0) 9.1 (9.3) 9.0 (9.9) 9.0 (9.7) 17.6 (17.7) 9.6 (9.9), 6 (10.6), 0 (10.6), 0 (9.8), 2 (10.1) S "® ~~ ', 6 (10.5), 1 (9.8) 1 19.2 (19.3) 9 , 3 (9.4) 8.1 (8.0) 8.2; (8.2), 1 (10.0) 8.6 (8.5) 9.5 (9.5), l (9.8) 9.6 (9.6) 8.6 (8.8 ) 9.2 (8.9) 7.6 (7.9) 8.9 (8.7) (8.5) 19.2 (19.3) 18.1 (18.0) 18.1 ( 18.9) 18.1 (17.7) 19.3 (19.4), 6 (10.5), 0 (10.0), 0 (19.8), 2 (10.5) 1 * ) with distribution **) The number in brackets is the theoretical value, calculated from the sum formula for cidiella; Phyllactinia; Phyllachora; Physalospora; Piricularia, e.g. P. oryzae; Plectodiscella; Pleosphaetil; Pleospora; Plowrighttia; Podosphaera, Pseu- dopeziza; Pyrenophora; Quvlaria; Ramularia; Rhytisma; Rosellinia; Rhizina; Sclerotinia, e.g. S. sclerotiorum; Septocylindrium; Sphaerotheca, e.g. S. fuliginea; Sphoerulin; Sterigmatocystus; Taphrina; Thielavia; Titea; Trochila; Tricholadia; Trichosphoria; Uncinula; Ustilaginoidea; Valsa; Venturia; Verticilium, e.g. V. lub-atrum. The above 4- (2-methyleneaminophenyl) -3-trioallophanates have a high systemic fungicidal activity, i.e. they protect the plant against fungal attack both from the outside and the inside. . A discussion of the mechanism of action of systemic fungicides can be found in the World Review of Pest Control 2 (3), 1963, which gives examples of this type of action with phenylthiosemicarbazides. The systemic development of fungicides in the decade preceding this article can be found in PANS 18 (1), 1972. This article discusses the systemic properties of 55,65 fungicides, including benzimidazoles and related structures, such as some 3-thioallophanates. The fungicides according to the invention can be applied to seeds, foliage or soil. As systemic fungicides, they are particularly effective when applied to soil. Preliminary evaluation of the fungicidal properties of the compounds used as active substances according to the invention was carried out by sprinkling the plants with a solution of 300 parts per million in an amount of about 14.25 m3 / ha. . A spray solution or suspension was prepared by dissolving a weighed amount of the compound in a 50:50 mixture of acetone with water and adding the same amount of water to the solution. The general method of carrying out the fungicidal tests was to spray the plant in the pot at the stage of development to which she was susceptible to the corresponding fungal disease. For this purpose, the pot was placed on a moving belt, sprayed and allowed to dry. Stepwise, the plant was inoculated with the appropriate germ-90691 16 Table 6 Plant diseases assessed in the preliminary study 1 Fungal disease (inoculum / spores ml) 1) Botrytis cinerea (150,000) 2) Erysiphe polygoni (10-25,000) 3) Piricularia oryzae ( 10-25,000) 4) Phytophtora infestans (50-60,000)) Plasmopora viticola (150,000) 6) Helminthosphorium teres (10-15,000) 7) Cercospora apii (25,000) 8) Puccinia recondita (60,000) Roslina ( age) beans <10 days) Vicia faba beans (2 weeks) Phaseolus vulgaris rice (2 weeks) Oryza sativa tomatoes (3 weeks) Lycopersicum esculentum grapevines (leaf stages 3-4) Vitis vinifera oats (6 days) Hordeum vulgare celery ( seedling 6-8 weeks) Apium graveolens wheat (6 days) Triticum vulgare Incubation time and temperature 3 days (27-28 ° C) days (ambient temperature) 1 day * + 5-8 days (27-28 ° C) 1, 5-2 days (13 ° C) 2-3 days (2l ° C) 2 days (21 ° C) * 4 days (ambient temperature) 1 day (21 ° C) * 1 day (27 ° C) * 3— 4 days and (24 ° C) 1 day (27 ° C) * 14-18 days ni (ambient temperature) 1 day (21 ° C) * 6-8 days (ambient temperature) *) high humidity Table 7 Degree of disease reduction at 300 parts per million Compound I II III IV V VI VII VIII IX X XI XII XIII XIV XVII XVIII XIX XX XXI XXII XXIII XXIV xxv XXVI XXVII B. cinerea AAAAEAAADABEBAABABDCB BABB E. polygoni AA 4 ABAAAAAACAAAAAAAEAAAA A P. oryzae AEABEBABEBEEEEEABEEEEC BCACA - infestans - EBEEBEEEEEEEEBEEE - BCACA - Ebeeeeeeeeeeeeeeeee - - E - - - - - EEE H. teres EEEEEEEEEEEEBEEEEEEEE EEEE C. apii A - - - - - - - - - - - - - - - -. - - - - - ^. ^ - P. recondita D B C D E E B C D D D E E C D D C B D E A D A ¦ D C 17 of the fungi and incubated until disease symptoms develop, and the degree of reduction in disease progression was assessed. The following scales were used: A = inhibition 97-100% B = inhibition 90-96% C = inhibition 70-89% D = inhibition 50-70% E = no activity, inhibition less than 50%. Plants and fungal diseases tested are given in Table 6. A preliminary evaluation of the fungicidal properties of the compounds is shown in Table 7. With some of the above examples being typical, further and specific tests were performed as described below. Example XI. Test A - dose / effect 1. Bean powder (Erysiphe polygoni). A weighed amount of potential fungicide was dissolved in acetone and diluted with demineralised water containing 0.05 ml of emulsifier - modified alkylglycerine-phthalic resin in 100 ml water. The concentration was adjusted to 25 parts per million and the stock solution was then diluted by doubling the volume to give a series of dilutions of up to 1.5 parts per million. The solutions of various concentrations were sprayed on the germinating bean seeds in an amount sufficient to ensure that the plant was completely wetted. For each concentration, the tests were carried out twice. The plants were dried within 20 hours and then inoculated with a spore suspension of Erysiphe polygoni, containing 2 × 10 4 spores per ml. The inoculated and control plants were kept for 10 hours in a greenhouse at a temperature of 24-27 ° C. The number of mildew spots was counted, and the degree of disease inhibition was calculated by the formula: Disease inhibition rate = number of spots on control plants number of spots on treated plants of spots on control plants X100. The results are shown in Table 8. 2. Cucumber powder (Sphaerotheca fuyginea). The germinating seeds of the cucumbers, with two well-developed leaves and a small third leaf, were sprayed until completely wetted with solutions of 4- [ 2 - or (Example I) with different concentrations. Plants dried within a few hours, and then inoculated- Table 8 Dose / effect on tested beans Compound I II III IV VI VII VIII IX X XI XII XVII XVIII XVIII XIX XXI XXII XXIII XXIV xxv XXVI XXVII% disease inhibition at partial concentrations per million 100 99.5 97.9 91.7 0 100 100 98.8 87.3 100 91.6 100 100 100 95.2 94.8 91.6 100 100 100 100 99.0 12.5 98.4 95.3 98.4 63.0 0 100 100 86.8 75.9 94.9 85.0 98.8 98.0 100 96.2 87.5 0 100 100 100 100 98.5 6.2 94, 6 86.6 83.1 29.7 0 100 98.4 68.8, 3 96.8 82.1 95.7 79.3 100 86.7 62.6 0 100 100 98.1 98.8 95, 0 3.1 96.1 36.6 85.5 34.0 0 95.5 92.1 0 39.8 49.3 0 92.7 78.1 96.2 80.5 0 0 96.8 94, 3 96.2 97.7 79.8 1.5 95.7 0 - - - - - 0 - - - 91.5 0 - ~ - - - - - - 89.7 53.719 90691 spore suspension of Sphaerotheca fulginea eaten, containing approximately 2 X 104 spores per ml. The plants were immediately placed in a greenhouse at 24-27 ° C. and the inhibition of disease was calculated after 11 days. The following results were obtained:% of inhibition of disease development at a concentration of parts per million of a compound according to 50 25 12.5 6.3 3.1 1.6 Example I 100 100 99.6 97.9 94.3 72 ^ 5 ' Example XII. Test B. Ridge activity after rain. After chemical spraying, some of the test plants were exposed to simulated rain, 4 mm, and then inoculated with spores of phytopathogenic fungi. The results are shown in Table 9. Example XIII. System tests. C. Absorption through the roots. 1. Rice blight (Piricularia oryzae). Rice seedlings up to a height of 2.5-8 cm were grown in plastic pots. Compound XVII was dissolved in a mixture of: acetone: methanol: water (1: 1 and 2), adjusting the concentration so that 15 ml of the solution contained the specified, in parts per million, dose, used for watering the plant through the 2nd Mushroom powder of cucumbers ( Sphaerotheca fuli ginea) Cucumber plants, having 2 well-developed leaves, growing in 8 cm plastic pots, were watered with 15 ml of a solution containing various concentrations, expressed in parts per million, Compound XVII parts per million in water for watering 150 300% of disease development inhibition 91.7 98.0 compound XVII. The plants were then sprayed with a spore suspension of S. fuliginea, containing 2 × 10 4 spores per ml. The inoculated plants were immediately placed in a greenhouse at 29-32 ° C and the disease development was observed periodically. The following results were obtained: In order to further evaluate the persistence of systemic function, the cucumber plants used in the rain resistance tests described in Part B, Table 9, periodically monitored for development. wheat recondita - *) BACBA 'C 1/16 rain + **) EBEAAB - BACBAB i / 8 rain + CBEAAA - AA BB - - 1/4 rain + BA EA - - - AABB - - 1/2 rain + AACA - - *) without rain **) with rain soil. The sprayed rice plants were kept under typical greenhouse conditions at a temperature of about 27 ° C for 8 days. They were inoculated with P. Oryzae spores, and the percent inhibition of disease development was read after 6 days. The following results were obtained; • * S. fuliginea. The following observations were made: The active compounds according to the invention at low doses provide good protection against disease for more than 5 weeks after foliar or soil spraying. 90 691 21 22 Compound XVII Parts per million in irrigation water 125 250 500 % Of inhibition of disease after 6 weeks of watering EEA Compound XVII Weeks after spraying - plants 3 4 Minimum effective concentration (parts per million), resulting in 50% inhibition of mildew growth without rain 150 150 300 with rain below 75 600 600 3. Wheat powder mold (Erysiphe graminis). a. Watering the Soil Wheat plants, 5 to 7 days old, grown in plastic pots, were cut to a height of 38-50 mm and watered with 15 ml of an aqueous solution of compound XVII, a typical representative of the compounds used in the invention. The plants were then placed for 2 days in a greenhouse at 24 ° C and then inoculated by spraying with spores from E. graminis wheat plants. Assessment of the development of the disease was carried out after 6 days. The following results were obtained: Compound XVII control Disease reduction 1 at a concentration of parts per million C (E) C b. Seed treatment Wheat seeds were treated with different doses of compound XVII, shaking 40 g of seeds with 1 ml of acetone, 0.5 ml. water and a fungicide in an amount corresponding to 31, 62, 124 and 248 g / 100 kg. The impregnated grains were placed in 8 cm soil pots, repeating each test in four series. The pots were placed in a greenhouse at 21 ° -24 ° C. After the plants had grown to a height of about 50 mm, they were inoculated with an E spore suspension, graminis, containing about 30,000 spores per mL. The plants were dried and returned to the greenhouse at 21-24 ° C. After 17 days, evaluation of disease development was made. The following results were obtained; 50 55 Treatment Compound I Compound XVII control Leaf spraying parts per million concentration 12.5 6.3 12.5 6.3% of eradication 100 100 100 100 100 100 0 40 Example XV. Test E. Protection of stored fruit from rot such as brown nectarine (Monilinia fructicola) by immersion after harvesting. To evaluate the effectiveness of fruit protection by immersion in the solution after harvesting, partially ripe peaches were damaged and then immediately immersed in the solution. of the test compound at a concentration of 300 or 600 parts per million in a mixture of acetone: methanol: water (1: 1: 2). Fruits were dried at room temperature and then inoculated with Monilinia fructicola spore suspension 30 × 103. Fruits then was stored at 24 and 14 ° C until brown rot appeared on the control fruit, the following results were obtained: Compound I control Concentration of the dipping solution per million 300 600% of disease Results of observation after inoculation ¬niu ° C / weeks / 1 1.4 1.6 4.0 14/1 0 0 4.0 14/2 0 0 23.0 W Example XVI. Study F. Comparison with known compounds. Several comparative studies have been carried out on Compound I and the compounds described in British Patent No. 1,214,415. Below are some representative results: 1. Protection against rice blight (Piricularia oryzae). The rice was sprayed with the test compound in a solution of varying concentration, expressed in parts per million, and then inoculated with P. oryzae spores as described above. A direct comparison was made with the effectiveness of the following compounds from British Patent Specification No. 1214 415: 23 90691 24 compound Name 1-benzylideneamino-2j (3-methoxycarbonyl-2-thioureido) -benzene 1- (4-chlorobenzylideneamino) -2- (3-methoxycarbonyl-2-thioureido) benzene 1H (4-methoxybenzylideneamino) -2 - (3-methoxycarbonyl-2-thioureido) benzene 1- (3-nitrobenzylideneamino) -2- (3-ethoxycarbonyl-2-thioureido) benzene The following results were obtained: BD Treatment Compound I compound A compound B compound C compound D • Control Restriction of development diseases at a concentration of parts per million 1200 A C C A B (E) 600 A D D B C 300 A E D B D 150 A E E D E 75 B E E E E 37.5 B E E E E 2. Determination of inhibition zone for various fungal organisms. ml of potato dextrose agar was poured onto a plastic plate with a diameter of 9 cm. Solutions of potential fungicides of varying concentrations were prepared. The solutions were impregnated with antibiotic discs 6.35 mm in diameter and placed on agar plates in the center of the plates. On the opposite sides, at the edges of the plates, hyphae of mycelium of various fungi were placed. The plates were then kept under conditions favorable to the development of appropriate organisms. After 3 to 6 days, the zones of inhibition of mycelial growth were measured. The following grades of growth inhibition were used: + + '+ strong + + moderate + weak - none. A comparison was made with the compounds of British Patent 1,214,415 (Compounds A-D). The results are shown in Table 11. Example XVII. Study G. Effect of the fungicide on the fermentation of grape juice It is desirable that the fungicide used for spraying grapevines should not affect the fermentation rate of grape juice in wine production. Comparative studies of these properties of the compound XVII and the well-known agent were carried out. fungicidal N-trichloromethylthiophthalamide. In these tests, fermentation media consisting of 3785 ml of grape juice and 454 g of glucose were divided into 200 ml of samples, which were poured into vessels containing a sufficient amount of test compounds, dissolved in acetone: methanol: water (1: 1: 2). The fungicide concentrations were 5 and 20 parts per million. A yeast suspension (Saccromyces cerevisiae) containing 3 X 10 7 cells per ml was added to each sample and the vessels were capped with a glass and plastic tubing stopper. The free end of the plastic tube was immersed in an inverted 125 ml vessel filled with water. Table 11 Inhibition of Fungal Growth Test Compound I Compound A Compound B Compound C Compound D Part Per Million on Antibiotic Disc 1000 500 250 125 1000 500 250 125 1000 500 250 1000 500 250 1000 500 250 Aspergillus terreus + H- + + i + + + + + + :, +; ++ ++ - - - '- - + + + + + + - Fusarium roseum "Culmorum" + + + - - - + - - -. - - - - - - +! - 1 Sclerotinia sclerotiorum +. + + + + + + + + - + + + + + + +: - - - - ++ ¦, + - - —. Zythia pinastria + ¦ + ¦ + + + ++ + + + + + + ¦ + '+ - - - -:' '- | 90691 26 The time required to release 125 ml of carbon dioxide was determined. The following results were obtained. : Table 11 Fungicide Compound XVII N-trichloromethylthiophthalamide control Parts per million - Working time 125 ml CO 2 hours 24 24 120 120 24 The compounds used as the active ingredient in the agent according to the invention never showed phytotoxicity when sprayed in plants, doses that give excellent protection against phytopathogenic fungi. These compounds have never shown any insecticidal properties and therefore do not harm predatory insects. They show anthelmintic activity. For example, it has been shown that they strongly affect Aspicularis tetraptera and Symphacia obvelata. 4- and (2-methyleneaminophenyl) -3-thioallophanates are useful as fungicidal plant care products and can be used for spraying seeds, soil or foliage. In general, the fight against phytopathogenic fungi involves treating cultivated plants, including In the cultivation stage, a fungicidally active dose of at least one of the above compounds. In fungicidal applications, the above 3-thioallophanates may be used in the form of solutions or other forms. One or more of the compounds of formula I may be mixed with one or more of the carriers conventionally used in fungicidal formulations. The compounds of formula I are usually dissolved in a carrier diluent or formulated in such a way that they can be sprayed on as fungicidal formulations. For example, thioallophanates can be prepared as wettable powders, emulsion concentrates, powders, granules, aerosols, etc. In such forms, the compounds used in the composition according to the invention are diluted with a liquid or solid carrier, to which are added, if desired, surfactants. It is preferable, especially in foliar spray preparations, that the preparations contain additives such as emulsifiers, wetting agents, dispersing agents, adhesion promoters and the like usually used in practice. Commonly used additives of this type can be found in John W. McCutcheon, Inc. Detergenty and Emulsifiers 1971 AnnuaL In general, the solubility of the compounds of standard 1 is limited, however, they dissolve in solvents such as dimethylformamide, pyridine or dimethylsulfoxide, and these solutions can be diluted with water. The concentration of the solution may be from 2 to 50%, preferably from 5 to 25%. For the preparation of an emulsion concentrate, the compound is dissolved in a suitable organic solvent or a mixture of solvents, with the addition of an emulsifier to disperse the fungicide in water. The concentration of the active agent in the emulsion concentrate is usually 10-25%, and in some cases up to 75%. Wettable spraying powders are prepared by mixing the compound with a fine solid body such as clays, inorganic silicates and carbonates, silica and with a wetting agent, an adhesion promoter and / or a dispersing agent. The concentration of active ingredient in such preparations is usually 20-98%, preferably 40-75%. A typical wettable powder is prepared by mixing 50 parts of Compound I, 45 parts of a synthetic, precipitated hydrated silicon dioxide under the trade name Hi-SilR, and 5 parts of sodium lignosulfate (MarasperseR N-22). In another preparation, in place of Hi-Sil, calcium clay (Barden) was used, and in another 25% of Hi-Sil was replaced with synthetic sodium aluminosilicate under the trade name Zeolex R 7. The powders are prepared by mixing 3-thioallophanates with a fine-grained inert solid, organic or inorganic. Suitable materials for this purpose are vegetable flours, silica, silicates, carbonates and clays. One method of obtaining powders is to dilute a wettable powder with a fine-grained carrier. Usually, powder concentrates with 20-80% active ingredient content are prepared, which are then diluted to a concentration of 1-10%. The 3-thioallophanate-containing fungicides can be sprayed by conventional means, for example by using water or air as a dispersant. Dilution and spray rate are dependent on the type of device, method of dispersion and the disease to be controlled. The active agent is usually used in amounts of 0.125-30 kg / ha. For seed impregnation, the active agent is usually used in amounts of 3-600 g. / 100 kg. In the case of application to the soil, it is used 0.125-68 kg / ha, and in the case of spraying plants 0.4-12.5 kg / ha. The compounds of formula I can be used together with known fungicides: such as: - dithiocarbamates and their derivatives, such as ferrous dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebisdithiocarbamate (maneb) and its coordination compound with zinc (etylencozeb Zinc dithiocarbamate (zineb), zinc propylenebisdithiocarbamate (propineb) sodium methyl dithiocarbamate (methham) tetramethylthiuram disulfide (thiram), zineb and polyethylenethiuram disulfide complex, 3,5-dimethyl-tetrahydro, 3,5-2H2H thion (dazomet) and mixtures of these compounds with each other and with copper salts; - nitrophenol derivatives, such as dinitro- (1-methylheptyl) phenyl crotonate (dinocap), 2-tert-butyl-4,6-dinitrophenylisopropyl 3,3-dimethylacrylate; - Heterocyclic compounds such as N-trichloromethylthietrahydrophthalamide (captan), N-trichloromethylthiophthalamide (folpet), 2-heptadecyl-2-imidazoline acetate (glyodin), 2-octylisothiazolone-3, 2,4-dichloro 6H (o-chloroanilino) -s-triazine, diethyl phthalidophosphothioate, 4-butyl-1,2,4-triazole, 5-amino-1- [di (dimethylamino) phosphinyl] -3-phenyl-1 , 2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2,3-dicyano-1,4-dithiaanthraquinone (dithianon), 2-thio-1,3-dithio [4,5-b] quinoxaline (thioqunox), methyl-1- (butylcarbamyl) -2-benzimidazole carbamate (benomyl), 2- (4'-thiazolyl) benzimidazole (thiabendazole), 4H (2-chlorophenylhydrate) - irritating) -3-methyl-5-isoxazolone, pyridine-2-thiol 1-oxide, 8-hydroxyquinolinic acid and its metallic salts, 4,4-dioxide, 2,3-dihydro-5-carboxanilide-6 -methylxatin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin, a- (phenyl) -a- - (2,4-dichlorophenyl) -5-pyrimidinyl-methanol (triarimol) , cis-N- [1,1,2,2-tetrachlor oethyl / thio] -4-cyclohexene-1,2-dicarboximide, 3- [2- (3,5-dimethyl-2-hydroxycyclohexyl-2-hydroxy] glutarimide (cycloheximide), dehydroacetic acid, N- - (1,1,2-tetrachlorothio) -3a, 4,7,7a-tetrahydrophthalamide (captafol), 5-butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine (ethirimol) 4-cyclodo acetate - decyl-2,6-dimethyl and morpholine (dodemorph), 6-methyl-2-keto-1,3-dithiol-4,5-b) -quinoxaline (auinomethionate); Various halogenated fungicides such as tetrachloro-p-benzoquinone (chloranil), 2,3-dichloro-1,4-naphthoquinone, (dichlone), 1,4-dichloro -2,5-dimethoxy) enen (chloroneb ), k * was 3,5,6-trichioro-anisine (tricamba), 2,4,5,6-tetrachloroisonaphthalonitrile (TCPN), 2,6-dichloro-4-nitroaniline (dicloran ), 2-chloro-1-nitro-propane, polychlorobenzenes such as pentachloronitrobenzene (PCNB) and tetrafluoride chloroacetone; - fungicidal antibiotics such as griseofulines, kasugamycin and streptomycin; Copper fungicides, such as cuprous oxide, basic cupric chloride, basic copper carbonate, copper naphthenate and Bordeux mixtures; - various other fungicides such as diphenyl 28, dodecanoguanidine acetate (dodine), copper phenyl acetate, N-ethyl orthecio-1,2,3,6-tetrahydro-3,6-endomethane-3,4,5,6, 7,7-hexachlorophthalamide, phenyl ortheciomonetariolammonium lactate, p-dimethylaminobenzenediazosodium sulphate, methyl isothiocyanate, l-thiocyano-2,4-dinitrobenzene, 1-phenylthiosemicarbazide, calcium sulfate compounds, calcium sulphate, calcium cyanide 2-di (3-methoxycarbonyl-2-thioureido) benzene PL

Claims (2)

Zastrzezenia patentowe 1. Srodek grzybobójczy znamienny tym, ze jako 15 skladnik aktywny zawieira co najmniej jeden zwiazek o wzorze ogólnym 1, w którym X oznacza grupe o wzorze R^O— lub R1S—, w którym R1 oznacza grupe alkilowa o lancuchu prostym lub rozgalezionym o 1—12 atomach wegla w lancuchu, 20 grupe alkilowa o 1—12 atomach wegla podsta¬ wiona atomami chlorowca lub grupami metoksy- lowymi, grupe alkenylowa o 2—12 atomach wegla, ' grupe alkinylowa o 3—12 atomach wegla, grupe fenyIowa ewentualnie podstawiona grupami me- 25 tylowa metoksylowa, nitro lub atomami chlorowca, grupe benzylowa ewentualnie podstawiona grupa¬ mi metylowa, metoksylowa, nitro lub atomami chlorowca, Y oznacza 5- lub 6-czlonowy rodnik heterocykliczny, w którym heteroaWmami sa O, S 30 lub N, ewentualnie dowolna kombinacja dwóch z posród podanych heteroatomów z tym, ze ogólna liczba heteroatomów w czlonie jest nie wieksza od 3, ewentualnie podstawiony grupami acetoksymety- lowa, metylowa, nitro lub atomami chlorowca, R, 35 oznacza atom wodoru lub grupe metylowa, Z ozna¬ cza atom chlorowca, grupe metylowa, metoksyme- tylowa, lub nitro a n oznacza liczbe calkowita 0—3 oraz jedna lub wieksza ilosc substancji pomocni¬ czych stosowanych zazwyczaj w preparatach grzy¬ wo bobójczych.Claims 1. A fungicide characterized in that the active ingredient is at least one compound of the general formula I, in which X is a group of the formula R10- or R1S-, in which R1 is a straight or branched chain alkyl group with 1-12 carbon atoms in the chain, 20 alkyl group with 1-12 carbon atoms substituted by halogen atoms or methoxy groups, alkenyl group with 2-12 carbon atoms, alkynyl group with 3-12 carbon atoms, phenyl group optionally substituted with methyl, methoxy, nitro or halogen groups, benzyl optionally substituted with methyl, methoxy, nitro or halogen groups, Y is a 5- or 6-membered heterocyclic radical in which the heteroWs are O, S 30 or N, optionally any combination of two of the heteroatoms mentioned, provided that the total number of heteroatoms in the member is no more than 3, optionally substituted with acetoxymethyl, methyl, nitro or halogen groups ca, R 35 is hydrogen or methyl, Z is halogen, methyl, methoxymethyl, or nitro an is 0-3 and one or more excipients usually used in mushroom preparations anti-killers. 2. Srodek wedlug zastrz. 1 znamienny tym, ze jako substancje pomocnicza zawiera jeden lub wieksza ilosc dodatków takich jak rozpuszczalnik zwiazku lub zwiazków o wzorze ogólnym 1, w 45 którym X, Y, Z, R i n maja znaczenie podane w zastrz. 1, rozcienczalnik w stanie stalym, srodek emulgujacy, srodek lepiacy, srodek dyspergujacy, srodek zwilzajacy i srodek rozpylajacy.90691 z„ R N=C-Y NHCNHC-X I " S 0 Wzór 1 Zn ^ z--c» Wzdr 4 N=CH^q NHCNHC-X ii ii S 0 Wzdr 2 s o NHCNHCO- aLka Z Wzór 3 Y-C-0 Wzdr 5 X-CNCS Z„- o Wzdr 6' -NH2 NHCNHC-X ii ii S 0 Wzdr 7 Zn N-C-Y Wzór 8 z„- NH2 NH, +¦ X-C-NCS—Zn NH, R i 2 +Y-C=0^- Wzdr i NHCNHC-X u I Schemat i S 0 X^L-Cl + KSCN rozpuszczaln;k - Schemal 2 XCNCS+KCl90691 z"-tOC N\ 0 -NHC-X +¦ H2S H Schemat 3 Zn "t/-NHCNHC-X + ^-^ ii ii S O x. R l rozpuszczalnik H—Q kwa 5, agrzezanie Schemat A s 6 — 7_-f*\N-L-Y •. %^-c-O — VtJ5J"T ^ CrOS^^-^8- Wzór { Schemat 5 N0t NHCNHC-X I 1 5 0 Wzór 9 *rr N-CH-^g^W NHCNHC-X k b Wzór iO NH2 ° \Nz6r ii NHC(S)NHC00CH3 NHC(S)NHC0OCH, Wzdr M OK-28/1856190691 Z, R jj—j NHCNHC-K » A S 0 Wzór 15 N=CHY NHCNHC00CHs Wzór 14 NH, i OCH-1! W o ¦ Ln Schemat S Schemat 7 N=CH NH, N=CHJ| 11 NH2 ° "XNH CNHC-X W 4 i -w i-to N=R< NH2 +- SCN-COR X ^.-2 Schemat 8 N=R4 NHCNHCOR PL2. The measure according to claim One or more additives, such as a solvent for a compound or compounds of the general formula 1, in which X, Y, Z, R and n are as defined in claim 1, characterized in that the excipient is 1, solid diluent, emulsifying agent, tackifier, dispersant, wetting agent and spraying agent. 90691 of "RN = CY NHCNHC-X I" S 0 Formula 1 Zn ^ z - c »Wzdr 4 N = CH ^ q NHCNHC-X ii ii S 0 Wzdr 2 so NHCNHCO- aLka Z Formula 3 YC-0 Wzdr 5 X-CNCS Z "- o Wzdr 6 '-NH2 NHCNHC-X ii ii S 0 Wzdr 7 Zn NCY Formula 8 z" - NH2 NH, + ¦ XC-NCS — Zn NH, R i 2 + YC = 0 ^ - Wzdr and NHCNHC-X u I Scheme i S 0 X ^ L-Cl + KSCN solvent; k - Scheme 2 XCNCS + KCl90691 z " -tOC N \ 0 -NHC-X + ¦ H2S H Scheme 3 Zn "t / -NHCNHC-X + ^ - ^ ii ii SO x. Rl solvent H — Q kwa 5, ccording Scheme A s 6 - 7_-f * \ NLY •.% ^ - cO - VtJ5J "T ^ CrOS ^^ - ^ 8- Formula {Scheme 5 N0t NHCNHC-X I 1 5 0 Formula 9 * rr N-CH- ^ g ^ W NHCNHC-X kb Formula iO NH2 ° \ Nz6r ii NHC (S) NHC00CH3 NHC (S) NHC0OCH, Wzdr M OK-28/1856190691 Z, R jj — j NHCNHC-K »AS 0 Formula 15 N = CHY NHCNHC00CHs Formula 14 NH, i OCH-1 ! W o ¦ Ln Scheme S Scheme 7 N = CH NH, N = CHJ | 11 NH2 ° "XNH CNHC-X W 4 i -w i-to N = R <NH2 + - SCN-COR X ^ .- 2 Scheme 8 N = R4 NHCNHCOR PL
PL1974168031A 1973-01-22 1974-01-10 Heterocyclic compounds and fungidical compositions[au6271173a] PL90691B1 (en)

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US00325783A US3852278A (en) 1973-01-22 1973-01-22 Preparation of 4-(2-(furfurylideneamino)-phenyl)-3-thioallophanates
US325277A US3860586A (en) 1973-01-22 1973-01-22 Derivatives of 4-(2-aminophenyl)-3-thioallophanic acid

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