DE289248C - - Google Patents
Info
- Publication number
- DE289248C DE289248C DENDAT289248D DE289248DA DE289248C DE 289248 C DE289248 C DE 289248C DE NDAT289248 D DENDAT289248 D DE NDAT289248D DE 289248D A DE289248D A DE 289248DA DE 289248 C DE289248 C DE 289248C
- Authority
- DE
- Germany
- Prior art keywords
- ether
- methylethylhydantoin
- diethylhydantoin
- melts
- acetone
- 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
- 238000000034 method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229940100198 ALKYLATING AGENTS Drugs 0.000 claims 1
- 239000002168 alkylating agent Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWTZZUPJEUZZLU-UHFFFAOYSA-N 5,5-diethylimidazolidine-2,4-dione Chemical compound CCC1(CC)NC(=O)NC1=O GWTZZUPJEUZZLU-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- TVKULRRHIFBSPZ-UHFFFAOYSA-N 5,5-dipropylimidazolidine-2,4-dione Chemical compound CCCC1(CCC)NC(=O)NC1=O TVKULRRHIFBSPZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- -1 methylethylcyanacetamide Chemical compound 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QKKMHRFBEXWQAK-UHFFFAOYSA-N 1,3,5-triethylimidazolidine-2,4-dione Chemical compound CCC1N(CC)C(=O)N(CC)C1=O QKKMHRFBEXWQAK-UHFFFAOYSA-N 0.000 description 1
- QIWORMKRMYXXJC-UHFFFAOYSA-N 2-cyanobutanamide Chemical compound CCC(C#N)C(N)=O QIWORMKRMYXXJC-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
- CUILPNURFADTPE-UHFFFAOYSA-N Hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N N-Propyl bromide Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 229940023488 Pill Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000435 bromine oxide Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 230000000147 hypnotic Effects 0.000 description 1
- KPJPHPFMCOKUMW-UHFFFAOYSA-N iodomethane Chemical group I[CH2] KPJPHPFMCOKUMW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- JVe 289248 -KLASSE \1p. GRUPPE - JVe 289248 - CLASS \ 1p. GROUP
Dr. ALFRED EINHORN in MÜNCHEN.Dr. ALFRED EINHORN in MUNICH.
Verfahren zur Darstellung von Trialkylhydantoinen.Process for the preparation of trialkylhydantoins.
Patentiert im Deutschen Reiche vom 10. April 1914 ab. Patented in the German Empire on April 10, 1914.
Das Diäthylhydantoin ist trotz seiner nahen Beziehungen in chemischer Hinsicht zu der Diäthylbarbitursäure kein brauchbares Schlafmittel (vgl. Fränkel, Arzneimittel-Synthese, 3. Auflage [1912], S. 484).Diethylhydantoin is, in chemical terms, in spite of its close relationships with the Diethylbarbituric acid not a usable sleeping pill (cf.Frankel, Drug Synthesis, 3rd edition [1912], p. 484).
Es wurde nun gefunden, daß sich γ · y-Dialkylhydantoine (2 · 4-Diketo-5 · 5-dialkyltetrahydroimidazole), wie Diäthylhydantoin und Dipropylhydantoin, durch weitere Alkylierung in Trialkylhydantoine (2,· 4-Diketo-5 · 5 · 3-trialkyltetrahydroimidazole) überführen lassen, welche durch ihre hypnotische Wirkung wertvoll sind.It has now been found that γ · y-dialkylhydantoins (2 · 4-diketo-5 · 5-dialkyltetrahydroimidazoles), such as diethylhydantoin and dipropylhydantoin, are converted into trialkylhydantoins (2, · 4-diketo-5 · 5 · 3- trialkyltetrahydroimidazole), which are valuable due to their hypnotic effect.
Die als Ausgangsstoffe dienenden Verbin- 1S düngen, wie y ■ y-Diäthylhydantoin, y · y-Dipropylhydantoin, y · y-Methyläthylhydantoin, sind bekannt (vgl. Gazz. chim. ital., 26, I [1896], S. 205 bis 207; Chem. Centralbl. 1910, II, S. 553 und 554); sie gehen entsprechend den Formeln:Serving as starting materials connects fertilize 1 S as y ■ y Diäthylhydantoin, y * y-Dipropylhydantoin, y * y-Methyläthylhydantoin, are known (cf.. Gazz. Chim. Ital., 26, I [1896], p 205 to 207; Chem. Centralbl. 1910, II, pp. 553 and 554); they go according to the formulas:
(5) (1) (5) (1)(5) (1) (5) (1)
R2C-NH (2) R2C-NH (2) R 2 C-NH (2) R 2 C-NH (2)
>co> co
CO-CO-
NHNH
(3)(3)
CO-CO-
(4)(4)
(R = Alkyl)(R = alkyl)
NR'NO'
(3)(3)
in die neuen Trialkylhydantoine über.
Beispiele.into the new trialkylhydantoins.
Examples.
i. Man versetzt 6,25 g Diäthylhydantoin mit einer absolut alkoholischen Lösung von 2,24 g Ätzkali, fügt 6 g Bromäthyl hinzu und erhitzt 12 Stunden unter Druck auf ioo°; dann wird der Alkohol abdestilliert und der Rückstand in Äther aufgenommen. Zur Entfernung von unverändertem Diäthylhydantoin schüttelt man die ätherische Lösung mit Natriumcarbonat und trocknet sie dann mit Natriumsulfat. Beim Verdunsten des Äthers hinterbleibt das Triäthylhydantoin zunächst als öl; bei der Destillation im Vakuum siedet es unter 8 bis 9 mm Druck bei 174 bis 180 ° und erstarrt dann zu einer kristallinischen Masse, welche bei 37 bis 38 ° schmilzt und in absolutem Alkohol, Methylalkohol und Äther leicht löslich ist.i. 6.25 g of diethylhydantoin are added an absolutely alcoholic solution of 2.24 g of caustic potash, 6 g of bromoethyl is added and the mixture is heated 12 hours under pressure at 100 °; then the alcohol is distilled off and the residue in Ether added. Shake to remove unchanged diethylhydantoin the essential solution with sodium carbonate and then dry it with sodium sulfate. At the When the ether evaporates, the triethylhydantoin initially remains as an oil; in the distillation in a vacuum it boils under 8 to 9 mm pressure at 174 to 180 ° and then solidifies a crystalline mass which melts at 37 to 38 ° and in absolute alcohol, methyl alcohol and ether is easily soluble.
2. Monoäthylcyanacetamid liefert mit Jodmethyl und metallischem Natrium, in alkoholischer Lösung behandelt, Methyläthylcyanacetamid, welches in weißen Nadeln kristallisiert, bei 87 ° schmilzt und bei der Einwirkung von Brom und Kalilauge in γ · y-Methyläthylhydantoin übergeht, das aus Wasser in langen Nadeln kristallisiert, bei 141 bis 1420 schmilzt und verschieden ist von dem bekannten optisch aktiven d-Methyläthylhydantoin (Chem. Centralbl. 1910, II, S. 554).2. Monoethylcyanacetamid with iodomethyl and metallic sodium, treated in alcoholic solution, gives methylethylcyanacetamide, which crystallizes in white needles, melts at 87 ° and, when exposed to bromine and potassium hydroxide, converts into γ · y-methylethylhydantoin, which crystallizes from water in long needles , melts at 141 to 142 0 and is different from the known optically active d-methylethylhydantoin (Chem. Centralbl. 1910, II, p. 554).
8 g y · y-Methyläthylhydantoin vom F. 141 bis 142 °, 8 g kohlensaures Kali und 11 g Jodäthyl werden mit 50 g Aceton versetzt und 5 Stunden unter Rückfluß gekocht; hierauf filtriert man das Aceton ab, wäscht mit denselben Lösungsmitteln nach und dunstet ein. Der Rückstand wird in Äther aufgenommen, den man mit verdünnter Natronlauge durchschüttelt, um etwa unverändertes y · y-Methyläthylhydantoin zu entfernen. Hierauf trocknet man die Flüssigkeit mit Natriumsulfat und destilliert den Äther wieder ab. Es hinterbleibt dann das y · y-Methyläthyl-s-äthylhydantoin, welches unter 20 mm Druck bei 188° als farbloses öl destilliert und in Wasser löslieh ist.8 g of y-methylethylhydantoin of F. 141 up to 142 °, 8 g of carbonate of potash and 11 g of iodoethyl 50 g of acetone are added and the mixture is refluxed for 5 hours; the acetone is then filtered off and washed with the same Solvents and evaporates. The residue is taken up in ether, which is shaken with dilute sodium hydroxide solution, in order to remove roughly unchanged y · y-methylethylhydantoin. The liquid is then dried with sodium sulfate and distills the ether off again. The y-methylethyl-s-ethylhydantoin then remains, which distilled under 20 mm pressure at 188 ° as a colorless oil and soluble in water is.
3, -Man ,verrührt 11 g Dipropylhydantoin,3, -Man, stirs 11 g of dipropylhydantoin,
9 g kohlensaures Kali und ίο g Propylbromid mit Aceton zu einem Brei, erhitzt einige Stunden unter Rückfluß, extrahiert dann die Reaktionsmasse mit Aceton in der Wärme, destilliert das Lösungsmittel ab und nimmt den Rückstand in Äther auf. Zur Entfernung unveränderten Dipropylhydantoins schüttelt man die Ätherlösung nun mit verdünnter Natronlauge durch und trocknet sie mit entwässertem Natriumsulfat. Beim Verdunsten des Äthers hinterbleibt y-y-E-Tripropylhydantoin, welches unter 13 mm Druck bei 186 bis 188 ° siedet und zu einer kristallinischen Masse erstarrt, welche bei 35 bis 35,5° schmilzt.9 g of carbonate of potash and ίο g of propyl bromide with acetone to a slurry, refluxed for a few hours, then extracted the reaction mass with acetone in the warm, the solvent is distilled off and the residue is taken up in ether. Unchanged for removal Dipropylhydantoins you shake the ethereal solution with dilute caustic soda and dry it with dehydrated Sodium sulfate. When the ether evaporates, y-y-E-tripropylhydantoin remains, which boils under 13 mm pressure at 186 to 188 ° and solidifies to a crystalline mass which melts at 35 to 35.5 °.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE289248C true DE289248C (en) |
Family
ID=544294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT289248D Active DE289248C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE289248C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370058A (en) * | 1993-11-15 | 1994-12-06 | Whiting Equipment Canada Inc. | Low rise drop yoke system |
| WO2005090316A1 (en) * | 2004-03-12 | 2005-09-29 | Wyeth | HYDANTOINS HAVING RNase MODULATORY ACTIVITY |
-
0
- DE DENDAT289248D patent/DE289248C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370058A (en) * | 1993-11-15 | 1994-12-06 | Whiting Equipment Canada Inc. | Low rise drop yoke system |
| WO2005090316A1 (en) * | 2004-03-12 | 2005-09-29 | Wyeth | HYDANTOINS HAVING RNase MODULATORY ACTIVITY |
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