NO780426L - BISDITIOKARBAMATESTERE. - Google Patents

BISDITIOKARBAMATESTERE.

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Publication number
NO780426L
NO780426L NO780426A NO780426A NO780426L NO 780426 L NO780426 L NO 780426L NO 780426 A NO780426 A NO 780426A NO 780426 A NO780426 A NO 780426A NO 780426 L NO780426 L NO 780426L
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Norway
Prior art keywords
carbon atoms
compound according
formal
bis
aryl
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NO780426A
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Norwegian (no)
Inventor
Eugene Ribello Bertozzi
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Thiokol Corp
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Publication of NO780426L publication Critical patent/NO780426L/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/21—Radicals derived from sulfur analogues of carbonic acid
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three 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
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BisditiokarbamatestereBisdithiocarbamate esters

Foreliggende oppfinnelse vedrører bisditiokarbamat-estere av di-lavere alkyl formaler, polymere av disse og forbindelser med analog struktur til disse og fremgangsmåte for fremstilling og anvendelse av dera. The present invention relates to bisdithiocarbamate esters of di-lower alkyl formals, polymers thereof and compounds with an analogous structure to these and methods for their production and use.

Foreliggende oppfinnelse tilveiebringer en forbindelse med formel I The present invention provides a compound of formula I

hvor Q er where Q is

hvor R og R<1>uavhengig er hydrogen, C-^-C^g alkyl, C^-C^q alkenyl, C^-C-^q alkenyl, karbocyklisk aryl med 6 til 10 karbonatomer i arylkjernen, heterocyklisk aryl med 1 eller 2 heteroatomer og 3 til 9 karbonatomer i arylkjernen, aralkyl hvor aryldelen er heterocyklisk eller karbocyklisk aryl som tidligere angitt, og alkyl er som forut angitt, og hvor hydro-karbyldelene av de forannevnte rester enten er usubstituerte eller ytterligere substituert med alkyl, alkenyl, alkynyl som tidligere angitt, hydroksy eller alkoksy med 1 til 10 karbonatomer i alkylresten, og R og R' er sammenknyttet og da sammen med nitrogenatomet danner piperidino, pyrrolidino, morfolino, piperazino, pyridino, pyridazino, tetrahydrotiazol, dehydroindol, tetrahydrooksazol eller tiamorfolino, eller where R and R<1> are independently hydrogen, C-^-C^g alkyl, C^-C^q alkenyl, C^-C-^q alkenyl, carbocyclic aryl with 6 to 10 carbon atoms in the aryl nucleus, heterocyclic aryl with 1 or 2 heteroatoms and 3 to 9 carbon atoms in the aryl nucleus, aralkyl where the aryl part is heterocyclic or carbocyclic aryl as previously indicated, and alkyl is as previously indicated, and where the hydrocarbyl parts of the aforementioned residues are either unsubstituted or further substituted with alkyl, alkenyl , alkynyl as previously indicated, hydroxy or alkoxy with 1 to 10 carbon atoms in the alkyl residue, and R and R' are linked and then together with the nitrogen atom form piperidino, pyrrolidino, morpholino, piperazino, pyridino, pyridazino, tetrahydrothiazole, dehydroindole, tetrahydrooxazole or thiamorpholino, or

(B) 2-merkaptotiazol enten usubstituert eller substituert med alkyl eller aryl som forut angitt, eller kondensert til (B) 2-mercaptothiazole either unsubstituted or substituted with alkyl or aryl as previously indicated, or condensed to

mono eller bicyklisk heteroaryl eller karbocyklisk arylkjerne<:>som foran angitt, eller mono or bicyclic heteroaryl or carbocyclic aryl ring<:>as indicated above, or

hvor Y er alkylendiamin med fra 2 til ca. 10 karbonatomer,' cykloalkylendiamin med 5 eller 6 karbonatomer i cykloalkylen-ringen, alkenylendiamin med 4 til 10 karbonatomer, cyklo-alkenylendiamin med 5 eller 6 karbonatomer i cykloalkenylen-ringen, alkynylendiamin med fra 4 til 10 karbonatomer eller X er Cl, O eller hvor Y er som forut definert, Z er Q eller klor, og x er tilstrekkelig til å gi en total molekylvekt på 1000, n er et helt tall fra 2 til ca. 10, m er 0 eller et helt tall fra 1 til 3 med det forbehold at hvis m er 0 er X where Y is alkylenediamine with from 2 to approx. 10 carbon atoms,' cycloalkylenediamine with 5 or 6 carbon atoms in the cycloalkylene ring, alkenylenediamine with 4 to 10 carbon atoms, cycloalkenylenediamine with 5 or 6 carbon atoms in the cycloalkenylene ring, alkynylenediamine with from 4 to 10 carbon atoms or X is Cl, O or where Y is as previously defined, Z is Q or chlorine, and x is sufficient to give a total molecular weight of 1000, n is an integer from 2 to approx. 10, m is 0 or an integer from 1 to 3 with the proviso that if m is 0 then X

hvor Y, n, m og Z er som forut angitt, og addisjonsalter derav. De konkrete utførelsesformer av dette komposisjonsaspektet av oppfinnelsen ligger i anvendelseskarakteristika som antioksydanter, korrosjonsinhibitorer, svovelholdige oljeadditiver, biocider for inhibering av veksten av plante-infeksjoner og når X er identisk med Q og Q er X som angitt i formel I under (A) eller (B) som gummiherdingsakselratorer. where Y, n, m and Z are as previously stated, and addition alters thereof. The concrete embodiments of this compositional aspect of the invention lie in application characteristics such as antioxidants, corrosion inhibitors, sulfur-containing oil additives, biocides for inhibiting the growth of plant infections and when X is identical to Q and Q is X as indicated in formula I under (A) or ( B) as rubber curing accelerators.

Foretrukne utførelsesformer av forbindelsene med formel I er Preferred embodiments of the compounds of formula I are

slike hvor m er 1.such where m is 1.

Oppfinnelsen gir også en herdbar komposisjon omfattendeThe invention also provides a curable composition comprehensively

a) en vulkaniserbar gummi, oga) a vulcanizable rubber, and

b) en forbindelse med formel I hvor O er (A) eller (B) og X er identisk med Q, og m og n b) a compound of formula I where O is (A) or (B) and X is identical to Q, and m and n

er som angitt for formel I.is as stated for formula I.

De konkrete utførelsesformer av dette komposisjonsaspektet av oppfinnelsen ligger i anvendelseskarakteristika og kunne herdes til herdet.gummi med større hastighet under behandling med konvensjonelle gummiherdingsmidler enn de tilsvarende vulkaniserbare gummityper alene. The concrete embodiments of this compositional aspect of the invention lie in application characteristics and could be hardened into cured rubber at a greater rate during treatment with conventional rubber curing agents than the corresponding vulcanizable rubber types alone.

Oppfinnelsen tilveiebringer også en fremgangsmåte for å kontrollere plantesykdommer som omfatter applikasjon på en plante eller i jorden som umiddelbart ongir denne planten av en forbindelse med formel I. The invention also provides a method for controlling plant diseases which comprises the application to a plant or to the soil which immediately infests that plant of a compound of formula I.

Fremstilling og anvendelse av komposisjonene ifølge oppfinnelsen skal nå beskrives under henvisning til spesifikke utførelsesformer av denne nemlig bis-(dimetylditiokarbamyl-etyl) formal (II). Production and use of the compositions according to the invention will now be described with reference to specific embodiments of this, namely bis-(dimethyldithiocarbamyl-ethyl) formal (II).

For å fremstille II kan dimetylamin behandles med tilnærmet støkiometriske mengder av karbondisulfid og vandig natriumhydroksyd mens varme ledes vekk fra den eksoterme reaksjonen som oppstår. Når reaksjonsblandingen som inneholder dimetyl-ditiokarbaminsyrenatriumsalt er blitt homogen kan tilnærmet en halv ekvivalent bis-(2-kloretyl)formal tilsettes langsomt under varming, gjerne ved en temperatur mellom 60°C og løs-ningens tilbakeløpstemperatur, fortrinnsvis ved ca. 80°C og reaksjonsblandingen holdes i dette temperaturområdet ved leilighetsvis tilsetning av små deler deionisert vann og etterfølgende fjerning av vannfasen fra tofasesystemet inntil reaksjonsblandingens pH forblir ved ca. 7. II kan om ønsket utvinnes ved standardiserte tekniske metoder, gjerne ved fortynning av den avkjølte reaksjonsblandingen med ytterligere deionisert vann fulgt av gjenvinning av det resul-terende felte produktet ved filtrering og tørking. To prepare II, dimethylamine can be treated with approximately stoichiometric amounts of carbon disulfide and aqueous sodium hydroxide while heat is diverted from the resulting exothermic reaction. When the reaction mixture containing dimethyl-dithiocarbamic acid sodium salt has become homogeneous, approximately half an equivalent of bis-(2-chloroethyl)formal can be added slowly while heating, preferably at a temperature between 60°C and the reflux temperature of the solution, preferably at approx. 80°C and the reaction mixture is kept in this temperature range by occasional addition of small portions of deionized water and subsequent removal of the water phase from the two-phase system until the pH of the reaction mixture remains at approx. 7. II can, if desired, be recovered by standardized technical methods, preferably by diluting the cooled reaction mixture with additional deionized water followed by recovery of the resulting precipitated product by filtration and drying.

For en fagmann ville det være åpenbart at substitusjon av andre kjente aminer'i stedet for det angitte dimetylamin og av andre kjente bis-(oj -halogenalkyl)-etere og formaler i stedet for bis-(2-kloretyl)formal som angitt, vil ved analog fremgangsmåte gi fremstilling av andre forbindelser med formel I hvor m er 0 eller 1. Forbindelser med formel It would be obvious to one skilled in the art that substitution of other known amines in place of the indicated dimethylamine and of other known bis-(oj -haloalkyl) ethers and formals in place of bis-(2-chloroethyl)formal as indicated would by an analogous method give preparation of other compounds of formula I where m is 0 or 1. Compounds of formula

hvor n er som ovenfor angitt og m er 2 eller 3 kan frem^stilles ved å kondensere a- cohalogenalkylforbindelser med formaldehyd i nærvær av en sur katalysator som ved fremstillingen av de analogiske forbindelser hvor m er 1 men ved å doble eller tredoble andelen av formaldehyd for m = where n is as stated above and m is 2 or 3 can be prepared by condensing α-cohaloalkyl compounds with formaldehyde in the presence of an acidic catalyst as in the preparation of the analogous compounds where m is 1 but by doubling or tripling the proportion of formaldehyde for m =

2 og m = 3 henholdsvis, og kontrollere temperaturen til2 and m = 3 respectively, and control the temperature to

det nødvendige minimum for fjerning av vann. Disse forbindelsene kan også anvendes i stedet for det angitte bis-(2-kloretyl)formal for å fremstille forbindelser med formel I hvor m = 2 eller 3 som ønsket. the necessary minimum for the removal of water. These compounds can also be used instead of the indicated bis-(2-chloroethyl)formal to prepare compounds of formula I where m = 2 or 3 as desired.

Det er også åpenbart av med monoaminer vil monomere pro-dukter fremstilles og at kontroll av de relativt molare andeler av ditiokarbonatsalt og dihalogenformal eller eter-reaktant vil gi substitusjon av et eller begge halogenatomer. Likeledes vil det være åpenbart at hvis diaminer anvendes kan andelen av karbondisulfid og natriumhydroksyd varieres slik at en eller begge aminofunksjoner reagerer. Hvis bare ditiokarbamatet dannes vil selvfølgelig reaksjonen med dihalogenformaler eller etere forløpe som ved monoaminer. Hvis på den annen side to ditiokarbamatfunksjoner dannes, It is also obvious that monoamines will produce monomeric products and that control of the relative molar proportions of dithiocarbonate salt and dihaloformal or ether reactant will result in substitution of one or both halogen atoms. Likewise, it will be obvious that if diamines are used, the proportion of carbon disulphide and sodium hydroxide can be varied so that one or both amino functions react. If only the dithiocarbamate is formed, the reaction with dihaloformals or ethers will of course proceed as with monoamines. If, on the other hand, two dithiocarbamate functions are formed,

vil reaksjonen med like molare andeler dihalogenforbindelser resultere i polymerer med en molekylvekt på opptil ca. 1000. Det antas at i så tilfelle vil en ende av polymeren ha en halogenavslutning og den« andre enden en ditiokarbamatavslut- the reaction with equal molar proportions of dihalogen compounds will result in polymers with a molecular weight of up to approx. 1000. It is assumed that in that case one end of the polymer will have a halogen end and the other end a dithiocarbamate end

ning selv om fagmannen vil erkjenne-at molekyler som inne-<!>holder endegrupper av hver enkelt funksjonell gruppe også kan dannes. ning although the person skilled in the art will recognize that molecules which contain end groups of each individual functional group can also be formed.

Hvis imidlertid et betydelig overskudd av bis-ditiokarbamat-forbindelsen eller dihalogenforbindelsen i forhold til den andre reaktanten anvendes vil polymerdannelsen inhiberes og lavmolekylvekts-adduktet dannes, f.eks. for et 2 til 1 molar forhold av reaktanter vil en forbindelse av typen D-E-D hvor D er resten av reaktanten med det høyere molarforholdet og If, however, a significant excess of the bis-dithiocarbamate compound or the dihalogen compound in relation to the second reactant is used, the polymer formation will be inhibited and the low molecular weight adduct will be formed, e.g. for a 2 to 1 molar ratio of reactants, a compound of the type D-E-D where D is the remainder of the reactant with the higher molar ratio and

E er resten av reaktanten med det lavere molarforholdet dannes. E is the remainder of the reactant with the lower molar ratio formed.

Merkaptotiazol-derivatene som betraktes som del av formel I kan'fremstilles fra natriumsaltene av kjente merkaptotiazoler og de foran nevnte dihalogenforbindelser på analog måte med den som anvendes for andre forbindelser med formel I. Fremstilling av merkaptotiazoler fra aromatiske aminer og karbondisulfid eller fra 2 hydroksymonoalifatiske. monoaminer og karbondisulfid er velkjent. The mercaptothiazole derivatives which are considered part of formula I can be prepared from the sodium salts of known mercaptothiazoles and the aforementioned dihalogen compounds in an analogous manner to that used for other compounds of formula I. Preparation of mercaptothiazoles from aromatic amines and carbon disulphide or from 2 hydroxy monoaliphatic. monoamines and carbon disulfide are well known.

Ved bruk av forbindelsene ifølge oppfinnelsen, særlig forbindelsene med formel I hvor X er identisk med Q og Q og Y er som angitt i (A) eller (B) under disse, som gummiherdingsakselratorer kommer anvendelsen av dem i kombinasjon med When using the compounds according to the invention, especially the compounds of formula I where X is identical to Q and Q and Y are as indicated in (A) or (B) below, as rubber curing accelerators their use comes in combination with

eller i stedet for andre kjente gummiherdingsakselratoreror instead of other known rubber curing accelerators

i konvensjonelle kjente gumraiformuleringer på tale. Formuleringene vil være av sådanne naturlige og syntetiske gummityper som er kjent for å gjenomgå ;svovelherding, men vil ikke nødvendigvis være svovelherdingsformuleringer. Andre konvensjonelle gummiherdingsmidler som er kjente for in conventional known gumrai formulations in speech. The formulations will be of such natural and synthetic rubber types which are known to bypass sulfur curing, but will not necessarily be sulfur curing formulations. Other conventional rubber curing agents known to

å erstatte svovel som herdingsreagenser for, gummi kan anvendes. to replace sulfur as curing reagents for rubber can be used.

Ved bruk av komposisjoner ifølge oppfinnelsen som biocider for behandling eller forhindring av plantesykdommér kan de anvendes på frø, hele planten eller den angrepne delen av When using compositions according to the invention as biocides for the treatment or prevention of plant diseases, they can be applied to seeds, the whole plant or the attacked part of

planten eller jorden som imiddelbart omgir planten ettersom hva er funnet og være virksomt ved jevne behandlinger av det the plant or the soil that immediately surrounds the plant according to what has been found and be effective by regular treatments of it

spesielle aktuelle patogenet. Selvfølgelig kan forbindelsen anvendes alene eller i kombinasjon med et i jordbruket aksepterbart bæremiddel i form av pulver eller væske enten som spray, støv, dusj eller hvis. det passer immersjon på gjenstanden som skal behandles. Doseringen vil selvfølgelig variere med infeksjonsgraden, typen patogen, type plante som behandles og applikasjonsmetoden. Da forbindelsene med mulig unntakelse av visse merkaptotiazol-derivater generelt er relativt ikke-toksiske ovenfor planter, vil doseringer i overskudd utover det nødvendige minimum for virkning mot patogene ikke ventes å være skadelige på kulturer som ikke brukes som næringsmidler. Normalt vil anvendelse av en fortynnet konsent.rasjonserie muliggjøre valg av effektive konsentrasjoner mot et patogen og vil ikke gi permanente toksiske virkninger på en spesiell plantetype. På nærings-middelkulturer bør anvendelsen selvsagt være slik at rester av forbindelsene vil være minimale ved innhøstingstidspunktet i hvert fall på de spiselige deler. Generelt kan en vandig suspensjon som inneholder mellom 1 og 10 000 ppm aktiv bestanddel, fortrinnsvis mellom 100 og 1 000 ppm anvendes som spray. particular pathogen in question. Of course, the compound can be used alone or in combination with an agriculturally acceptable carrier in the form of powder or liquid either as a spray, dust, shower or if. immersion is suitable for the object to be treated. The dosage will of course vary with the degree of infection, the type of pathogen, the type of plant being treated and the method of application. As the compounds, with the possible exception of certain mercaptothiazole derivatives, are generally relatively non-toxic to plants, dosages in excess of the required minimum for effect against pathogens are not expected to be harmful to cultures that are not used as food. Normally, the use of a diluted concentration series will enable the selection of effective concentrations against a pathogen and will not produce permanent toxic effects on a particular plant type. On food crops, the application should of course be such that residues of the compounds will be minimal at the time of harvest, at least on the edible parts. In general, an aqueous suspension containing between 1 and 10,000 ppm of active ingredient, preferably between 100 and 1,000 ppm, can be used as a spray.

Ved anvendelse av komposisjoner ifølge oppfinnelsen som antioksydanter, korrosjonsinhibitorer eller svovelholdige oljeadditiver, kan de brukes i kombinasjon med eller i stedet for andre kjente antioksydanter, korresjonsinhibitorer og svovelholdige oljeadditiver i liknende formuleringer som den som nå anvendes for disse formål. When using compositions according to the invention as antioxidants, corrosion inhibitors or sulphur-containing oil additives, they can be used in combination with or instead of other known antioxidants, corrosion inhibitors and sulphur-containing oil additives in similar formulations to the one currently used for these purposes.

Slik det her brukes og i de medfølgende krav betyr uttrykket alkyl rettlinjet, forgrenet kjede eller cykliske alkylrester slik som uten å være begrenset til disse metyl, etyl, i-butyl, cykloheksyl og liknende. Uttrykket alkenyl betyr en rettlinjet, forgrenet kjede eller cyklisk alkenylrest med den begrensning at når den er knyttet til et nitrogenatom kan det ikke foreligge ikke-aromatiske umettning i 1,2-stilling slik som uten å være begrenset til disse 2-propenyl, 2-butenyl, 2-cykloheksenyl, 3-metyl-2-pentenyl og liknende. Uttrykket alkynyl betyr rettlinjet eller forgrenet kjede-alkynylrester med det forbehold at ikke-aromatisk umettning ikke foreligger i 1,2-stilling som f.eks. uten å være begrenset til disse 2-propynyl, 2-butynyl, 4. metyl-2-pentynyl og liknende. As used herein and in the accompanying claims, the term alkyl means straight, branched chain or cyclic alkyl residues such as, but not limited to, methyl, ethyl, i-butyl, cyclohexyl and the like. The term alkenyl means a straight, branched chain or cyclic alkenyl residue with the limitation that when attached to a nitrogen atom there can be no non-aromatic unsaturation in the 1,2 position such as but not limited to 2-propenyl, 2- butenyl, 2-cyclohexenyl, 3-methyl-2-pentenyl and the like. The term alkynyl means straight or branched chain alkynyl residues with the proviso that non-aromatic unsaturation is not present in the 1,2 position such as e.g. without being limited to these 2-propynyl, 2-butynyl, 4. methyl-2-pentynyl and the like.

Uttrykket addisjonsalter omfatter kationiske salter av tiokarbamatfunksjoner i et spesielt molekyl som kan gi saltdannelse. De kationiske saltene som omfattes innbefatter sådanne at alkali- og jordalkali-metaller som natrium, kalium, kalsium, magnesium eller liknende, tunge metaller som jern og kopper og kationer avledet fra ammoniakk eller et basisk amin. Uttrykket kation avledes fra ammoniakk eller et basisk amin betyr positivt ladede ammoniumioner og analoge ioner avledet fra organiske nitrogenholdige baser som er sterke nok til å danne slike kationer. Anvendelige baser for dette formål danner en klasse hvis avgrensning er åpenbar for en fagmann. For rent illustrerende formål kan de sies å omfatte i kationisk form sådanne med formel The term addition salt includes cationic salts of thiocarbamate functions in a particular molecule which can give salt formation. The cationic salts covered include such as alkali and alkaline earth metals such as sodium, potassium, calcium, magnesium or the like, heavy metals such as iron and copper and cations derived from ammonia or a basic amine. The term cation derived from ammonia or a basic amine means positively charged ammonium ions and analogous ions derived from organic nitrogenous bases which are strong enough to form such cations. Useful bases for this purpose form a class whose delimitation is obvious to a person skilled in the art. For purely illustrative purposes, they can be said to include in cationic form those with formula

2 3 4 2 3 4

hvor R , R og R som er uavhengige er hydrogen, alkyl medwhere R , R , and R , which are independent, are hydrogen, alkyl med

1 til 10 karbonatomer, monokarbocyklisk aryl med ca. 6 karbonatomer, monokarbocyklisk arylakyl med fra ca. 7 til 11 karbonatomer, hydroksyalkyl med fra ca. 1 til 3 karbonatomer eller monokarbocyklisk arylhydroksyalkyl med fra ca. 7 til 15 karbonatomer, eller som sammen med nitrogenatomer hvortil 2 3 4 1 to 10 carbon atoms, monocarbocyclic aryl with approx. 6 carbon atoms, monocarbocyclic arylalkyl with from approx. 7 to 11 carbon atoms, hydroxyalkyl with from approx. 1 to 3 carbon atoms or monocarbocyclic arylhydroxyalkyl with from approx. 7 to 15 carbon atoms, or as together with nitrogen atoms to which 2 3 4

de er bundet to av R , R og R danner dél av en 5- eller 6-leddet heterocyklisk ring og disse monokarbocykliske aryl-gruppene er usubstituert eller mono- eller dialkylsubstituert og alkylgruppene inneholder fra 1 til ca. 10 karbonatomer. they are bound two of R , R and R form part of a 5- or 6-membered heterocyclic ring and these monocarbocyclic aryl groups are unsubstituted or mono- or dialkyl substituted and the alkyl groups contain from 1 to approx. 10 carbon atoms.

Illustrerende kationer avledet fra ammoniakk eller et basisk amin er ammoniakk, mono-, di- og trimetylammoniakk, mono-, di- og trietylammoniakk, mono, di- og tripropyl-ammoniakk.(iso og normal), etyldimetylammoniakk, benzyldimetylammoniakk, cykloheksylammoriiakk , benzylammoniakk , dibenzylaarmoniakk, piperidinium, morfolinium pyrrolidinium, piperazinium, 1-metylpiperidinium, 4-etylmorfolinium, 1-isopropylpyrroli-dinium, 1,4-dimetylpiperazinium, 1-n-butyl<p>iperidinium, 2-metylpiperidinium, lr-etyl-2-metylpiperidinium, mono-, di- Illustrative cations derived from ammonia or a basic amine are ammonia, mono-, di- and trimethylammonia, mono-, di- and triethylammonia, mono-, di- and tripropyl-ammonia (iso and normal), ethyldimethylammonia, benzyldimethylammonia, cyclohexylammonia, benzylammonia , dibenzylammonia, piperidinium, morpholinium pyrrolidinium, piperazinium, 1-methylpiperidinium, 4-ethylmorpholinium, 1-isopropylpyrrolidinium, 1,4-dimethylpiperazinium, 1-n-butyl<p>iperidinium, 2-methylpiperidinium, lr-ethyl-2- methylpiperidinium, mono-, di-

og trietanolammoniakk, etyldietanolammoniakk, n-butyl-mono-etanoammoniakk, tris(hydroksymetyl)metylammoniakk, fenylmono-etanolammoniakk og liknende. Likeledes innbefatter det syre-addisjonsalter av slike forbindelser med formel I med en nitrogenfunksjon som er i stand til å danne slike syreaddi-sjonssalter. De gjeldende salter er sådanne fra både orga-' niske og uorganiske syrer som saltsyre, bromhydrogensyre, svovelsyre, salpetersyre, fosforsyre, metansulfonsyre, benzen-sulfonsyre og liknende. and triethanol ammonia, ethyl diethanol ammonia, n-butyl mono-ethane ammonia, tris(hydroxymethyl) methyl ammonia, phenyl mono ethanol ammonia and the like. Likewise, it includes acid addition salts of such compounds of formula I with a nitrogen function capable of forming such acid addition salts. The applicable salts are those from both organic and inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid and the like.

Fagmannen vil selvfølgelig se at ditiokarbamatsyrer er usta-bile og at følgelig overføringen fra en kationisk saltform til en annen lettest utføres ved å sende en saltform gjennom en kationbytter ladet med kationet av den salt som er ønsket. Syreaddisjonssaltene kan lett fremstilles ved å blande The person skilled in the art will of course see that dithiocarbamic acids are unstable and that consequently the transfer from one cationic salt form to another is most easily carried out by passing one salt form through a cation exchanger charged with the cation of the desired salt. The acid addition salts can be easily prepared by mixing

vandige løsninger av syrer og den riktige nitrogenbase-forbindelsen og tørke. Det er åpenbart at tiokarbamatsalt-funksjoner ikke må foreligge i en forbindelse som skal over-føres til et syreaddisjonsalt. aqueous solutions of acids and the appropriate nitrogen base compound and drying. It is obvious that thiocarbamate salt functions must not be present in a compound which is to be transferred to an acid addition salt.

Uttrykket i jordbruket aksepterbar bærer omfatter vanligeThe term agriculturally acceptable carrier includes ordinary

og i handelen førte substanser innbefattende, men ikke begrenset til vann, kerosen, alkohol og dimetylsulfoksyd som anvendes for å formulere suspensjoner, løsninger eller pulver-doseringsformer for anvendelse på frø, planter eller jord for behandling av patogeninfeksjoner, og det omfatter også slike former som fremstilles enten tørt eller som en kønsentrat for senere omdannelse til doseringsformer for applikasjon. and commercially available substances including but not limited to water, kerosene, alcohol and dimethylsulfoxide used to formulate suspensions, solutions or powder dosage forms for application to seeds, plants or soil for the treatment of pathogen infections, and it also includes such forms as manufactured either dry or as a sex concentrate for later conversion into dosage forms for application.

De følgende eksempler illustrerer den beste metoden oppfinneren har funnet for utførelse av sin oppfinnelse. The following examples illustrate the best method the inventor has found for carrying out his invention.

EKSEMPEL 1 EXAMPLE 1

Bis( 2- dimetylitiokarbamyl- etyl) formalBis(2-dimethylthiocarbamyl-ethyl) formal

A. I en 25% vandig løsning av dimetylamin (1,0 mol) tilsettes fast natriumhydroksyd (1,0 mol) under røring og kjøling. Når blandingen er avkjølt til 30°e tilsettes karbondisulfid (1,0 mol) tilstrekkelig langsomt til å A. Solid sodium hydroxide (1.0 mol) is added to a 25% aqueous solution of dimethylamine (1.0 mol) while stirring and cooling. When the mixture has cooled to 30°, carbon disulfide (1.0 mol) is added slowly enough to

holde temperaturen i blandingen ved ca. 30°C ved røring. Etter røring ved ca.. 30°C i ca. 4,5 timer blir blandingen homogen. keep the temperature of the mixture at approx. 30°C when stirring. After stirring at approx. 30°C for approx. 4.5 hours, the mixture becomes homogeneous.

B. Den vandige løsningen av dimetylditiokarbaminsyre som var fremstilt i A ovenfor tilsettes bis(2-kloretyl)formal (0,5 mol) under oppvarming til 6 0°C. Etter at alt formale B. The aqueous solution of dimethyldithiocarbamic acid which was prepared in A above is added bis(2-chloroethyl)formal (0.5 mol) while heating to 60°C. After everything formal

er tilsatt oppvarmes reaksjonen ved tilbakeløp i ca. 1/2 time og får deretter stå ved omgivelsestemperaturer i ca. 16 timer. Det foreligger to faser og den vandige fasen gir en alkalisk reaksjon i pH-området 12. Reaksjonsblandingen varmes så i et tidsrom av 4 timer til ca. 70°C til 80°C under røring. Etter ca. 1 time tilsettes en liten mengde deionisert vann og etter grundig blanding dekanteres det. vandige skiktet. Mer deionisert vann tilsettes og dekanteres igjen etter grundig blanding. Denne fremgangsmåten følges to ganger til i løpet av en 2 timers periode mens pH i det vandige skiktet forblir konstant ved 7. Fulgt av endelig dekantering tilsettes deionisert vann langsomt under røring til den varme reaksjonsblandingen. Det oppnås en granulær felling. Etter filtrering og tørking av fellingen til konstant vekt oppnås sluttproduktet (84,9%) smeltepunkt tykning 6.80 - 75°C, smelter ved 78° - 82°C. is added, the reaction is heated at reflux for approx. 1/2 hour and then allowed to stand at ambient temperatures for approx. 16 hours. There are two phases and the aqueous phase gives an alkaline reaction in the pH range 12. The reaction mixture is then heated for a period of 4 hours to approx. 70°C to 80°C with stirring. After approx. After 1 hour a small amount of deionized water is added and after thorough mixing it is decanted. aqueous layer. More deionized water is added and decanted again after thorough mixing. This procedure is followed two more times over a 2 hour period while the pH of the aqueous layer remains constant at 7. Following final decantation, deionized water is added slowly with stirring to the hot reaction mixture. A granular precipitate is obtained. After filtering and drying the precipitate to constant weight, the final product (84.9%) is obtained, melting point thickening 6.80 - 75°C, melting at 78° - 82°C.

EKSEMPEL 2 EXAMPLE 2

Bis[- 2-( 2- merkaptobenzotioazolyl) etyl] formalBis[- 2-( 2- mercaptobenzothioazolyl) ethyl] formal

Et mol merkaptobenzotiazol tilsettes natriumhydrid (1 mol som 25% løsning) fulgt av røring av blandingen i 1 time.Blandingen oppvarmes så til ca. 60° - 70°C og føres i 1 time ytterligere. Bis-(2-kloretyl)formal (1/2 mol) tilsettes så langsomt under røring mens temperaturen holdes mellom 60° One mole of mercaptobenzothiazole is added to sodium hydride (1 mole as a 25% solution) followed by stirring the mixture for 1 hour. The mixture is then heated to approx. 60° - 70°C and heated for a further 1 hour. Bis-(2-chloroethyl)formal (1/2 mol) is then added slowly with stirring while the temperature is kept between 60°

og 70°C. Etter at alt formal er tilsatt varmes reaksjonsblandingen ved tilbakeløp i 2 timer. Oppvarmingen avsluttes så og ca. 500 ml H20 tilsettes. Et oljeaktig skikt utskilles som fordeles og vaskes med vann inntil pH i vaskevannet er ca. 6. Det oljekatige produkt tørkes over fortynning med toluen etterfulgt av vakuumdestillasjon av løsningsmiddelet i vakuum. 89,4% sluttprodukt oppnås derved. and 70°C. After all the formalin has been added, the reaction mixture is heated at reflux for 2 hours. The heating then ends and approx. 500 ml H20 is added. An oily layer is separated which is distributed and washed with water until the pH in the wash water is approx. 6. The oily product is dried over dilution with toluene followed by vacuum distillation of the solvent in a vacuum. 89.4% final product is thereby achieved.

EKSEMPEL 3 EXAMPLE 3

Bis-( 2- N- morfolinotiokarbonylmerkaptoetyl)- formalBis-(2-N-morpholinothiocarbonylmercaptoethyl)-formal

Et mol natriumhydroksyd oppløst i 120 g F^O tilsettes etA mole of sodium hydroxide dissolved in 120 g of F^O is added to a

mol morfolin under røring og temperaturen holdes ved ca. 30°C. Etter at alt morfolin er tilsatt, tilsettes 1 mol karbondisulfid ved tilstrekkelig hastighet til å holde temperaturen i blandingen på ca. 35°C. Etter at alt karbondisulfid er tilsatt tilsettes ytterligere vann (120 ml) for å bringe alt fast materiale i løsning, og blandingen holdes 1 time ved 30°C. Blandingen oppvarmes så til 60°C og 1/2 moles of morpholine while stirring and the temperature is kept at approx. 30°C. After all the morpholine has been added, 1 mole of carbon disulfide is added at a sufficient rate to maintain the temperature of the mixture at about 35°C. After all the carbon disulphide has been added, additional water (120 ml) is added to bring all solids into solution, and the mixture is held for 1 hour at 30°C. The mixture is then heated to 60°C and 1/2

mol bis-(2-kloretyl)formal tilsettes over et tidspunkt påmol of bis-(2-chloroethyl)formal is added over a time of

ca. 1 time. Etter at alt formal er tilsatt oppvarmes reak-sjonblandingen så til mellom 90° og 100°C i 1 time. På slutten av denne peroiden skyller reaksjonsblandingen seg i 2 faser. about. 1 hour. After all the formalin has been added, the reaction mixture is then heated to between 90° and 100°C for 1 hour. At the end of this period, the reaction mixture elutes in 2 phases.

Etter kjøling ble den vandige fasen dekantert og den resterende olje vasket med sukkessive andeler av varmt vann inntil vaskevannet ga negativ reaksjon med sølvnitrat på kloridioner og hadde pH 7. Tilsetning av is til det resterende produktet forårsaker at dette blir fast. Fjerning av vann og vakuumtørking.over drieritt gir sluttproduktet (86,9%). After cooling, the aqueous phase was decanted and the residual oil washed with successive portions of hot water until the wash water reacted negatively with silver nitrate for chloride ions and had a pH of 7. Addition of ice to the residual product causes it to solidify. Removal of water and vacuum drying over drierite gives the final product (86.9%).

EKSEMPEL 4 EXAMPLE 4

Bis-( di- isopropanolylditiokarbamyletyl)- formalBis-(di-isopropanolyldithiocarbamylethyl)-formal

Et mol natriumhydroksyd oppløst i vann (120 ml) tilsettes 1 mol diisopropanolamin og karbondisulfid (1 mol) under røring. Etter tilsetning av karbondisulfid oppvarmes blandingen til ca. 60°C og så tilsettes 1/2 mol bis-(2-kloretyl)formal. Etter tilsetning av formalet oppvarmes reaksjonsblandingen til tilbakeløp under vedvarende røring. Etter ca. 3 1/2 time kjøles reaksjonsblandingen og det oljeaktige produkt som utskilles fordeles, vaskes med sukksesive andeler friskt vann til pH 7 og negativ sølv-nitrat-kloridreaksjon. Etterfølgende•fortynning med og fjerning av toluen i vakuum og tørking til konstant vekt gir sluttproduktet (75,5%). One mol of sodium hydroxide dissolved in water (120 ml) is added with 1 mol of diisopropanolamine and carbon disulphide (1 mol) while stirring. After adding carbon disulphide, the mixture is heated to approx. 60°C and then 1/2 mol of bis-(2-chloroethyl)formal is added. After adding the formalin, the reaction mixture is heated to reflux with continuous stirring. After approx. The reaction mixture is cooled for 3 1/2 hours and the oily product that separates out is distributed, washed with successive portions of fresh water to pH 7 and negative silver-nitrate-chloride reaction. Subsequent•dilution with and removal of toluene in vacuum and drying to constant weight gives the final product (75.5%).

EKSEMPEL 5 EXAMPLE 5

Bis-( 2- di- 2- hydroksyetylditiokarbamyletyl) formalBis-(2-di-2-hydroxyethyldithiocarbamylethyl) formal

Ved å følge en analog fremgangsmåte som i eksempel 4 oppnås fra dietanolamin (1 mol), natriumhydroksy (1 mol), karbondisulfid (1 mol) og bis-(2-kloretyl)formal (1/2 mol) 62,3% av sluttproduktet. By following an analogous procedure as in example 4, 62.3% of the final product is obtained from diethanolamine (1 mol), sodium hydroxy (1 mol), carbon disulfide (1 mol) and bis-(2-chloroethyl)formal (1/2 mol) .

EKSEMPEL 6 EXAMPLE 6

Poly- bis-[ 2-( 4- ditiokarboksyltiokarbamylmerkapto) etyl] formal Poly-bis-[2-(4- dithiocarboxylthiocarbamyl mercapto) ethyl] formal

6,0 mol natriumhydroksyd oppløst i 720 ml F^O tilsettes 3,0 mol piperazin i løpet av 1/2 time. Denne blandingen tilsettes under røring og kjøling under 35°C i løpet av 1 time 6,0 mol karbondisulfid. Det kreves kjøling 1 time ytterligere etter at alt karbondisulfid er tilsatt. Reaksjonsblandingen oppvarmes til 90°C og bis-(2-kldretyl)formal 6.0 mol of sodium hydroxide dissolved in 720 ml of F^O is added to 3.0 mol of piperazine over the course of 1/2 hour. 6.0 mol of carbon disulphide is added to this mixture while stirring and cooling below 35°C over the course of 1 hour. A further 1 hour of cooling is required after all the carbon disulphide has been added. The reaction mixture is heated to 90°C and bis-(2-chloroethyl)formal

(3,0 mol) tilsettes tilstrekkelig raskt til å holde temperaturen nær 90°C. Etter at alt formal er tilsatt røres reaksjonsblandingen ved 90°C i ytterligere 3 timer. Det hvite uløselige produktet som dannes fjernes fra reaksjonen, kjøles, pulveriseres og vaskes fritt, for kloridioner med vann. Sluttproduktet som således oppnås som natriumsalt tørkes til konstant vekt ved 60°C og 1,0 mm vakuum (96% utbytte).. (3.0 mol) is added quickly enough to keep the temperature close to 90°C. After all the formalin has been added, the reaction mixture is stirred at 90°C for a further 3 hours. The white insoluble product that forms is removed from the reaction, cooled, pulverized and washed freely for chloride ions with water. The final product thus obtained as sodium salt is dried to constant weight at 60°C and 1.0 mm vacuum (96% yield).

EKSEMPEL 7 EXAMPLE 7

Poly- bis-( 2- ditiokarbamyletylenditiokarbamyletyl) formalPoly-bis-(2-dithiocarbamylethylenedithiocarbamylethyl) formal

6,0 mol natriumhydroksyd ble oppløse i 480 ml F^O tilsettes langsomt etylendiamin under røring og med tilstrekkelig ytre kjøling til å holde temperaturen ved eller under 30°C. 6,0 mol karbondisulfid tilsettes langsomt under røring og kjøling til under tilbakeløpstemperaturen. Etter at karbondisulfid-tilsetningen er ferdig får tilbakeløp fortsette inntil reaksjonen avtar. Reaksjonsblandingen oppvarmes så til 85°C og 3,0 mol bis-(2-kloretyl)formal tilsettes over et tidsrom på 1 time. Etter formaltilsetningen er ferdig holdes temperaturen på 85°C i 2 timer ytterligere. Et produkt utskilles som fordeles fra det vandige skiktet, vaskes med varmt vann til pH 6 og negativ sølvnitrat-klorid-påvirning og tørkes ved 7 5°C og 1 til 2 mm vakuum og gir sluttproduktet som et natriumsalt (94,9% utbytte). 6.0 mol of sodium hydroxide was dissolved in 480 ml of F^O, ethylenediamine is added slowly with stirring and with sufficient external cooling to keep the temperature at or below 30°C. 6.0 mol of carbon disulphide is added slowly while stirring and cooling to below the reflux temperature. After the carbon disulfide addition is complete, reflux is allowed to continue until the reaction subsides. The reaction mixture is then heated to 85°C and 3.0 mol of bis-(2-chloroethyl)formal is added over a period of 1 hour. After the formal addition is complete, the temperature is kept at 85°C for a further 2 hours. A product is separated which is separated from the aqueous layer, washed with hot water to pH 6 and negative silver nitrate chloride action and dried at 75°C and 1 to 2 mm vacuum to give the final product as a sodium salt (94.9% yield) .

EKSEMPEL 8 EXAMPLE 8

Bis-[ 2-( 2- merkaptotiazoyl) etyl] formalBis-[2-(2- mercaptothiazoyl) ethyl] formal

Et mol natriumhydroksyd i 120 g vann tilsettes under røringOne mole of sodium hydroxide in 120 g of water is added while stirring

1 mol monoetanolamin mens temperaturen holdes under 30°c.1 mol of monoethanolamine while the temperature is kept below 30°c.

Når tilsetningen er ferdig tilsettes 1 mol karbondisulfid mens temperaturen holdes ved ca. 35°C. Reaksjonsblandingen oppvarmes så til 90°C og.etter at temperaturen er holdt der ca 1/2 time tilsettes 0,5 mol bis-(2-klofet<y>l)formal. Løs-ningen oppvarmes så ved tilbakeløp i ca. 3 timer. Oljen som utskilles ved kjøling vaskes til PH 7 og negativ sølv-nitrat-kloridreaksjon og vakuum tørkes. When the addition is finished, 1 mol of carbon disulphide is added while the temperature is kept at approx. 35°C. The reaction mixture is then heated to 90°C and, after the temperature has been maintained there for about 1/2 hour, 0.5 mol of bis-(2-clofet<y>1)formal is added. The solution is then heated at reflux for approx. 3 hours. The oil that separates during cooling is washed to PH 7 and negative silver-nitrate-chloride reaction and vacuum dried.

EKSEMPEL 9EXAMPLE 9

Forbindelsene fra eksemplene 1, 2,3, 4, 6 og 8 fremstilles som vandige løsninger ved å oppløse kjente mengder av forbindelsene i aceton (10 ml), og tilsette en dråpe Tween 20 (sorbitan-monolauratet-polyoksyalkylen-derivat fra Atlas Pov/der Co.) og fortynne konsentrasjonsserier med vann. The compounds from examples 1, 2, 3, 4, 6 and 8 are prepared as aqueous solutions by dissolving known amounts of the compounds in acetone (10 ml), and adding a drop of Tween 20 (sorbitan monolaurate polyoxyalkylene derivative from Atlas Pov/ der Co.) and dilute concentration series with water.

Disse suspensjonene ble så brukt for behandling av angrepne planter som angitt nedenfor ved å sprøyte sus<p>ensjonen på bladoverflaten slik at de drypper, eller i tilfelle av rot-knollnematoder ved å tilføre jorden suspensjonen før infek-sjon av jorden med nematodelarver. These suspensions were then used to treat infested plants as indicated below by spraying the suspension onto the leaf surface so that they drip, or in the case of root-knot nematodes by applying the suspension to the soil prior to infection of the soil with nematode larvae.

De ble utført forsøk mot bakterier, sopper, virus og nematode-sykdommer. Samtidige sammenlikninger ble kjørt mot (a) blad-og rotpatogener, (b) overfladiske og indre patogener og (c) fakultative og obligate parasitter. Sopp, den mest vanlige grunnn til plantesykdommer, omfatter tre klasser, phycomycetes, ascomycetes ogbasidomycetes. Representanter for hver klasse ble inntatt i prøven. De undersøkte sykdommene har alle økono-misk betydning. They were tested against bacteria, fungi, viruses and nematode diseases. Simultaneous comparisons were run against (a) leaf and root pathogens, (b) superficial and internal pathogens and (c) facultative and obligate parasites. Fungi, the most common cause of plant disease, comprise three classes, phycomycetes, ascomycetes and basidomycetes. Representatives of each class were included in the sample. The examined diseases all have economic significance.

Tomatplanter var på 5 - 6 bladtrinnet, bønnespirer hadde sine første blad 2/3 utsprungne og det andre bladet var nettopp i ferd med å springe ut hos hvete på tidspunktet for behandlingen. En eller to dager etter behandling ble planter eller jord holdt ettérsom inokulert med det aktuelle patogenet. De resultater som oppnås er vist i de følgende tabeller: Tomato plants were at the 5-6 leaf stage, bean sprouts had their first leaves 2/3 emerged and the second leaf was just emerging in wheat at the time of treatment. One or two days after treatment, plants or soil were kept as inoculated with the pathogen in question. The results obtained are shown in the following tables:

EKSEMPEL 10 EXAMPLE 10

Gummiformuleringer fremstilles og herdes ved bruk av kjente herdingsakselratorer og forbindelser ifølge oppfinnelsen i parallelle formuleringer. Formuleringene og fysikalske egen-skaper av de herdede materialer er som vist. Forsøk på å fremstille en formulering i likhet med den av B eller C forut for forbindelsen fra eksempel 6 lyktes ikke grunnet vanskeligheten ved å dispergere den faste for^bindelsen under fremstillingen av formuleringsblandingen. Rubber formulations are prepared and cured using known curing accelerators and compounds according to the invention in parallel formulations. The formulations and physical properties of the cured materials are as shown. Attempts to prepare a formulation similar to that of B or C prior to the compound of Example 6 were unsuccessful due to the difficulty in dispersing the solid compound during preparation of the formulation mixture.

Claims (17)

1. Forbindelsen med formelen1. The connection with the formula karakterisert ved at 0 er characterized in that 0 is hvor R og R' uavhengig er hydrogen, alkyl med 1 til 10 karbonatomer, alkenyl med 3 til 10 karbonatomer, alkynyl med 3. til 10 karbonatomer, karbocyklisk aryl med 6 eller 10 karbonatomer i arylkjernen, heterocyklisk aryl med 1 eller 2 heteroatomer og 3 til 9 karbonatomer i arylkjernen, aralkyl hvor aryldelen er heterocyklisk eller karbocyklisk aryl som forut angitt og alkyl som forut angitt., og hydro-karbyldelene av hver av de foran nevnte rester enten er usubstituert eller videre substituert med alkyl som forut angitt, alkenyl som forut angitt, alkynyl som forut angitt, hydroksy eller alkoksy med 1 til 10 karbonatomer i alkylresten, eller R og R' er sammenknyttet og danner sammen med nitrogenatomet piperidino, pyrrolidino ,. morf olino, piperazino, pyf idino, pyridanino, tetrahydrotiazol, di-hydroindolo, tetrahydroksazol eller tiamorfolino, hvor restene som dannes ved sammenkoplingen er usubstituert eller substituert ved alkyl, eller(B) 2-merkapto-tiazol enten usubstituert eller substituert med alkyl, karbocyklisk aryl som forut angitt, heterocyklisk aryl som forut angitt eller kondensert til en mono- eller bicyklisk karbocyklisk aryl som forut angitt eller heterocyklisk arylkjerne som forut angitt, eller where R and R' are independently hydrogen, alkyl of 1 to 10 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, carbocyclic aryl with 6 or 10 carbon atoms in the aryl nucleus, heterocyclic aryl with 1 or 2 heteroatoms and 3 to 9 carbon atoms in the aryl nucleus, aralkyl where the aryl part is heterocyclic or carbocyclic aryl as previously stated and alkyl as previously stated., and the hydrocarbyl moieties of each of the aforementioned residues are either unsubstituted or further substituted with alkyl as defined above, alkenyl as defined above, alkynyl as defined above, hydroxy or alkoxy with 1 to 10 carbon atoms in the alkyl residue, or R and R' are linked together and together with the nitrogen atom form piperidino, pyrrolidino,. morpholino, piperazino, pyf idino, pyridanino, tetrahydrothiazole, dihydroindolo, tetrahydroxazole or thiamorpholino, where the residues formed by the coupling are unsubstituted or substituted by alkyl, or (B) 2-mercaptothiazole either unsubstituted or substituted by alkyl, carbocyclic aryl as defined above, heterocyclic aryl as defined above or fused to a mono- or bicyclic carbocyclic aryl as defined above or heterocyclic aryl ring as defined above, or hvor. Y er ålkylendiamin:méd 2 til 10 karbonatomer, cykloalkylendiamin med 5 eller 6 karbonatomer i den cykliske ringen, alkenylendiamin med 4 til 10. karbonatomer, cyklo-alkenylendiamin med 5 eller 6 karbonatomer i den cykliske ringen, alkynylendiamin med 4 til 10 karbonatomer eller where. Y is alkylene diamine: with 2 to 10 carbon atoms, cycloalkylenediamine with 5 or 6 carbon atoms in the cyclic ring, alkenylenediamine with 4 to 10 carbon atoms, cycloalkenylenediamine with 5 or 6 carbon atoms in the cyclic ring, alkynylenediamine with 4 to 10 carbon atoms or hvor hydrokarbylrestene av nevnte Y-rest enten er usubstituert eller substituert med alkyl,- alkynyl, karbo-, cyklisk aryl som forut angitt, heterocyklisk aryl som forut angitt, X er Q, Cl eller where the hydrocarbyl residues of said Y-residue either is unsubstituted or substituted with alkyl,- alkynyl, carbo-, cyclic aryl as defined above, heterocyclic aryl as defined above, X is Q, Cl or hvor Y er som forut angitt, Z er 0 eller Cl og x er tilstrekkelig . til å gi en total molekylvekt på. opptil ca. 1000, n er et helt tall fra 2 til 10, m er 0 eller et helt tall 1 til 3 under det forbehold at nar m er 0 er X where Y is as previously indicated, Z is 0 or Cl and x is sufficient. to give a total molecular weight of up to approx. 1000, n is an integer from 2 to 10, m is 0 or an integer 1 to 3 with the proviso that when m is 0, X og addisjonssaltef av disse. and addition salts thereof. 2. Forbindelse ifølge krav 1 karakterisert ved atm er 1. 2. Compound according to claim 1 characterized by atm is 1. 3. Forbindelse ifølge krav 2 karakterisert ved at X er identisk med 0. 3. Compound according to claim 2 characterized in that X is identical to 0. 4. Forbindelse ifølge krav 3 karakteri- sert ved at Q er 4. Connection according to claim 3 charac- sert in that Q is hvor R og R' er alkyl eller hydroksyalkyl. where R and R' are alkyl or hydroxyalkyl. 5. Forbindelse ifølge krav 4 karakterisert ved at den er bis-(2-dimetylditiokarbamyletyl)-formal. 5. Compound according to claim 4, characterized in that it is bis-(2-dimethyldithiocarbamylethyl)-formal. 6. Forbindelse ifølge krav 4 karakterisert ved at den er bis-(2-diisopropanolylditiokar-bamyletyl)formal. 6. Compound according to claim 4, characterized in that it is bis-(2-diisopropanolyldithiocarbamylethyl)formal. 7. Forbindelse ifølge krav 4 karakterisert ved at den er bis-(2-di-2-hydroksyetylditiokarbamyletyl)formal. 7. Compound according to claim 4, characterized in that it is bis-(2-di-2-hydroxyethyldithiocarbamylethyl)formal. 8. Forbindelse ifølge krav 3 karakteri- sert ved at 0 er 8. Connection according to claim 3 charac- sert in that 0 is hvor R og R' er sammenknyttet og sammen med nitrogenatomet danner en heterocyklisk ring. where R and R' are linked and together with the nitrogen atom forms a heterocyclic ring. 9. Forbindelse ifølge krav karakterisert ved at den er bis-(2-N-morfolino-tiokarbonyl-merkaptoetyl)formal.. 9. Compound according to claim characterized in that it is bis-(2-N-morpholino-thiocarbonyl-mercaptoethyl)formal.. 10- Forbindelse ifølge krav 3 karakterisert ved at Q er 2-merkaptotiazolyl. 10- Compound according to claim 3 characterized in that Q is 2-mercaptothiazolyl. 11. Forbindelse ifølge krav 10 karakterisert ved at den er bis[2-(2-merkaptobenzotiazolyl) etyl]formal. 11. Compound according to claim 10, characterized in that it is bis[2-(2-mercaptobenzothiazolyl)ethyl]formal. 12. Forbindelse ifølge krav 1 karakteri- sert ved at Q er 12. Compound according to claim 1 charac- sert in that Q is og X er and X is hvor Y, Z, n, m og x- er som forut angitt. where Y, Z, n, m and x are as previously indicated. 13. Forbindelse ifølge krav 12 karakterisert ved at den er poly-bis-[2-(4-ditiokarboksyl-piperazino-tiokarbonylmerkapto)etyl]formal. 13. Compound according to claim 12, characterized in that it is poly-bis-[2-(4-dithiocarboxyl-piperazino-thiocarbonylmercapto)ethyl]formal. 14. Forbindelse ifølge krav 12 karakterisert ved at den er poly-bis-(2-ditiokarbamyl-etylen-ditiokarbamyletyl)formal. 14. Compound according to claim 12, characterized in that it is poly-bis-(2-dithiocarbamyl-ethylene-dithiocarbamylethyl)formal. 15. Forbindelse ifølge krav 10 karakterisert ved at den er bis-[2-(2-merkaptotiazolyl)etyl]-formal.. 15. Compound according to claim 10 characterized in that it is bis-[2-(2-mercaptothiazolyl)ethyl]-formal.. 16. Herdbar komposisjon karakterisert ved at den omfatter a) en vulkaniserbar gummi, og b) en forbindelse med formel 0-(CH_) -(OCH„) -O-(CH-) -X n m zn hvor m og n er som angitt i krav. 1, Q er angitt i krav 1 eller 2-merkaptotiazolyl som angitt i krav 1 og. Q og X er like. 16. Curable composition characterized in that it comprises a) a vulcanizable rubber, and b) a compound of formula O-(CH_)-(OCH„)-O-(CH-)-X n m zn where m and n are as specified in requirements. 1, Q is indicated in claim 1 or 2-mercaptothiazolyl as indicated in claim 1 and. Q and X are equal. 17. Biocid komposisjon for kontroll av plantepatogener karakterisert ved at den omfatter: En for- bindelse med formel Q-(CH-) -(OCH-) -0-(CH„) -X hvor 0, X, 2 n 2 m 2 n n og m er som angitt i krav 1 og et i jordbruket fordragelig bæremiddel.17. Biocidal composition for the control of plant pathogens, characterized in that it comprises: A pre- bond with formula Q-(CH-) -(OCH-) -0-(CH„) -X where 0, X, 2 n 2 m 2 n n and m are as stated in claim 1 and an agriculturally tolerable carrier.
NO780426A 1977-02-08 1978-02-07 BISDITIOKARBAMATESTERE. NO780426L (en)

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