DE596004C - Process for the recovery of urea and thiourea pellets of the aromatic series - Google Patents

Process for the recovery of urea and thiourea pellets of the aromatic series

Info

Publication number
DE596004C
DE596004C DEI41876D DEI0041876D DE596004C DE 596004 C DE596004 C DE 596004C DE I41876 D DEI41876 D DE I41876D DE I0041876 D DEI0041876 D DE I0041876D DE 596004 C DE596004 C DE 596004C
Authority
DE
Germany
Prior art keywords
urea
aromatic
thiourea
pellets
recovery
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.)
Expired
Application number
DEI41876D
Other languages
German (de)
Inventor
Dr Erich Bartholomaeus
Dr Max Bockmuehl
Dr Walter Persch
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.)
IG Farbenindustrie AG
Original Assignee
IG Farbenindustrie 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
Priority to DE1930553278D priority Critical patent/DE553278C/en
Application filed by IG Farbenindustrie AG filed Critical IG Farbenindustrie AG
Priority to DEI41876D priority patent/DE596004C/en
Application granted granted Critical
Publication of DE596004C publication Critical patent/DE596004C/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C07D213/60—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 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation 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
    • C07C273/1809—Preparation 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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
    • C07D235/28—Sulfur atoms

Landscapes

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

Description

Verfahren zur Gewinnung von Harnstoff- und Thioharnstoffabkömmlingen der aromatischen Reihe -Im Patent 553 278 ist ein Verfahren- zur Darstellung von Harnstoff- und Thioharnstoffabk ömmlingen der aromatischen, heterocyclischen und aromatisch-heterocyclischen Reihe beschrieben, welches darin besteht, daß man aromatische, heterocyclische oder aromatischheterocyclische Amine, welche eine basische Seitenkette mit aliphatisch gebundenem Stickstoff tragen, in Harnstoffe bzw. Thioharnstoffe überführt oder daß man in Harnstoff-und Thioharnstoffabkö:mmlinge der aromatischen, heterocyelischen oder aromatischheterocyclischen Reihe, welche keine basische Seitenkette mit aliphatisch gebundenem Stickstoff tragen, eine solche :einführt.Process for the production of urea and thiourea derivatives of the aromatic series - in patent 553 278 is a method - for the preparation of Urea and thiourea derivatives of the aromatic, heterocyclic and aromatic-heterocyclic series described, which consists in the fact that aromatic, heterocyclic or aromatic heterocyclic amines, which have a basic side chain carry with aliphatically bound nitrogen, in ureas or thioureas or that one in urea and thiourea derivatives of the aromatic, heterocyclic or aromatic heterocyclic series which do not have a basic side chain carry with aliphatically bound nitrogen, one such: introduces.

Bei weiterer Bearbeitung dieses Gebietes wurde nun gefunden, daß auch aromatische Amine, welche statt einer basischen Seitenkette mit aliphatisch gebundenem Stickstoff mindestens eine an einem Kern sitzende quaternäre Stickstoffgruppe tragen, üi die zugehörigen Harnstoff- bzw. Thioharnstoffderivate übergeführt werden können, z. B. Cl(CHg)3N_ C6H4-NH2 _>- Cl(CHIN-C6H4-NH-CS-NH2. Die nach dem neuen Verfahren :erhältlichen Verbindungen zeigen .ebenso wie die des Hauptpatents eine stark bakterizide Wirkung, insbesondere gegen den Erreger des seuchenhaften Verkalbens. Diese Wirkung, die insbesondere im Tierversuch nachgewiesen werden konnte, ist überraschend, da beispielsweise andere an sich als bakterizid wirkende Mittel bekannte Präparate unter den gleichen Bedingungen völlig unwirksam sind und da für eine wirksame Bekämpfung des Abortus Bang geeignete Mittel bisher nicht zur Verfügung standen.In further processing of this area it has now been found that aromatic amines which, instead of a basic side chain with aliphatically bound nitrogen, carry at least one quaternary nitrogen group attached to a nucleus, can be converted to the associated urea or thiourea derivatives, e.g. B. Cl (CHg) 3N_ C6H4-NH2 _> - Cl (CHIN-C6H4-NH-CS-NH2. The compounds obtainable by the new process: show, just like those of the main patent, a strong bactericidal effect, in particular against the pathogen causing the epidemic of calving. This effect, which could be demonstrated in animal experiments in particular, is surprising since, for example, other preparations known per se as bactericidal agents are completely ineffective under the same conditions and since suitable agents for effective control of the Bang Abortion have not been available until now.

Beispiele i. 44,6 Gewichtsteile p-AmÜnophenyltrimethylammoniumchloridchlorhydrat und 19,6 Gewichtsteile Rhodankalium werden in t oo Raumteilen Wasser ,gelöst und einige Zeit auf dem Dampfbad erhitzt oder mehrere Tage bei Zimmertemperatur stehengelassen. Die Lösung wird alsdann eingedampft, der Rückstand mit Alkohol ausgekocht und die erhaltene alkoholische Lösung abgekühlt. Das dann in Form farbloser N ädelchen auskristallisierende p-Thiour eidophenyltrimethylammoniumchlorid Cl(CH3)3N-C,,H4-NH-CS-NH2 zersetzt sich bei 183 bis 184e.Examples i. 44.6 parts by weight of p-amophenyltrimethylammonium chloride chlorohydrate and 19.6 parts by weight of potassium rhodium are in t oo Parts of the room water , dissolved and heated for some time on the steam bath or for several days at room temperature ditched. The solution is then evaporated, the residue is boiled with alcohol and the alcoholic solution obtained is cooled. Then in the form of colorless needles crystallizing p-thioureidophenyltrimethylammonium chloride Cl (CH3) 3N-C ,, H4-NH-CS-NH2 decomposes at 183 to 184e.

Die wäßrige Lösung der Verbindung scheidet erst bei Zusatz von viel Lauge die freie Ammoniumbase in öligem Zustande ab.The aqueous solution of the compound separates only when a lot is added Leach the free ammonium base in an oily state.

a. 22,3 Gewichtsteile m-Aminophenyltrimethylammoniumchloridchlorhydrat und 8,1 Gewichtsteile Kaliumcyanat werden in 4o Raumteilen Wasser gelöst und nach Beispiel i aufgearbeitet. Die erhaltenen Kristalle des m-Ureidophenyltrimethylammoniumchlorids Cl (CH3)3N-C,,H4-NH-CO-NH2 zersetzen sich gegen 202e.a. 22.3 parts by weight of m-aminophenyltrimethylammonium chloride chlorohydrate and 8.1 parts by weight of potassium cyanate are dissolved in 40 parts by volume of water and worked up according to Example i. The obtained crystals of the m-ureidophenyltrimethylammonium chloride Cl (CH3) 3N-C ,, H4-NH-CO-NH2 decompose to 202e.

3. 1 Molm-Aminophenyltrimethylammoniumchlorid wird in der zwei- bis dreifachen Menge Wasser gelöst und mit i Mol Phenylisocyanat kräftig geschüttelt unter zeitweiser Kühlung. Nach beendeter Umsetzung wird die Lösung im Vakuum eingedampft. Der Sirupöse Rückstand wird beim Behandeln mit Aceton kristallin. Das so in theoretischer Menge erhaltene m-Phenylur.eidophenyltrimethylammoniumchlorid ist in Wasser leicht löslich und zersetzt sich nach dem Umlösen aus Sprit bei 218 bis 219e.3. 1 mole of aminophenyltrimethylammonium chloride is used in the two to dissolved three times the amount of water and shaken vigorously with 1 mole of phenyl isocyanate with temporary cooling. When the reaction has ended, the solution is evaporated in vacuo. The syrupy residue becomes crystalline on treatment with acetone. So in theory The amount of m-Phenylur.eidophenyltrimethylammonium chloride obtained is light in water soluble and decomposes after dissolving from fuel at 218 to 219e.

Beim Versetzen der wäßrig en Lösung dieses Chlorids mit einer wäßrigen Lösung von ;Jodkalium scheidet sich das m-Phenylureidophenyltrimethylammoniumj odid J(CH3)3N-C6H4 'NH-CO-NH-CC.H5 in schönen, farblosen, anscheinend rhombischen Kristallen mit dem Zersetzungspunkt 189 bis igoe ab. Aus Wasser erhält man kristallwasserhaltige Kristalle vom Zersetzungspunkt i35 bis 136e.When the aqueous solution of this chloride is added to an aqueous one Solution of; iodotassium iodide separates the m-phenylureidophenyltrimethylammonium iodide J (CH3) 3N-C6H4 'NH-CO-NH-CC.H5 in beautiful, colorless, apparently rhombic crystals with the decomposition point 189 to igoe. Water containing water of crystallization is obtained from water Crystals from decomposition point i35 to 136e.

4. Aus i Mol m-Aminophenyltrimethylammoniumchloridchlorhydrat und z Mol eines Rhodansalzes erhält man nach der in Beispiel i beschriebenen Arbeitsweise in guter Ausbeute das m-Thioureidophenyltrimethylammoniumrhodanid, das aus verdünntem Alkohol in farblosen Kristallen vom Schmelzpunkt 162 bis 163e kristallisiert.4. From 1 mole of m-aminophenyltrimethylammonium chloride chlorohydrate and z moles of a rhodane salt, the m-thioureidophenyltrimethylammonium thioureidophenyltrimethylammonium thioureidophenyltrimethylammonium rhodanide is obtained in good yield by the procedure described in example i, which crystallizes from dilute alcohol in colorless crystals with a melting point of 1 62 to 163e.

5. Läßt man äquimolekulare Mengen von Allylsenföl und m-Aminophenyltrimethylaminoniumehlorid in methylalkoholischer Lösung aufeinander einwirken und dampft das Gemisch ein, so erhält man das m-Allylthioureidophenyltrimethylammoniumchlorid Cl (CH3)3N-C,H4-NH-CS-NH-C,H, in nahezu theoretischer Ausbeute. Farblose Kristalle, Zersetzungspunkt 173`.5. If equimolecular amounts of allyl mustard oil and m-aminophenyltrimethylaminonium chloride in a methyl alcoholic solution are allowed to act on one another and the mixture is evaporated, the m-allylthioureidophenyltrimethylammonium chloride Cl (CH3) 3N-C, H4-NH-CS-NH-C, H, in almost theoretical yield. Colorless crystals, decomposition point 173`.

6. 15,2 Gewichtsteile z-Methyl-4-amüioazobenzol-31-trimethylammoniumchlorid werden in 5o Raumteilen n-Salzsäure gelöst. Zu dieser Lösung gibt man 5 Gewichtsteile Rhodankalium, das sich beim Umrühren auflöst, während sich gleichzeitig das 2-Methyl-4-t11ioureidoazobenzol- 3'-trimethylammoniumchlorid in theoretischer Ausbeute abscheidet. Beim Umlösen aus Methanol erhält man bordeauxrote Nadeln mit grünem Oberflächenglanz vom Zersetzungspunkt 186 bis 187e.6. 15.2 parts by weight of z-methyl-4-aminoazobenzene-31-trimethylammonium chloride are dissolved in 5o parts by volume of n-hydrochloric acid. 5 parts by weight are added to this solution Potassium rhodium, which dissolves when stirred, while at the same time the 2-methyl-4-t11ioureidoazobenzene- 3'-trimethylammonium chloride is deposited in theoretical yield. When redeemed Methanol gives you burgundy red needles with a green surface luster from the decomposition point 186 to 187e.

Claims (1)

PATENTANSPRUCH: Abänderung des Verfahrens des Patents 553 278 zur Gewinnung von Harnstoff-und Thioharnstoffabkömmlingen der aromatischen, heterocyclischen und ar omatisch-heterocyclischen Reihe, dadurch gekennzeichnet, daß man aromatische Amine, welche mindestens eine an einem Kern sitzende quaternäre Stickstoffgruppe tragen, nach an sich bekannten Verfahren in die entsprechenden Harnstoffe bzw. Thioharnstoffe überführt.PATENT CLAIM: Modification of the procedure of patent 553 278 for Production of urea and thiourea derivatives of the aromatic, heterocyclic ones and aromatic-heterocyclic series, characterized in that aromatic Amines, which have at least one quaternary nitrogen group attached to a nucleus wear, according to methods known per se in the corresponding ureas or thioureas convicted.
DEI41876D 1931-06-21 1931-06-21 Process for the recovery of urea and thiourea pellets of the aromatic series Expired DE596004C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE1930553278D DE553278C (en) 1931-06-21 1930-10-10 Process for the recovery of urea and thiourea emissions of the aromatic, heterocyclic and aromatic-heterocyclic series
DEI41876D DE596004C (en) 1931-06-21 1931-06-21 Process for the recovery of urea and thiourea pellets of the aromatic series

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEI41876D DE596004C (en) 1931-06-21 1931-06-21 Process for the recovery of urea and thiourea pellets of the aromatic series

Publications (1)

Publication Number Publication Date
DE596004C true DE596004C (en) 1934-04-26

Family

ID=7190646

Family Applications (2)

Application Number Title Priority Date Filing Date
DE1930553278D Expired DE553278C (en) 1931-06-21 1930-10-10 Process for the recovery of urea and thiourea emissions of the aromatic, heterocyclic and aromatic-heterocyclic series
DEI41876D Expired DE596004C (en) 1931-06-21 1931-06-21 Process for the recovery of urea and thiourea pellets of the aromatic series

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DE1930553278D Expired DE553278C (en) 1931-06-21 1930-10-10 Process for the recovery of urea and thiourea emissions of the aromatic, heterocyclic and aromatic-heterocyclic series

Country Status (1)

Country Link
DE (2) DE553278C (en)

Also Published As

Publication number Publication date
DE553278C (en) 1932-06-27

Similar Documents

Publication Publication Date Title
DE514248C (en) Process for the preparation of substituted guanidines
DE596004C (en) Process for the recovery of urea and thiourea pellets of the aromatic series
DE506282C (en) Process for the preparation of highly alkylated guanidines
DE3443232A1 (en) Process for the preparation of clear aqueous disinfectant solutions
DE910779C (en) Process for the preparation of N-sulfonylureas
DE1177633B (en) Process for the preparation of aminoalkylated 9,10-dihydroanthracenes
DE544211C (en) Process for the preparation of disubstituted carbamic acid esters
DE852391C (en) Process for the preparation of new esters of dithiocarbamic acid
DE1042569B (en) Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acid
DE713079C (en) Process for the preparation of clusters of 4-aminobenzenesulfonamides
DE901053C (en) Process for the production of guanidine thiocyanate
DE955055C (en) Process for the preparation of aminooxyphenylisothiourea
DE1225185B (en) Process for the preparation of a salt of 2,4-diamino-5- (p-chlorophenyl) -6-aethylpyrimidine
DE894994C (en) Process for the production of aliphatic mercury ketone compounds
DE606400C (en) Process for the preparation of complex compounds of secondary or tertiary oxyalkylamines
DE914857C (en) Process for the production of pharmacologically active ethers
AT126139B (en) Process for the preparation of basic nitro derivatives of 9-aminoacridine.
DE1220430B (en) Process for the preparation of 2-thio-3- (beta-phenylaethyl) -5-carboxymethyl-tetrahydro, 3, 5-thiadiazine
AT216486B (en) Process for the preparation of new mercaptoacylamides
DE86148C (en)
DE1024954B (en) Process for the preparation of N-disubstituted dithiocarbamic acid esters which contain sulfonic acid groups in the alcohol residue
DE964495C (en) Process for the preparation of a new thiosemicarbazide
DE360424C (en) Process for the preparation of carbamic acid derivatives of the pyrazolone series
DE726740C (en) Process for the production of water-soluble compounds of 4-aminobenzene sulfonamides
DE727473C (en) Process for the production of clumps of 4-aminobenzenesulfonamides