DE166266C - - Google Patents
Info
- Publication number
- DE166266C DE166266C DENDAT166266D DE166266DA DE166266C DE 166266 C DE166266 C DE 166266C DE NDAT166266 D DENDAT166266 D DE NDAT166266D DE 166266D A DE166266D A DE 166266DA DE 166266 C DE166266 C DE 166266C
- Authority
- DE
- Germany
- Prior art keywords
- acids
- heated
- acid
- dialkylthiobarbituric
- aniline
- 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.)
- Active
Links
- 239000002253 acid Substances 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000002429 hydrazines Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 acids Arylamines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N Thiocarbanilide Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- RYCFRVNAZOREPC-UHFFFAOYSA-N 1,1,2-triphenylguanidine Chemical compound C=1C=CC=CC=1N(C=1C=CC=CC=1)C(N)=NC1=CC=CC=C1 RYCFRVNAZOREPC-UHFFFAOYSA-N 0.000 description 1
- SRVNDMUBUJPHFX-UHFFFAOYSA-N 5,5-dimethyl-2-sulfanylidene-1,3-diazinane-4,6-dione Chemical compound CC1(C)C(=O)NC(=S)NC1=O SRVNDMUBUJPHFX-UHFFFAOYSA-N 0.000 description 1
- FTOAOBMCPZCFFF-UHFFFAOYSA-N Barbital Chemical compound CCC1(CC)C(=O)NC(=O)NC1=O FTOAOBMCPZCFFF-UHFFFAOYSA-N 0.000 description 1
- 229960002319 Barbital Drugs 0.000 description 1
- 229940083094 Guanine derivatives acting on arteriolar smooth muscle Drugs 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N Phenylthiocarbamide Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- QGVNJRROSLYGKF-UHFFFAOYSA-N Thiobarbital Chemical compound CCC1(CC)C(=O)NC(=S)NC1=O QGVNJRROSLYGKF-UHFFFAOYSA-N 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N Thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JDXKTOBMLZLCSB-UHFFFAOYSA-N anilinothiourea Chemical compound NC(=S)NNC1=CC=CC=C1 JDXKTOBMLZLCSB-UHFFFAOYSA-N 0.000 description 1
- 125000004467 aryl imino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083145 peripherally acting antiadrenergic agents Guanine derivatives Drugs 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
- C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Es wurde gefunden, daß Dialkylthiobarbitursäuren beim Erhitzen mit aromatischen Aminen Schwefel gegen den Aminrest austauschen und so Dialkylaryliminobarbitursäuren entstehen. Dieses Verfahren ist von praktischem Wert, da es einen neuen Weg zur Herstellung der Dialkylbarbitursäuren eröffnet; beim Erhitzen mit Säuren gehen nämlich jene Guanidinderivate unter AbspaltungIt has been found that dialkylthiobarbituric acids when heated with aromatic Amines exchange sulfur for the amine residue and thus dialkylaryliminobarbituric acids develop. This process is of practical value as it opens up a new route for the preparation of the dialkylbarbituric acids; when heated with acids, those guanidine derivatives are split off
ίο der entsprechenden aromatischen Amine in Dialkylmalonylharnstoffe über.ίο the corresponding aromatic amines in Dialkylmalonylureas over.
Über die Einwirkung von Arylaminen auf Dialkylthiobarbitursäuren war nichts bekannt, denn eine allgemeine Regel hinsichtlich des Verhaltens des Thioharnstoffe gegenüber organischen Basen ist nicht gegeben.Nothing was known about the action of arylamines on dialkylthiobarbituric acids, because a general rule regarding the behavior of thioureas towards organic ones Bases are not given.
Wohl weiß man, daß Diphenylthioharnstoff mit Anilin erhitzt Triphenylguanidin liefert, aber eine analoge glatte Umsetzung wurde beim Thioharnstoff und Phenylthioharnstoff nicht beobachtet.It is well known that diphenylthiourea heated with aniline yields triphenylguanidine, but an analogous smooth conversion was made with thiourea and phenylthiourea not observed.
Auch Diphenylthioharnstoff verhält sich gegen verschiedene Basen verschieden. Im Gegensatz zu Anilin wirkt Hydrazin auf ihn ein unter Bildung von Phenylthiosemicarbazid (Ber. 33 [1901], S. 1.058). Es wird also in diesem Fai ein phenylierter Ammoniakrest durch die einwirkende Base verdrängt. Vielleicht ist dies durch die geringere Basizität jenes Restes bedingt.Diphenylthiourea also behaves differently towards different bases. in the In contrast to aniline, hydrazine acts on it with the formation of phenylthiosemicarbazide (Ber. 33 [1901], p. 1.058). So it will be in This Fai displaced a phenylated ammonia residue by the acting base. Maybe this is due to the lower basicity of that remainder.
Solche Bedingung konnte möglicherweise auch bei den Dialkylthiobarbitursäuren, um so mehr, als sie ein Säureradikal enthalten, eine Rolle spielen und beim Erhitzen dieser Verbindungen mit Arylaminen zu einer Abspaltung des Malonsäureradikals führen oder.eine Zersetzung des cyklischen Atomkomplexes veranlassen. Im Gegensatz zu den verschiedenartigen, aus der Strukturformel herauszulesenden Möglichkeiten führt aber die Umsetzung der Dialkylthiobarbitursäuren mit Arylaminen mit guter Ausbeute zu den Aryliminoderivaten. Such a condition could possibly also be the case with the dialkylthiobarbituric acids, more so more than they contain an acid radical play a role in heating these compounds lead with arylamines to cleavage of the malonic acid radical or.eine Induce decomposition of the cyclic atomic complex. In contrast to the diverse, However, the possibilities to be read out from the structural formula involve the implementation of the dialkylthiobarbituric acids Arylamines in good yield to the arylimino derivatives.
1. 4 Teile Diäthylthiobarbitursäure und 2 Teile Anilin werden 18 Stunden auf 120 bis 1300 erhitzt, bis die bald eintretende Entwicklung von Schwefelwasserstoff beendet ist. Die erstarrte Reaktionsmasse wird aus kochendem Alkohol kristallisiert, und man erhält die neue Verbindung in weißen Nädelchen, die bei 253 ° schmelzen.1. 4 parts Diäthylthiobarbitursäure and 2 parts of aniline are heated for 18 hours 120 to 130 0, is completed until the evolution of hydrogen sulfide entering soon. The solidified reaction mass is crystallized from boiling alcohol, and the new compound is obtained in white needles that melt at 253 °.
Die Diäthyl-2-phenyliminobarbitursäure ist sehr schwer in Äthylalkohol, schwer in Holzgeist löslich und kristallisiert daraus beim Erkalten in weißen Nädelchen bezw. prismatischen Blättchen, die bei 253° schmelzen; in verdünnter Natronlauge ist sie unlöslich, beim Kochen mit Mineralsäuren liefert sie unter Aspaltung von Anilin Diäthylbarbitursäure. The diethyl-2-phenyliminobarbituric acid is very difficult to dissolve in ethyl alcohol, difficult to dissolve in wood spirit and crystallizes from it in the Cool in white needles or prismatic leaflets melting at 253 °; in It is insoluble in dilute caustic soda; when boiled with mineral acids, it delivers with splitting of aniline diethylbarbituric acid.
2. 3,5 Teile Diäthylthiobarbitursäure und 2 Teile Phenylhydrazin werden 5 bis 6 Stunden auf 120 bis 1300 erhitzt. Nach beendeter Schwefelwasserstoffentwicklung kri-2. 3.5 parts Diäthylthiobarbitursäure and 2 parts of phenylhydrazine are heated for 5 to 6 hours to 120 to 130 0th After the evolution of hydrogen sulfide has ceased,
stallisiert man die Reaktionsmasse aus heißem Alkohol und erhält die neue Verbindung in
schwachgelbstichigen Kriställchen, die gegen 215 ° unter Zersetzung schmelzen.
Die Diäthyl-2-phenylhydrazinobarbitursäure ist schwer löslich in heißem Äthylalkohol
und scheidet sich daraus in gelbstichigen Kriställchen ab, die bei 215 bis 2160 unter
Zersetzung schmelzen. Aus Methylalkohol, in dem sie ebenfalls schwer löslich ist, kristallisiert
sie in Blättchen. In verdünnter Natronlauge ist sie löslich, dabei färbt sich die Flüssigkeit braun und geht durch rotbraun
allmählich in intensives Violett über, nach längerer Zeit bräunt sich die Flüssigkeit
jedoch wieder, indem sie gleichzeitig trübe wird. In verdünnter Salzsäure ist die
Verbindung nicht löslich, beim Kochen mit i Mineralsäuren geht sie in Diäthylbarbitursäure
über. 'If the reaction mass is installed from hot alcohol and the new compound is obtained in pale yellowish crystals which melt towards 215 ° with decomposition.
The diethyl 2-phenylhydrazinobarbitursäure is sparingly soluble in hot ethyl alcohol and separates therefrom in yellowish small crystals from melting at 215-216 0 with decomposition. From methyl alcohol, in which it is also difficult to dissolve, it crystallizes into flakes. It is soluble in dilute sodium hydroxide solution; the liquid turns brown and gradually turns into an intense violet through red-brown, but after a long time the liquid browns again by becoming cloudy at the same time. The compound is not soluble in dilute hydrochloric acid; when boiled with mineral acids it changes into diethylbarbituric acid. '
Ebenso wie Diäthylthiobarbitursäure verhalten sich auch deren Homologe, welche an Stelle von Äthyl andere Alkyle enthalten, beim Erhitzen mit Arylaminen. Beispielsweise wird durch Erhitzen der Dimethylthiobarbitursäure mit Anilin die Dimethyl-2-phenyliminobarbitursäure erhalten, welche aus Alkohol in Nadeln kristallisiert, die bei 251° schmelzen. \Just like diethylthiobarbituric acid, its homologs, which are, also behave Instead of ethyl containing other alkyls, when heated with arylamines. For example By heating the dimethylthiobarbituric acid with aniline, the dimethyl-2-phenyliminobarbituric acid becomes obtained, which crystallizes from alcohol in needles that are at 251 ° melt. \
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE166266C true DE166266C (en) |
Family
ID=431676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT166266D Active DE166266C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE166266C (en) |
-
0
- DE DENDAT166266D patent/DE166266C/de active Active
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