DE1670146A1 - Process for the preparation of addition compounds of guanidinothiourea - Google Patents
Process for the preparation of addition compounds of guanidinothioureaInfo
- Publication number
- DE1670146A1 DE1670146A1 DE19661670146 DE1670146A DE1670146A1 DE 1670146 A1 DE1670146 A1 DE 1670146A1 DE 19661670146 DE19661670146 DE 19661670146 DE 1670146 A DE1670146 A DE 1670146A DE 1670146 A1 DE1670146 A1 DE 1670146A1
- Authority
- DE
- Germany
- Prior art keywords
- guanidinothiourea
- preparation
- addition compounds
- parts
- dicyandiamide
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
- C07G99/002—Compounds of unknown constitution containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Additionsverbindungen des Guanidinothioharnstoffs Es ist bekannt, daß Dicyandiamid in Wasser oder Alkohol Schwefelwasserstoff anlagert unter Bildung von Guanidinothioharnstoff.Process for the preparation of addition compounds of guanidinothiourea It is known that dicyandiamide accumulates hydrogen sulfide in water or alcohol with formation of guanidinothiourea.
Trotz langer Reaktionszeiten (40 Stunden) si. nd die Ausbeuten nur mäßige Es wurde nun gefunden, daß man Additionsverbindungen von N-Alkylpyrrolidonen mit Guanidinothioharnstoff auf sehr einfache Weise und mit ausgezeichneten Ausbeuten erhält, wenn man Dicyandiamid mit Schwefelwasserstoff in Gegenwart eines N-Alkylpyrrolidons als Lösungsmittel und in Gegenwart eines sekundären oder tertiären Amins im Temperaturbereich zwischen 20 und 120 C, gegebenenfalls unter erhöhtem Druck, umsetzte Bevorzugt verwendet man N-Alkylpyrrolidone, deren Alkylgruppen 1 bis 4 Kohlenstoffatome besitzen. Insbesondere verwendet man N-Methylpyrrolidon. Die N-Alkylpyrrolidone werden in der Regel in ~ Mengen von 100 bis 500 Gew.% bezogen auf angewandtes Dicyandiamidyverwendet.Despite long reaction times (40 hours) si. nd the yields only It has now been found that addition compounds of N-alkylpyrrolidones can be used with guanidinothiourea in a very simple manner and with excellent yields obtained when dicyandiamide is combined with hydrogen sulfide in the presence of an N-alkylpyrrolidone as a solvent and in the presence of a secondary or tertiary amine in the temperature range between 20 and 120 ° C., optionally under increased pressure, preferably used one N-alkylpyrrolidones whose alkyl groups have 1 to 4 carbon atoms. In particular one uses N-methylpyrrolidone. The N-alkylpyrrolidones are usually used in ~ Amounts of 100 to 500% by weight based on the dicyandiamidy used.
Geeignete Amine sind z. B. Piperidin, Morpholin, Diäthylamin, Dibutylaminy Diisopropylamin, Dicyclohexylamin, Trimethylamin, Triäthylamin, Tripropylamin, Tributylamin, Methyldiäthylamin, Dimethylanilin, Diäthylanilin, Dimethyltoluidin oder Pyridin. Man wendet sie zweckmäßig in Mengen von 1 bis 20 Gew. %, bezogen auf angewandtes Dicyandiamid, an.Suitable amines are e.g. B. piperidine, morpholine, diethylamine, dibutylamine Diisopropylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, Methyl diethylamine, dimethylaniline, diethylaniline, dimethyltoluidine or pyridine. They are expediently used in amounts of 1 to 20% by weight, based on the amount used Dicyandiamide.
Man kann das Verfahren z.B. so durchfuhren, da8 man das Dicyandiamid, des Amin und das N-Alkylpyrrolidon zusammen auf die gewunschte Reaktionstemperatur erwärmt und dann Schwefelwasserstoff bei Normaldruck oder erhöhtem Druck, z. B. bis 5 atü, durch das Gemisch leitet. Nachdem einige Stunden Schwefelwasserstoff eingeleitet wurde, läßt man das Gemisch sich abkühlen. Dabei fällt die Additionsverbindung des Guanidinothioharnstoffs mit dem N-Alkylpyrrolidon (Molverhältnis 1 : 1) in Form farbloser Kristalle aus, die leicht aus dem Reaktionsgemisch abgetrennt werden können.The process can be carried out, for example, by using the dicyandiamide, of the amine and the N-alkylpyrrolidone together to the desired reaction temperature heated and then hydrogen sulfide at normal pressure or elevated pressure, z. B. up to 5 atm, passes through the mixture. After a few hours of hydrogen sulfide was initiated, the mixture is allowed to cool. Thereby the addition connection falls of guanidinothiourea with the N-alkylpyrrolidone (molar ratio 1: 1) in the form colorless crystals, which can be easily separated from the reaction mixture.
Nach dem Waschen des Niederschlags mit z.B. Äther und Trocknen sind sie rein. Die Additionsverbindung kann aus wenig Alkohol umkristallisiert werden. Durch Auflosen in einer größeren Menge Alkohol, z.B. 5- bis 20fachen Gewichtsmenge, bezogen auf die Additionsverbindung, am besten unter Erwärmen, erhält man beim Abkuhlen den Guanidinothioharnstoff frei von N-Alkylpyrrolidon.After washing the precipitate with e.g. ether and drying it them in. The addition compound can be recrystallized from a little alcohol. By dissolving in a larger amount of alcohol, e.g. 5 to 20 times the amount by weight, based on the addition compound, preferably with heating, is obtained on cooling the guanidinothiourea free of N-alkylpyrrolidone.
Für die meisten Umsetzungen kann die Additionsverbindung wie der freie Guanidinothioharnstoff verwendet werden.For most reactions, the addition compound can be like the free Guanidinothiourea can be used.
Guanidinothioharnstoff ist ein wichtiges Vorprodukt zur Hertellung von Triazinen, die als Farbstoffe, Herbizide und optische Aufheller Verwendung finden.Guanidinothiourea is an important precursor for production of triazines, which are used as dyes, herbicides and optical brighteners.
Die in dem Beispiel angegebenen Teile bedeuten Gewichtsteile.The parts given in the example are parts by weight.
Beispiel 100 Teile Dicyandiamid, 280 Teile N-Methylpyrrolidon und 10 Teile Tripropylamin werden auf 70°C erhitzt und 8 Stunden Schwefelwasserstoff eingeleitete Man läßt über Nacht bei 20 bis 25°C stehen, saugt von den ausgefallenen Kristallen ab, wäscht sie mit etwas Äther und trocknete Man erhält 240 Teile der Additionsverbindung von Guanidinothioharnstoff mit N-Methylpyrrolidon. Example 100 parts of dicyandiamide, 280 parts of N-methylpyrrolidone and 10 parts of tripropylamine are heated to 70 ° C. and hydrogen sulfide for 8 hours The one introduced is allowed to stand overnight at 20 to 25 ° C. and the precipitated products are sucked off Crystals off, washed with a little ether and dried. 240 parts of the are obtained Addition compound of guanidinothiourea with N-methylpyrrolidone.
Der Schmelzpunkt beträgt 94 bis 96°C. Aus wenig Butanol ist eie umkristallisierbaro Aus etwa der 10fachen Menge Äthanol kristallisiert der N-Methylpyrrolidon freien Guanidinothioharnstoff vom Schmelzpunkt 160 bis 164°C. Die Ausbeute fUr die Additionsverbindung beträgt 93 % der Theorieg bezogen auf angewandtes Dicyandiamid.The melting point is 94 to 96 ° C. It can be recrystallized from a little butanol The free N-methylpyrrolidone crystallizes from about 10 times the amount of ethanol Guanidinothiourea with a melting point of 160 to 164 ° C. The yield for the addition compound is 93% of the theory based on applied dicyandiamide.
Analyse der Additionsverbindung: C7H15N5O S (217) berechnet: C 38,7 % H 699 % N 32, 25 % S 14, 75 % gefunden: C 39, 2 % H 7,2 % N 31,6 % S 14,4%.Analysis of the addition compound: C7H15N5O S (217) calculated: C 38.7 % H 699% N 32, 25% S 14, 75% found: C 39.2% H 7.2% N 31.6% S 14.4%.
Verwendet man anstelle von 10 Teilen Tripropylamin 15 Teile Triäthylamin oder 15 Teile Pyridin so erhält man die gewünschte Additioneverbindung in gleicher Weise.If 15 parts of triethylamine are used instead of 10 parts of tripropylamine or 15 parts of pyridine, the desired addition compound is obtained in the same way Way.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB0088854 | 1966-09-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1670146A1 true DE1670146A1 (en) | 1970-10-29 |
Family
ID=6984499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19661670146 Pending DE1670146A1 (en) | 1966-09-10 | 1966-09-10 | Process for the preparation of addition compounds of guanidinothiourea |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1670146A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480438A1 (en) * | 1990-10-11 | 1992-04-15 | SKW Trostberg Aktiengesellschaft | Process for the preparation of guanylthiourea |
-
1966
- 1966-09-10 DE DE19661670146 patent/DE1670146A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480438A1 (en) * | 1990-10-11 | 1992-04-15 | SKW Trostberg Aktiengesellschaft | Process for the preparation of guanylthiourea |
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