DE901053C - Process for the production of guanidine thiocyanate - Google Patents
Process for the production of guanidine thiocyanateInfo
- Publication number
- DE901053C DE901053C DEA936A DEA0000936A DE901053C DE 901053 C DE901053 C DE 901053C DE A936 A DEA936 A DE A936A DE A0000936 A DEA0000936 A DE A0000936A DE 901053 C DE901053 C DE 901053C
- Authority
- DE
- Germany
- Prior art keywords
- guanidine thiocyanate
- thiocyanate
- guanidine
- production
- carbon disulfide
- 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
Links
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- -1 guanidine compound Chemical class 0.000 description 2
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
Verfahren zur Herstellung von Cuanidinthiocyanat Es ist bekannt, daß Ammoniumthiocyanat in einer geschlossenen Röhre erhitzt werden kann und Guanidinthiocyanat ergibt. Es ist auch bekannt, daß Schwefelkohlenstoff und Ammoniak zusammen erhitzt werden können und dabei Ammoniumthiocyanat entsteht. Jedoch wurde Guanidinthiocyanat noch nicht direkt aus Schwefelkohlenstoff und Ammoniak erhalten.Process for the preparation of cuanidine thiocyanate It is known that Ammonium thiocyanate can be heated in a closed tube and guanidine thiocyanate results. It is also known that carbon disulfide and ammonia heat together and ammonium thiocyanate is formed. However, guanidine thiocyanate was found not yet obtained directly from carbon disulfide and ammonia.
Auf Grund der vorliegenden Erfindung wurde nun ein Verfahren zur Herstellung von Guanidinthiocyanat ausgearbeitet, das darin besteht, daß man Ammoniak und Schwefelkohlenstoff in einem geschlossenen Reaktionsraum auf 185 bis 450'C erhitzt und das gebildete Guanidinthiocyanat dann in bekannter Weise aus dem Reaktionsgemisch ausscheidet. Die folgenden Beispiele erläutern die Erfindung. Beispiel 1 o,261 Mol Schwefelkohlenstoff und 0,94 Mol Ammoniak werden in einem Autoklav von 300 ccm 5 Stunden lang ,auf 35o° C erhitzt. Nach Kühlung und Öffnung des Autoklavs wird die Reaktionsmasse herausgekratzt und in eine kleine Menge Wasser, z. B. etwa 5o ccm, gebracht. Guanidinthiocyanat ist leicht löslich und löst sich unter Zurücklassung von unlöslichen Stoffen im Wasser. Die Lösung wird dann filtriert. Das Filtrat besteht hauptsächlich aus einer wäßrigen Lösung von Guanidinthiocyanat und Ammoniumthiocyanat. Die Guanidinverbindung kann durch Zugabe von Ammoniumnitrat abgeschieden werden, wobei das schwerlösliche Guanidinnitrat ausfällt, das dann abfiltriert wird. Die Ausbeute an Guanidinthiocyanat, bezogen auf Schwefelkohlenstoff, beträgt 47,60;ö.On the basis of the present invention, a process for the production of guanidine thiocyanate has now been worked out, which consists in heating ammonia and carbon disulfide in a closed reaction chamber to 185 to 450 ° C. and then separating the guanidine thiocyanate formed from the reaction mixture in a known manner. The following examples illustrate the invention. EXAMPLE 1 0.261 moles of carbon disulfide and 0.94 moles of ammonia are heated to 35 ° C. for 5 hours in a 300 ccm autoclave. After cooling and opening the autoclave, the reaction mass is scraped out and poured into a small amount of water, e.g. B. about 50 cc, brought. Guanidine thiocyanate is easily soluble and dissolves in the water, leaving behind insoluble substances. The solution is then filtered. The filtrate consists mainly of an aqueous solution of guanidine thiocyanate and ammonium thiocyanate. The guanidine compound can be separated out by adding ammonium nitrate, the sparingly soluble guanidine nitrate precipitating, which is then filtered off. The yield of guanidine thiocyanate, based on carbon disulfide, is 47.60.
Zur Abscheidung des Guanidinthiocyanats von anderen im Filtrat gelösten Substanzen lassen sich auch die übrigen bekannten Verfahren anwenden. Beispiel 2 24g Ammoniak (i,42 Mol) und ioo g Schwefelkohlenstoff (i,31 Mol) werden in eine=n 3oo-ccm-Autoklav etwa 3 Stunden lang auf ungefähr 250° C erhitzt. Der maximale Druck, der sich während der Umsetzung entwickelt, beträgt 86,5 at; der Druck schwankt je nach Füllung des Autoklavs. Man erhält Guanidinthiocyanat in einer Ausbeute von 4 50 °'0 .To separate the guanidine thiocyanate from others dissolved in the filtrate The other known methods can also be used for substances. Example 2 24g ammonia (i, 42 mol) and 100 g carbon disulfide (i, 31 mol) are in a = n 300 cc autoclave heated to about 250 ° C for about 3 hours. The maximum pressure that develops during the implementation is 86.5 at; the pressure varies after filling the autoclave. Guanidine thiocyanate is obtained in a yield of 4 50 ° '0.
Die Reaktionsdauer ist von der Temperatur abhängig. Bei i 8 5'C wird etwa nach 2 Stunden Guanidinthiocyanat erhalten; für die Einstellung des Gleichgewichts sind ungefähr 8 bis 2o Stunden erforderlich. Bei 24o' C wird etwas Guanidinthiocyanat in wenigen Minuten erhalten und das Gleichgewicht in ungefähr 2 Stunden erreicht.The reaction time depends on the temperature. At i 8 it becomes 5'C obtained guanidine thiocyanate after about 2 hours; for setting the balance It takes about 8 to 20 hours. At 24o 'C some guanidine thiocyanate becomes obtained in a few minutes and reached equilibrium in about 2 hours.
Die Isolierung des Guanidinthiocyanats kann durch geeignete Maßnahmen erfolgen, z. B. durch Kühlen oder Eindampfen der wäßrigen Lösung bis zur Kristallisation oder durch Zufügen. einer mit Wasser mischbaren organischen Flüssigkeit, wie Äthanol, um die Löslichkeit des Salzes herabzusetzen und dessen Ausfällung zu bewirken. Die Guanidinverbindung kann auch in Form eines weniger löslichen Salzes, etwa .des Pikrats, Carbonats, Nitrats oder Phosphats, isoliert werden. Die Bildung eines derartigen schwerlöslichen Salzes wird durch einfaches Zufügen einer äquivalenten Menge des Ammonium- oder eines Metallsalzes der entsprechenden Säure zu der wäßrigen Lösung des Thiocyanats erreicht und die Kristallisation durch irgendwelche Maßnahmen, wie sie oben erwähnt wurden, eingeleitet. Ein vorteilhaftes Verfahren besteht darin, Ammoniumnitrat einer wäßrigen Lösung von Guanidinthiocyanat zuzufügen, wodurch das schwerlösliche Guanidinnitrat ausfällt.The guanidine thiocyanate can be isolated by suitable measures take place, e.g. B. by cooling or evaporation of the aqueous solution until crystallization or by adding. an organic liquid that is miscible with water, such as ethanol, to reduce the solubility of the salt and cause its precipitation. the Guanidine compound can also be in the form of a less soluble salt, such as the picrate, Carbonate, nitrate or phosphate, are isolated. The formation of such a The sparingly soluble salt is simply added by adding an equivalent amount of the Ammonium or a metal salt of the corresponding acid to the aqueous solution of the thiocyanate and the crystallization by some means, such as they were mentioned above. A beneficial practice is to Add ammonium nitrate to an aqueous solution of guanidine thiocyanate, whereby the poorly soluble guanidine nitrate precipitates.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US901053XA | 1949-03-31 | 1949-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE901053C true DE901053C (en) | 1954-01-07 |
Family
ID=22221346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA936A Expired DE901053C (en) | 1949-03-31 | 1950-03-02 | Process for the production of guanidine thiocyanate |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE901053C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE963421C (en) * | 1953-09-29 | 1957-05-09 | Bergwerksverband Zur Verwertun | Process for the production of guanidine rhodanide |
-
1950
- 1950-03-02 DE DEA936A patent/DE901053C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE963421C (en) * | 1953-09-29 | 1957-05-09 | Bergwerksverband Zur Verwertun | Process for the production of guanidine rhodanide |
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