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DE1117561B - Process for the production of urea derivatives - Google Patents

Process for the production of urea derivatives

Info

Publication number
DE1117561B
DE1117561B DEF31340A DEF0031340A DE1117561B DE 1117561 B DE1117561 B DE 1117561B DE F31340 A DEF31340 A DE F31340A DE F0031340 A DEF0031340 A DE F0031340A DE 1117561 B DE1117561 B DE 1117561B
Authority
DE
Germany
Prior art keywords
urea derivatives
production
cyanomethyl
isocyanate
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DEF31340A
Other languages
German (de)
Inventor
Dr Ludwig Eue
Dr Rudolf Hiltmann
Dr Hartmund Wollweber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF31340A priority Critical patent/DE1117561B/en
Publication of DE1117561B publication Critical patent/DE1117561B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1836Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from derivatives of carbamic acid
    • C07C273/1845Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from derivatives of carbamic acid comprising the -N-C(O)-Hal moiety
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1818Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
    • C07C273/1827X being H

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von Harnstoffderivaten Die herbizide Wirksamkeit von N-Phenyl-N'-alkyl-N'-carboxymethyl-harnstoffen ist bereits bekannt.Process for the preparation of urea derivatives Herbicidal effectiveness of N-phenyl-N'-alkyl-N'-carboxymethyl ureas is already known.

Es wurde nun gefunden, daß man durch Umsetzung von Arylisocyanaten oderArylcarbaminsäurechloriden, die im Kern durch Alkyl- bzw. Alkoxyreste oder Chlor substituiert sein können, mit Cyanomethylaminen zu Harnstoffderivaten gelangt, die sich durch eine überraschende, ausgesprochen selektive Wirkung als Unkrautvernichtungsmittel auszeichnen. Als für die genannte Umsetzung geeignete Arylisocyanate seien beispielsweise genannt: Phenylisocyanat, p-Chlorphenylisocyanat, 3,4-Dichlorphenylisocyanat, 2,4-Dichlorphenylisocyanat, p-Methylisocyanat, p-Methoxyphenylisocyanat. Unter Cyanomethylaminen sind vor allem Verbindungen mit einem gesättigten oder ungesättigten Alkylrest mit I bis 4 C-Atomen zu verstehen, wie z. B. Cyanomethylamin, Cyanomethyl-methylamin, Cyanomethyl-butylamin, Cyanomethyl-isobutylamin, Cyanomethyl-tert.-butylamin, Cyanomethyl-äthylamin, Cyanomethyl-propylamin, Cyanomethyl-allylamin. It has now been found that by reacting aryl isocyanates orArylcarbamic acid chlorides, the nucleus by alkyl or alkoxy radicals or chlorine can be substituted, with cyanomethylamines to obtain urea derivatives that has a surprising, extremely selective effect as a herbicide distinguish. Examples of suitable aryl isocyanates for the reaction mentioned are named: phenyl isocyanate, p-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, p-methyl isocyanate, p-methoxyphenyl isocyanate. Among the most important are cyanomethylamines Compounds with a saturated or unsaturated alkyl radical with 1 to 4 carbon atoms to understand how B. cyanomethylamine, cyanomethyl-methylamine, cyanomethyl-butylamine, Cyanomethyl-isobutylamine, cyanomethyl-tert-butylamine, cyanomethyl-ethylamine, cyanomethyl-propylamine, Cyanomethyl allylamine.

Die erfindungsgemäß erhältlichen Harnstoffderivate stellen im allgemein gut kristallisierte Verbindungen dar. The urea derivatives obtainable according to the invention generally represent well crystallized compounds.

Unter Unkräutern, die mit Hilfe der verfahrensgemäß erhältlichen Verbindungen bekämpft werden können, sollen dabei im weitesten Sinne des Wortes Pflanzen verstanden werden, die an Stellen aufwachsen, wo sie unerwünscht sind. Die erfindungsgemäß herstellbaren Substanzen wirken bereits in geringerer Konzentration als Herbizide, wobei sich die Wirkung vornehmlich gegen keimende Samen richtet, d. h., die Samen keimen normal, und die Sämlinge zeigen eine normale Jugendentwicklung. 10 bis 14 Tage nach der Keimung sterben die Pflanzen jedoch unter Chlorose-und Welkerscheinungen ab. Auch bei einer Postemergence-Spritzung gelingt bei geeigneter Wahl der Konzentration an Wirkstoff die Vernichtung der Pflanzen. In Gewächshausversuchen wurde aber nun gefunden, daß sich die verfahrensgemäßen Produkte überraschenderweise besonders zur selektiven Unkrautbekämpfung eignen. Among weeds that can be obtained with the aid of the Connections can be combated, should in the broadest sense of the word Plants are understood that grow in places where they are undesirable. The substances which can be prepared according to the invention are already effective in a lower concentration as herbicides, whereby the effect is primarily directed against germinating seeds, d. that is, the seeds germinate normally and the seedlings show normal juvenile development. However, 10 to 14 days after germination, the plants die with symptoms of chlorosis and wilting away. With a suitable choice of concentration, a post-emergence spray is also successful in active ingredient the destruction of the plants. In greenhouse trials, however, was now found that the products according to the process are surprisingly special suitable for selective weed control.

Die Unkrautvernichtungsmittel können dabei sowohl einen als auch mehrere Vertreter der obengenannten Verbindungsklasse enthalten. Sie werden mit einem festen oder flüssigen Streckmittel ausgebracht. The herbicides can be either one or the other contain several representatives of the above-mentioned class of compounds. They will with a solid or liquid extender applied.

Der Zusatz bekannter Herbizide ist dabei möglich.The addition of known herbicides is possible.

Wäßrige Dispersionen, Emulsionen oder Lösungen der genannten Wirkstoffe können Netzmittel, Emulgatoren oder andere Dispergierhilfsmittel enthalten.Aqueous dispersions, emulsions or solutions of the active ingredients mentioned may contain wetting agents, emulsifiers or other dispersing aids.

Die Ausbringung erfolgt im Spritz-, Stäube- oder Streuverfahren.The application is carried out by spraying, dusting or littering.

Die herbizide Wirksamkeit der erfindungsgemäßen Verbindungen im Vergleich zu analog gebauten bekannten Stoffen sei durch die folgenden Gewächshausversuche erläutert: Gemischte Aussaaten von Gossypium, Sinapis, Chenopodium, Hordeum, Zea und Soleum werden post-emergence (24 Stunden nach der Aussaat) mit einer bestimmten Aufwandmenge der verschiedenen Unkrautbekämpfungsmittel behandelt und bei sechs Schädigungsgraden das Wachstum der einzelnen Pflanzenarten bonitiert (0 = keine Wirkung, 5 = totale Vernichtung). Die Ergebnisse der entsprechenden Versuche sind aus der nachfolgenden Tabelle ersichtlich. The herbicidal activity of the compounds according to the invention in comparison The following greenhouse experiments can be used to describe known materials constructed in the same way explained: Mixed sowing of Gossypium, Sinapis, Chenopodium, Hordeum, Zea and brine will be post-emergence (24 hours after sowing) with a certain Application rate of the various weed control agents and treated at six Degree of damage the growth of the individual plant species is rated (0 = none Effect, 5 = total annihilation). The results of the corresponding tests are can be seen in the following table.

Wie aus der Tabelle hervorgeht, zeichnen sich die erfindungsgemäßen Verbindungen 1 und 2 gegenüber den bekannten Substanzen 3 und 4 durch eine größere Selektivität aus. Die Präparate 1 und 2 sind in hervorragendem Maße zur selektiven Unkrautbekämpfung in Baumwoll- und Maiskulturen geeignet. As can be seen from the table, the inventive Compounds 1 and 2 compared to the known substances 3 and 4 by a larger one Selectivity off. Preparations 1 and 2 are excellent for selective use Suitable for weed control in cotton and maize crops.

Die nachfolgenden Beispiele erläutern die Herstellung einiger Vertreter der erfindungsgemäß nach dem beanspruchten Verfahren erhältlichen Verbindungen: Beispiel 1 Zu 20 g Methylaminoacetonitril fügt man unter Kühlung bei 10 bis 20"C 35,6 g Phenylisocyanat. Nach beendeter Reaktion wird die gebildete kristalline Substanz aus Benzol umkristallisiert. Man erhält in fast quantitativer Ausbeute N-Phenyl-N'-methyl-N'-cyanomethyl-harnstoff. F. 103 bis 104°C. The following examples explain the production of some representatives of the compounds obtainable according to the invention by the claimed process: EXAMPLE 1 20 g of methylaminoacetonitrile are added with cooling at 10 to 20 ° C 35.6 grams of phenyl isocyanate. After the completion of the reaction, the formed crystalline substance becomes recrystallized from benzene. You get in almost quantitative yield N-phenyl-N'-methyl-N'-cyanomethyl urea. M.p. 103 to 104 ° C.

Analyse: CloHllN3o.Analysis: CloHllN3o.

Molgewicht 189.Molecular weight 189.

Berechnet ... H 5,87, C 63,54, N22,23; gefunden ... H5,87, C63,22, N21,92. Calculated ... H 5.87, C 63.54, N22.23; found ... H5.87, C63.22, N21.92.

Beispiel 2 Zu 15 g Methylaminoacetonitril tropft man bei 10 bis 20"C eine Lösung von 33 g p-Chlorphenylisocyanat in 200 ccm Benzol. Man erhält N-(p-Chlorphenyl)-N'-methyl-N'-cyanomethyl-harnstoff vom F.110°C. Example 2 15 g of methylaminoacetonitrile are added dropwise at 10 to 20 ° C a solution of 33 g of p-chlorophenyl isocyanate in 200 cc of benzene. N- (p-chlorophenyl) -N'-methyl-N'-cyanomethylurea is obtained from 110 ° C.

Analyse: C10H10N3OCl.Analysis: C10H10N3OCl.

Molgewicht 223,5.Molecular weight 223.5.

Berechnet ... C 53,74, H 4,51; gefunden .. C 53,63, H 4,59. Calculated ... C 53.74, H 4.51; found .. C 53.63, H 4.59.

Auf analoge Weise erhält man aus Methylaminoacetonitril und 3,4-Dichlorphenylisocyanat, das in Chlorbenzol gelöst ist, den N-(3,4-Dichlorphenyl)-N'-methyl-N'-cyanomethyl-harnstoff vom F. 162 bis 163°C. In an analogous manner, from methylaminoacetonitrile and 3,4-dichlorophenyl isocyanate, which is dissolved in chlorobenzene, the N- (3,4-dichlorophenyl) -N'-methyl-N'-cyanomethyl urea from 162 to 163 ° C.

Analyse: CloH9N3oCl2-Molgewicht 258.Analysis: CloH9N3oCl2 molecular weight 258.

Berechnet ... C 46,55, H 3,52, N 16,29, Cl 27,49; gefunden ... C 46,82, H 3,46, N I5,98, C127,73. Auf- Schädigungsgrad bei Anwendung gegen wand- Präparat menge kg/ha Gossy- S Clzeno- pium Soleum CH / H3 20 3 5 5 4 3 bis 4 4 bis 5 -NH-CO-N' 10 2 bis 3 5 5 3 2 bis 3 4 bis 5 CH2-CN 5 1 5 4 bis 5 1 bis 2 1 bis 2 4 CH3 20 O bis 1Obisl 5 5 2 bis 3 1 4 2. C1J<NHCON/ 10 O 5 5 2 Obis 1 3 CH2-CN 5 0 5 0 5 5 0 O 2 bis 3 CH3 / CH3 20 3 bis 4 3 bis 4 3bis4 5 2 4 4 3. Cl%NH-CO-N$ 10 3 2bis3 4bis5 1 3 3 ½, CH2-COONa 5 bis 2 2 bis 3 2 bis 3 0 bis 2 2 CH3 20 5 5 5 5 5 5 4. ClM/½NHCoNi' 10 3 5 5 5 5 5 CH8 \ CH3 5 2 5 5 4 4 5 Calculated ... C 46.55, H 3.52, N 16.29, Cl 27.49; Found ... C 46.82, H 3.46, N I 5.98, C 127.73. On- degree of damage when used against Wall- Amount of preparation kg / ha Gossy- S Clzenopium Soleum CH / H3 20 3 5 5 4 3 to 4 4 to 5 -NH-CO-N '10 2 to 3 5 5 3 2 to 3 4 to 5 CH2-CN 5 1 5 4 to 5 1 to 2 1 to 2 4 CH3 20 O to 10 to 5 5 2 to 3 1 4 2. C1J <NHCON / 10 O 5 5 2 Obis 1 3 CH2-CN 5 0 5 0 5 5 0 O 2 to 3 CH3 / CH3 20 3 to 4 3 to 4 3 to 4 5 2 4 4 3. Cl% NH-CO-N $ 10 3 2 to 3 4 to 5 1 3 3 ½, CH2-COONa 5 to 2 2 to 3 2 to 3 0 to 2 2 CH3 20 5 5 5 5 5 5 4. ClM / ½NHCoNi '10 3 5 5 5 5 5 CH8 \ CH3 5 2 5 5 4 4 5

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Harnstoffderivaten, dadurch gekennzeichnet, daß Arylisocyanate oder Arylcarbaminsäurehalogenide, die gegebenenfalls im Kern durch Alkyl- bzw. Alkoxygruppen oder Halogen substituiert sein können, mit Cyano methylaminen umgesetzt werden.PATENT CLAIM: Process for the production of urea derivatives, characterized in that aryl isocyanates or aryl carbamic acid halides, the optionally in the nucleus by alkyl or alkoxy groups or substituted by halogen can be reacted with cyano methylamines. In Betracht gezogene Druckschriften: Chemistry and Industry, 1957, S. 1106. References considered: Chemistry and Industry, 1957, P. 1106.
DEF31340A 1960-05-31 1960-05-31 Process for the production of urea derivatives Pending DE1117561B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF31340A DE1117561B (en) 1960-05-31 1960-05-31 Process for the production of urea derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF31340A DE1117561B (en) 1960-05-31 1960-05-31 Process for the production of urea derivatives

Publications (1)

Publication Number Publication Date
DE1117561B true DE1117561B (en) 1961-11-23

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Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
DE (1) DE1117561B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0417256A4 (en) * 1989-04-03 1991-09-25 The Nutrasweet Company Novel n-(sulfomethyl)-n'-arylureas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0417256A4 (en) * 1989-04-03 1991-09-25 The Nutrasweet Company Novel n-(sulfomethyl)-n'-arylureas

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