DE871756C - Process for the preparation of thiosemicarbazides - Google Patents
Process for the preparation of thiosemicarbazidesInfo
- Publication number
- DE871756C DE871756C DEF6304A DEF0006304A DE871756C DE 871756 C DE871756 C DE 871756C DE F6304 A DEF6304 A DE F6304A DE F0006304 A DEF0006304 A DE F0006304A DE 871756 C DE871756 C DE 871756C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- thiosemicarbazides
- preparation
- hydrazine
- acid
- 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
- 150000003583 thiosemicarbazides Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- 150000003585 thioureas Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic amino acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008164 mustard oil Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003584 thiosemicarbazones Chemical class 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
- C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung Von Thiosemicarbaziden Unter den bekannten
Methoden zur Herstellung von in .-Stellung mit einem aromatischen Rest (Ar.) substituierten
Thiosemicarbaziden der allgemeinen Formel
Es wurde nun gefunden, daB symmetrisch aromatisch oder heterocyclisch und aliphatisch substituierte Thioharnstoffe bei der Umsetzung mit Hydrazinhydrat .-substituierte Thiosemicarbazidn, ergeben. Statt Hydrazin können auch alkyl- oder arylsubstituierte Hydrazine Verwendung finden. Unter anderem lassen sich auf diesem Wege die bisher nicht bekannten in -Stellung substituierten Thiosemicarbazide von aromatischen Aminosäuren herstellen, die ebenso wie ihre Thiosemicarbazone im Vergleich zu den bisher verwendeten Vertretern dieser Verbindungsgruppe den Vorteil aufweisen, leicht lösliche Salze von Alkalien oder Ammoniumbasen zu bilden.It has now been found that symmetrically aromatic or heterocyclic and aliphatic substituted thioureas when reacted with hydrazine hydrate . -substituted thiosemicarbazides. Instead of hydrazine, alkyl or Find aryl-substituted hydrazines use. Among other things, can be found on this Ways the previously unknown in -position substituted thiosemicarbazides of produce aromatic amino acids as compared to their thiosemicarbazones to the so far representatives of this liaison group used the Have the advantage of forming readily soluble salts of alkalis or ammonium bases.
Die neuen Verbindungen sollen ebenso wie ihre funktionellen Derivate, z. B. die Thiosemicarbazone, als bakteriostatische Heilmittel Verwendung finden. Beispiel i 6o Teile N'-[i-Phenyl-5-oxo-2, 3-dimethyl-pyrazolidyliden-(q.)] N-allylthioharnstoff der Formel (F. = ?,o5 bis2o6°, aus i-Phenyl-2, 3-dimethyl-q.-aminopyrazolon-(5) und Allylsenföl) werden in 3oo Teilen Glykol und io Teilen Hydrazinhydrat gelöst und 8 Stunden auf 115° erhitzt. Nach Entfernen des Lösungsmittels durch Vakuumdestillation wird aus dem Rückstand das Thiosemicarbazid als Benzalverbindung vom F. = zig bis 22o° abgeschieden. Aus dem Thiosemicarbazon erhält man nach den üblichen Spaltungsmethoden, z. B. mittels verdünnter Schwefelsäure, das i-Phenyl-2, 3-dimethyl-q.-thiosemicarbazid-(4.')-pyrazolon-(5) der Formel mit dem Schmelzpunkt igz bis i93°. Beispiel 2 168 Teile m-Methylthioharnstoffbenzoesäure (F. 189 bis igo°, aus m-Aminobenzoesäure und Methylsenföl) werden in 96o Teilen Glykolmonornethyläther und 98 Teilen Natronlauge (33 °/o) gelöst und mit 4. Teilen Hydrazinhydrat 6 Stunden bei iio bis i12.° unter RückfluB erwärmt. Nach Entfernen des Lösungsmittels im Vakuum wird in 5oo Teilen Wasser aufgenommen, filtriert und mit Salzsäure angesäuert. Das kristallinisch ausgefallene Rohprodukt wird abgesaugt und mit einer Lösung von Pyridin in Wasser umkristallisiert. Die so- erhaltene m-Thiosemicarbazidbenzoesäure der Formel schmilzt bei gor bis 2o2° unter Zersetzung und ist leicht löslich in wäßrigen Lösungen von Alkalien, Ammoniumbasen und Alkalicarbonaten.The new compounds, like their functional derivatives, e.g. B. the thiosemicarbazones, are used as bacteriostatic remedies. Example i 60 parts of N '- [i-phenyl-5-oxo-2,3-dimethyl-pyrazolidylidene- (q.)] N-allylthiourea of the formula (F. = .05 to 206 °, from i-phenyl-2, 3-dimethyl-q.-aminopyrazolone- (5) and allyl mustard oil) are dissolved in 300 parts of glycol and 10 parts of hydrazine hydrate and heated to 115 ° for 8 hours. After removing the solvent by vacuum distillation, the thiosemicarbazide is deposited from the residue as a benzal compound with a temperature of tens to 220 °. From the thiosemicarbazone obtained by the usual cleavage methods, for. B. by means of dilute sulfuric acid, the i-phenyl-2, 3-dimethyl-q.-thiosemicarbazid- (4. ') - pyrazolone- (5) of the formula with the melting point igz up to 193 °. Example 2 168 parts of m-methylthioureabenzoic acid (mp 189 to igo °, from m-aminobenzoic acid and methyl mustard oil) are dissolved in 96o parts of glycol monomethyl ether and 98 parts of sodium hydroxide solution (33%) and mixed with 4 parts of hydrazine hydrate for 6 hours at 10 to 12 hours . ° heated under reflux. After removing the solvent in vacuo, the mixture is taken up in 500 parts of water, filtered and acidified with hydrochloric acid. The crystalline precipitated crude product is filtered off with suction and recrystallized with a solution of pyridine in water. The m-thiosemicarbazidbenzoic acid of the formula obtained in this way melts at gor up to 2o2 ° with decomposition and is easily soluble in aqueous solutions of alkalis, ammonium bases and alkali carbonates.
Beispiel 3 226 Teile p-Methylthioharnstoff-salicylsäure (F. i8o bis i82°, aus p-Aminosalicylsäure und Methylsenföl) werden in i2oo Teilen Glykohnonornethyläther und 122 Teilen Natronlauge (33 °/,) gelöst und mit 55 Teilen Hydrazinhydrat 7 Stunden bei iio bis 112° unter RückfluB erwärmt. Nach Abdestillieren des Lösungsmittels wird in 6oo Teilen Wasser aufgenommen, filtriert und mit Salzsäure angesäuert. Die kristallinische Fällung wird abgesaugt und gereinigt.Example 3 226 parts of p-methylthiourea-salicylic acid (F. i8o bis i82 °, from p-aminosalicylic acid and methyl mustard oil) are i2oo parts of Glykohnonornethyläther and 122 parts of sodium hydroxide solution (33%) dissolved and 55 parts of hydrazine hydrate for 7 hours heated to reflux at 110 to 112 °. After distilling off the solvent is taken up in 600 parts of water, filtered and acidified with hydrochloric acid. the crystalline precipitate is filtered off and cleaned.
Die so erhaltene p-Thiosemicarbazidsalicylsäure der Formel schmilzt bei 192 bis 1g5° unter Zersetzung und ist leicht löslich in wäBrigen Lösungen von Alkalien, Ammoniumbasen und Alkalicarbonaten.The p-thiosemicarbazide salicylic acid thus obtained of the formula melts at 192 to 1g5 ° with decomposition and is easily soluble in aqueous solutions of alkalis, ammonium bases and alkali carbonates.
In analoger Weise lassen sich auch die entsprechenden Alkylthioharnstoffderivate aus Aminoarylsulfosäuren und Aminoarylarsinsäuren mit Hydrazin umsetzen.The corresponding alkylthiourea derivatives can also be prepared in an analogous manner convert from aminoarylsulfonic acids and aminoarylarsinic acids with hydrazine.
Statt Hydrazinhydrat bzw. Hydrazin kann auch ein Alkyl- oder Arylhydrazin Verwendung finden.Instead of hydrazine hydrate or hydrazine, an alkyl or aryl hydrazine can also be used Find use.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF6304A DE871756C (en) | 1951-05-27 | 1951-05-27 | Process for the preparation of thiosemicarbazides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF6304A DE871756C (en) | 1951-05-27 | 1951-05-27 | Process for the preparation of thiosemicarbazides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE871756C true DE871756C (en) | 1953-03-26 |
Family
ID=7084947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF6304A Expired DE871756C (en) | 1951-05-27 | 1951-05-27 | Process for the preparation of thiosemicarbazides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE871756C (en) |
-
1951
- 1951-05-27 DE DEF6304A patent/DE871756C/en not_active Expired
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