DE1081000B - Process for the preparation of thiosemicarbazide - Google Patents
Process for the preparation of thiosemicarbazideInfo
- Publication number
- DE1081000B DE1081000B DED29601A DED0029601A DE1081000B DE 1081000 B DE1081000 B DE 1081000B DE D29601 A DED29601 A DE D29601A DE D0029601 A DED0029601 A DE D0029601A DE 1081000 B DE1081000 B DE 1081000B
- Authority
- DE
- Germany
- Prior art keywords
- thiosemicarbazide
- ketone
- hydrazonium
- preparation
- rhodanide
- 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
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- -1 ketone hydrazone Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FQUDPIIGGVBZEQ-UHFFFAOYSA-N acetone thiosemicarbazone Chemical compound CC(C)=NNC(N)=S FQUDPIIGGVBZEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- LLKHYFYYSFYSNF-UHFFFAOYSA-N cyclohexylidenehydrazine Chemical compound NN=C1CCCCC1 LLKHYFYYSFYSNF-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von Thiosemicarbazid Im Patent 1067 426 und in der Patentanmeldung D 28489 IV b/12 o wird ein einstufiges Verfahren zur Gewinnung von Thiosemicarbazid beschrieben, nach welchem Hydrazoniumrhodanid in Gegenwart katalytisch wirkender Mengen eines Ketons, vorzugsweise Aceton oder gewisser Ketonderivate, wie z. B. Ketonthiosemicarbazon, Ketazin oder Ketonhydrazon, in mindestens 60%igem wäßrigem Alkohol zum Sieden erhitzt wird. Die Ausbeute an Thiosemicarbazid beträgt dabei 900/a der Theorie.Process for the preparation of thiosemicarbazide In the patent 1067 426 and in the patent application D 28489 IV b / 12 o a one-step process for the production of thiosemicarbazide is described, according to which hydrazonium rhodanide in the presence of catalytically active amounts of a ketone, preferably acetone or certain ketone derivatives such. B. ketone thiosemicarbazone, ketazine or ketone hydrazone, is heated to boiling in at least 60% aqueous alcohol. The yield of thiosemicarbazide is 900 / a of theory.
Es wurde nun gefunden, daß man Thiosemicarb@azid mit Ausbeuten von ebenfalls 90% der Theorie erhält, wenn man wäßrig-alkoholischeHydrazoniumrhodanidlösungen mit einer Alkoholkonzentration bis zu 60% in Gegenwart katalytisch wirkender Mengen eines Ketons oder Ketonderivates erhitzt.It has now been found that thiosemicarb @ azide with yields of 90% of theory is also obtained when aqueous-alcoholic hydrazonium rhodanide solutions are used with an alcohol concentration of up to 60% in the presence of catalytically active quantities of a ketone or ketone derivative heated.
Und weiter wurde gefunden, daß man Thior semicarbazid mit gleichguten Ausbeuten auch erhält, wenn man den Alkohol ganz wegläßt und nur eine wäßrige Hydrazoniumrhodanidlösung in Gegenwart katalytisch wirkender Mengen eines Ketons oder Ketonderivates, erhitzt.And it was further found that Thior semicarbazide is equally good Yields are also obtained if the alcohol is omitted entirely and only an aqueous hydrazonium thiocyanate solution heated in the presence of catalytically active amounts of a ketone or ketone derivative.
Bei Verwendung von Wasser als Lösungsmittel ist von großem Vorteil, daß die Wassermenge so, gewählt werden kann, daß die bei der Herstellung des Hydrazoniumrhodanids aus Hydrazinhydrat, Hydrazinsalzen und vorzugsweise Alkalirhodaniden entstehenden Salze, z. B. Ammoniumsulfat, Natriumsulfat oder Kaliumsulfat, in der Reaktionslösung verbleiben können, und daß durch ihre Anwesenheit die Abscheidung des Thiosemicarbazids begünstigt wird. Beispiel 1 In eine Lösung von 224m1 25%igem Hydrazinhydrat und 100 ml Wasser werden unter Rühren bei 40°C 144g Hydrazinsulfat eingetragen und die Lösung auf pH 3 bis 4 eingestellt. Zu dieser Lösung werden bei 40°C 240g Ammo@niumrhodanid gegeben. Man setzt nun 6 ml Aceton zu und erhitzt 8 Stunden auf 95 bis 110° C. Nach Beendigung der Reaktion wird auf 8° C abgekühlt und das ausgefallene Thiosemicarbazid abgesaugt, mit Wasser genraschen und getrocknet. Man erhält 178 g Thiosemicarbazid=89°/o der Theorie.When using water as a solvent it is of great advantage that the amount of water can be chosen so that that in the preparation of the hydrazonium rhodanide arising from hydrazine hydrate, hydrazine salts and preferably alkali metal rhodanides Salts, e.g. B. ammonium sulfate, sodium sulfate or potassium sulfate, in the reaction solution can remain, and that by their presence the deposition of the thiosemicarbazide is favored. Example 1 In a solution of 224 ml of 25% hydrazine hydrate and 100 ml of water are added with stirring at 40 ° C 144g of hydrazine sulfate and the Solution adjusted to pH 3 to 4. 240 g of ammonium rhodanide are added to this solution at 40 ° C given. 6 ml of acetone are then added and the mixture is heated to 95 to 110 ° C. for 8 hours Completion of the reaction is cooled to 8 ° C. and the precipitated thiosemicarbazide Vacuumed, sprinkled with water and dried. 178 g of thiosemicarbazide = 89% are obtained the theory.
Beispiel 2 Zu einer gemäß Beispiel 1 hergestellten Hydrazoniumrhodanidlösung werden 6 g Acetonthiosemicarbazon gegeben und 10 Stunden auf 105 bis 115° C erhitzt. Nach Abkühlen auf 5 bis 10°C erhält man 181 g Thiosemicarbazid = 90,5 % der Theorie.Example 2 To a hydrazonium thiocyanate solution prepared according to Example 1 6 g of acetone thiosemicarbazone are added and the mixture is heated to 105 to 115 ° C. for 10 hours. After cooling to 5 to 10 ° C., 181 g of thiosemicarbazide = 90.5% of theory are obtained.
Beispiel 3 Zu einer gemäß Beispiel 1 hergestellten Hydrazoniumrhodanidlösung werden 6 ml Dimethylketazin gegeben und 8 Stunden auf 95 bis 100°C erhitzt. Man erhält 167g Thiosemicarbazid= 83,5% der Theorie.Example 3 To a hydrazonium thiocyanate solution prepared according to Example 1 6 ml of dimethyl ketazine are added and the mixture is heated to 95 to 100 ° C. for 8 hours. Man receives 167 g of thiosemicarbazide = 83.5% of theory.
Beispiel 4 Zu einer gemäß Beispiel 1 hergestellten Hydrazoniumrhodanidlösung werden 6 g Cyclohexanonhydrazon gegeben und 8 Stunden zum Sieden erhitzt. Man erhält 166 g Thiosemicarbazid---83% der Theorie.Example 4 To a hydrazonium thiocyanate solution prepared according to Example 1 6 g of cyclohexanone hydrazone are added and the mixture is heated to boiling for 8 hours. You get 166 g thiosemicarbazide --- 83% of theory.
Beispiel 5 In eine Lösung von 112m1 25%igem Hydrazinhydrat werden unter Rühren 72 g Hydrazinsulfat eingetragen und die Lösung auf p$ = 3 bis 4 eingestellt. Zu dieser Lösung werden bei 40° C 120 g Ammoniumrhodanid gegeben. Man rührt 10 Minuten nach und setzt dann 105 ml Methanol zu. Nach kurzem Nachrühren wird vom ausgefallenen Ammoniumsulfat abgesaugt. Das Filtrat wird nach Zugabe von 3 ml Aceton 16 Stunden unter Rückfluß gekocht. Nach Abkühlen auf 7° C wird das ausgefallene Thiosemicarbazid abgesaugt, gewaschen und getrocknet. Man erhält 87 g Thiosemicarbazid = 87% der Theorie.Example 5 25% hydrazine hydrate is added to a solution of 112 ml 72 g of hydrazine sulfate were added with stirring and the solution was adjusted to p $ = 3 to 4. 120 g of ammonium thiocyanate are added to this solution at 40.degree. The mixture is stirred for 10 minutes after and then adds 105 ml of methanol. After brief stirring, the precipitated Sucked off ammonium sulfate. The filtrate is after addition of 3 ml of acetone for 16 hours refluxed. After cooling to 7 ° C, the precipitated thiosemicarbazide is vacuumed, washed and dried. 87 g of thiosemicarbazide = 87% of the total are obtained Theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED29601A DE1081000B (en) | 1958-12-16 | 1958-12-16 | Process for the preparation of thiosemicarbazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED29601A DE1081000B (en) | 1958-12-16 | 1958-12-16 | Process for the preparation of thiosemicarbazide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1081000B true DE1081000B (en) | 1960-05-05 |
Family
ID=7040153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED29601A Pending DE1081000B (en) | 1958-12-16 | 1958-12-16 | Process for the preparation of thiosemicarbazide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1081000B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1107214B (en) | 1959-09-02 | 1961-05-25 | Basf Ag | Process for the conversion of hydrazonium rhodanide to thiosemicarbazide |
| DE1274574B (en) * | 1963-11-27 | 1968-08-08 | Bayer Ag | Process for the preparation of thiosemicarbazide |
| DE3234528A1 (en) * | 1982-09-17 | 1984-03-22 | Bayer Ag, 5090 Leverkusen | Preparation of thiosemicarbazide |
-
1958
- 1958-12-16 DE DED29601A patent/DE1081000B/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1107214B (en) | 1959-09-02 | 1961-05-25 | Basf Ag | Process for the conversion of hydrazonium rhodanide to thiosemicarbazide |
| DE1274574B (en) * | 1963-11-27 | 1968-08-08 | Bayer Ag | Process for the preparation of thiosemicarbazide |
| DE3234528A1 (en) * | 1982-09-17 | 1984-03-22 | Bayer Ag, 5090 Leverkusen | Preparation of thiosemicarbazide |
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