DE158592C - - Google Patents
Info
- Publication number
- DE158592C DE158592C DE1903158592D DE158592DA DE158592C DE 158592 C DE158592 C DE 158592C DE 1903158592 D DE1903158592 D DE 1903158592D DE 158592D A DE158592D A DE 158592DA DE 158592 C DE158592 C DE 158592C
- Authority
- DE
- Germany
- Prior art keywords
- solution
- guanidine
- parts
- water
- alcohol
- 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 - Lifetime
Links
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 230000001476 alcoholic Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XNINAOUGJUYOQX-UHFFFAOYSA-M 2-cyanobutanoate Chemical compound CCC(C#N)C([O-])=O XNINAOUGJUYOQX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IGRWHBBHXVNZEO-UHFFFAOYSA-N guanidine;hypochlorous acid Chemical compound ClO.NC(N)=N IGRWHBBHXVNZEO-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing Effects 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003230 pyrimidines Chemical class 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N Potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 acids salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- FYGRPGOHQCPZCV-UHFFFAOYSA-N ethyl 2-cyano-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)C#N FYGRPGOHQCPZCV-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts 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
- C07D239/48—Two nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KLASSEGREAT
Es wurde gefunden, daß durch EinwirkungIt has been found that by action
von dialkylierten Cyanessigestern auf Guanidin in Gegenwart von Alkalialkoholaten in glatter Weise die bisher unbekannten dialkylierten Diiminooxypyrimidine der Formel:of dialkylated cyanoacetic esters on guanidine in the presence of alkali alcoholates in smooth Way the previously unknown dialkylated diiminooxypyrimidines of the formula:
HN = CHN = C
NH- CONH- CO
,R, R
NH- NH- C=NHC = NH
(worin R Alkylradikale bedeutet) entstehen. Die neuen alkylierten Pyrimidinderivate zeichnen sich durch die überraschende und technisch wichtige Eigenschaft aus, daß sie beim Behandeln mit verseifenden Mitteln glatt beide Iminogruppen gegen Sauerstoff austauschen, wobei die bekannten wertvollen dialkylierten Barbitursäuren entstehen.(where R denotes alkyl radicals) arise. The new alkylated pyrimidine derivatives are distinguished by the surprising and technically important property that, when treated with saponifying agents, they smoothly exchange both imino groups for oxygen, the known valuable dialkylated barbituric acids being formed.
Von dem durch Patent 134984 geschützten Verfahren zur Darstellung nicht alkylierter Pyrimidinderivate unterscheidet sich das vorliegende Verfahren wesentlich dadurch, daß hier keine Metallverbindungen von Cyanessigestern, sondern freie Cyanessigester zur Anwendung gelangen.From the process protected by patent 134984 for the preparation of non-alkylated Pyrimidine derivatives, the present process differs significantly in that here no metal compounds of cyanoacetic esters, but free cyanoacetic esters for use reach.
Zu einer Lösung von 4,6 Teilen Natrium in 50 Teilen Alkohol wird eine alkoholische Lösung von 10 Teilen Guanidinchlorhydrat zugegeben. Die Hälfte des Natriums wird zum Freimachen des Guanidine verwendet.To a solution of 4.6 parts of sodium in 50 parts of alcohol is an alcoholic Solution of 10 parts of guanidine chlorohydrate were added. Half of the sodium will be used to clear the guanidine.
Nach dem Abfiltrieren des sich hierbei ausscheidenden Chlornatriums versetzt man die alkoholische Lösung von freiem Guanidin und Natriumäthylat mit 17 Teilen Diäthylcyanessigsäureäthylester und erhitzt das so erhaltene Gemisch 6 Stunden im siedenden Wasserbade. Nach dem Abdestillieren des Alkohols wird der sirupartige Rückstand in Wasser gelöst und aus der so erhaltenen Lösung das neue Produkt durch Neutralisieren mit Salzsäure abgeschieden.After the sodium chloride which separates out in the process has been filtered off, it is added the alcoholic solution of free guanidine and sodium ethylate with 17 parts of ethyl cyanoacetate and heated the resulting mixture for 6 hours in a boiling water bath. After the alcohol has been distilled off the syrupy residue is dissolved in water and the new solution is obtained from this Product deposited by neutralizing with hydrochloric acid.
Das 5-Diäthyl-2 · 4-diimino-6-oxypyrimidin schmilzt bei 2950. Es ist in kaltem Wasser, Ammoniak, verdünnter Sodalösung und den gebräuchlichen organischen Lösungsmitteln schwer löslich, leichter löslich in siedendem Wasser und verdünnter Natronlauge. Mit starken Säuren bildet es gut kristallisierende Salze.The 5-diethyl-2 · 4-diimino-6-oxypyrimidine melts at 295 0th It is sparingly soluble in cold water, ammonia, dilute soda solution and the common organic solvents, more easily soluble in boiling water and dilute sodium hydroxide solution. With strong acids it forms well crystallizing salts.
Zu einer Lösung von 8 Teilen Kalium in 120 Teilen Alkohol wird eine alkoholische Lösung von 10 Teilen Guanidinchlorhydrat gegeben. Nachdem von ausgeschiedenem Kaliumchlorid abfiltriert wurde, versetzt man die so erhaltene Lösung von Guanidin und Kaliumäthylat mit 15 Teilen Dimethylcyanessigsäureäthylester und erhitzt 3 Stunden auf dem Wasserbade. Zur Abscheidung des Kondensationsproduktes wird nach dem Abdestillieren des Alkohols der Rückstand mit Wasser aufgenommen, die so erhaltene Lösung darauf mit verdünnter Säure neutralisiert und das ausgefällte Produkt zur Reinigung in Säure gelöst und durch Neutralisieren mit Alkali wieder abgeschieden.A solution of 8 parts of potassium in 120 parts of alcohol becomes an alcoholic one Given a solution of 10 parts of guanidine chlorohydrate. After excreted Potassium chloride was filtered off, the resulting solution of guanidine and Potassium ethylate with 15 parts of ethyl dimethylcyanoacetate and heated for 3 hours on the water bath. After distilling off, the condensation product is separated out of the alcohol, the residue was taken up in water, and the solution thus obtained was then neutralized with dilute acid and the precipitated product dissolved in acid for purification and neutralized with Alkali deposited again.
Das 5"Dimethyl-2 ^-diimino-o-oxypyrimidin ist leicht löslich in verdünnten Alkalien, sehrThe 5 "dimethyl-2 ^ -diimino-o-oxypyrimidine is easily soluble in dilute alkalis, very
schwer löslich in Wasser und fast unlöslich in Alkohol und Äther. Mit Säuren bildet es gut kristallisierende Salze.sparingly soluble in water and almost insoluble in alcohol and ether. Forms with acids salts that crystallize well.
Zu einer Mischung von 170 g Diäthyl-To a mixture of 170 g of diethyl
cyanessigsäureäthylester und 60 g Guanidin werden 86 g trockenes Natriumäthylat zuge-ethyl cyanoacetate and 60 g of guanidine are added to 86 g of dry sodium ethylate.
■ fügt und das so erhaltene Gemisch 3 Stunden■ adds and the resulting mixture for 3 hours
lang im Ölbade auf iio° erhitzt. Nach dem Erkalten löst man das Reaktionsgemisch in Wasser auf und fällt aus der so erhaltenen Lösung das 5-Diäthyl-2 · 4-diimino-6-oxypyrimidin durch Neutralisieren mit. verdünnter Säure aus.heated to 10 ° in an oil bath for a long time. After this When cooling, the reaction mixture is dissolved in water and precipitated from the resultant Dissolve the 5-diethyl-2 · 4-diimino-6-oxypyrimidine by neutralizing with. thinner Acid off.
In analoger Weise verfährt man bei Verwendung anderer dialkylierter Cyanessigester..The procedure is analogous when using other dialkylated cyanoacetic esters.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT21547D AT21547B (en) | 1903-09-25 | 1904-04-21 | Method for the preparation of C -C dialkyl-2,4-diimino-6-oxypyrimidine. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE158592C true DE158592C (en) |
Family
ID=424758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1903158592D Expired - Lifetime DE158592C (en) | 1903-09-25 | 1903-09-25 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE158592C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1147950B (en) * | 1959-12-21 | 1963-05-02 | Ici Ltd | Process for the preparation of hexahydropyrimidine-4, 6-dione derivatives |
-
1903
- 1903-09-25 DE DE1903158592D patent/DE158592C/de not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1147950B (en) * | 1959-12-21 | 1963-05-02 | Ici Ltd | Process for the preparation of hexahydropyrimidine-4, 6-dione derivatives |
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