DE245491C - - Google Patents
Info
- Publication number
- DE245491C DE245491C DENDAT245491D DE245491DA DE245491C DE 245491 C DE245491 C DE 245491C DE NDAT245491 D DENDAT245491 D DE NDAT245491D DE 245491D A DE245491D A DE 245491DA DE 245491 C DE245491 C DE 245491C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- chloride
- benzene
- tertiary alcohols
- gasoline
- 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
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 5
- VYWQTJWGWLKBQA-UHFFFAOYSA-M urea;chloride Chemical compound [Cl-].NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-M 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 229940112021 centrally acting muscle relaxants Carbamic acid esters Drugs 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N Tert-Amyl alcohol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DSSYKIVIOFKYAU-UHFFFAOYSA-N Camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 2
- 229960000846 Camphor Drugs 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N Chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229930007890 camphor Natural products 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- -1 esters primary Chemical class 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- FRDAATYAJDYRNW-UHFFFAOYSA-N 3-Methyl-3-pentanol Chemical compound CCC(C)(O)CC FRDAATYAJDYRNW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N carbamoyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000147 hypnotic Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004540 pour-on Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-M urea-1-carboxylate Chemical compound NC(=O)NC([O-])=O AVWRKZWQTYIKIY-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
'■■-Jig 245491'-KLASSE 12 ο. GRUPPE'■■ -Jig 245491'-CLASS 12 ο. GROUP
in FRANKFURT a, M.in FRANKFURT a, M.
Die Herstellung von Estern tertiärer Alkohole bietet im Gegensatz zu der der Ester primärer und sekundärer Alkohole manche Schwierigkeiten. Es war deshalb bisher auch nicht gelungen, die Carbaminsäureester der tertiären Alkohole, also deren Urethane, herzustellen. Es ist nun trotzdem gelungen, diese Urethane zu gewinnen, indem man Harnstoffchlorid auf Metallverbindungen tertiärer Alkohole einwirken läßt. Das Amylenhydraturethan erhält man z. B. in folgender Weise:The production of esters of tertiary alcohols offers in contrast to that of the esters primary and secondary alcohols face some difficulties. So it hasn't been up to now succeeded in producing the carbamic acid esters of the tertiary alcohols, i.e. their urethanes. Nevertheless, it has now been possible to obtain these urethanes by adding urea chloride Metal compounds of tertiary alcohols can act. The amylenehydraturethane is obtained one z. B. in the following way:
88 Teile Amylenhydrat, vermischt mit 600 Teilen Benzol, werden mit 23 Teilen Natrium gekocht, bis fast alles gelöst ist. Man gießt nun klar ab, kühlt gut und setzt unter Rühren langsam 79,5 Teile Harnstoffchlorid zu, die mit 400 Teilen Benzol verdünnt sind. Nach einigem Stehen saugt man vom abgeschiedenen Kochsalz ab und destilliert das Benzol ab. Beim Versetzen des öligen Rückstandes mit Benzin findet Kristallisation statt. Man saugt ab, wäscht mit Benzin und kristallisiert aus verdünntem Alkohol um.88 parts of amylene hydrate mixed with 600 parts of benzene are mixed with 23 parts of sodium cooked until almost everything is resolved. It is now poured clear, cooled well and set while stirring slowly added 79.5 parts of urea chloride diluted with 400 parts of benzene. To After standing for some time, the precipitated table salt is suctioned off and the benzene is distilled away. When gasoline is added to the oily residue, crystallization takes place. Man sucks off, washes with gasoline and recrystallizes from diluted alcohol.
Amylenhydratcarbamat NH2 · CO2-C5 H11 besteht aus feinen farblosen Nadeln, die schwach nach Kampfer riechen und schmecken und bei 83 bis 86° schmelzen. Es ist leicht löslich in den meisten organischen Lösungsmitteln, schwer löslich in Benzin und Wasser. Vor dem Allophanat des Amylenhydrats, das ein fester, geruchloser Körper ist, hat es den Vorzug der wesentlich besseren hypnotischen Wirkung. Ob dies eine Folge leichterer .Zersetzlichkeit oder einer Eigenart der Urethane ist, bleibt dahingestellt.Amylene hydrate carbamate NH 2 · CO 2 -C 5 H 11 consists of fine, colorless needles that smell and taste faintly of camphor and melt at 83 to 86 °. It is easily soluble in most organic solvents, slightly soluble in gasoline and water. Over the allophanate of amylene hydrate, which is a solid, odorless body, it has the advantage of a much better hypnotic effect. It remains to be seen whether this is a result of easier decomposition or a peculiarity of the urethanes.
Zu dem in üblicher Weise aus 24,3 Teilen Magnesium, 200 Teilen Äther und 64,5 Teilen Äthylchlorid dargestellten Grignardschen Reaktionsprodukte fügt man langsam 88 Teile Amylenhydrat hinzu. Wenn die Entwicklung von Äthan vorüber ist, setzt man langsam unter Rühren und guter Kühlung 79,5 Teile Carbaminsäurechlorid, welche mit 200 Teilen Benzol verdünnt sind, zu. Nach einigem Stehen gießt man auf Eis, trennt die ätherische Lösung vom Wasser, wäscht sie mit Wasser, in dem etwas Soda gelöst ist, und trocknet mit Chlorcalcium. Sodann destilliert man Äther und Benzol ab und kristallisiert den Rückstand aus Benzin um.The usual way of 24.3 parts of magnesium, 200 parts of ether and 64.5 parts Grignard reaction products represented by ethyl chloride are slowly added to 88 parts Amylene hydrate added. When the development of Ethan is over, you slowly sit down with stirring and good cooling 79.5 parts of carbamic acid chloride, which with 200 parts Benzene are diluted, too. After standing for a while, pour on ice, separate the essential Solution of the water, wash it with water in which some soda is dissolved and dry with calcium chloride. Then distilled ether and benzene are removed and the residue is recrystallized from gasoline.
55 Beispiel III.55 Example III.
Aus 24,3 Teilen Magnesium, 250 Teilen wasserfreiem Äther und 64,5 Teilen Äthylchlorid wird in üblicher Weise die Grignardsche Verbindung dargestellt. Zu dieser fügt man 72 Teile (1 Mol.) Äthylmethylketon hinzu und läßt, wenn die Reaktion beendigt ist, unter Kühlung langsam 79,5 Teile Harnstoffchlorid .(1M0I.) zufließen. Das MagnesiumFrom 24.3 parts of magnesium, 250 parts of anhydrous ether and 64.5 parts of ethyl chloride the Grignard connection is represented in the usual way. To this adds 72 parts (1 mol.) of ethyl methyl ketone are added and, when the reaction is complete, 79.5 parts of urea chloride (1M0I) slowly flow in with cooling. The magnesium
zieht man aus dem Reaktionsprqdukt mit verdünnter Salzsäure aus, trocknet die ätherische Lösung mit Chlorcalcium, verjagt den Äther und destilliert den Rückstand im Vakuum. Man erhält so das Urethan des Diäthylmethylcarbinols in farlosen Nadeln von kampherähnlichem Geruch.If the reaction product is extracted with dilute hydrochloric acid, the ethereal one is dried Solution with calcium chloride, drives away the ether and distills the residue in vacuo. The urethane of diethylmethylcarbinol is thus obtained in colorless needles similar to camphor Odor.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE245491C true DE245491C (en) |
Family
ID=504446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT245491D Active DE245491C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE245491C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE959458C (en) * | 1954-07-13 | 1957-03-07 | Rheinpreussen Ag | Process for the preparation of allophanates of ª ‡ -Aethynyl carbinols |
| DE1021843B (en) * | 1953-09-14 | 1958-01-02 | Rheinpreussen Ag | Process for the preparation of the allophanate of 1-AEthynylcyclohexanols- (1) |
| US6664113B2 (en) | 2001-04-23 | 2003-12-16 | Tosoh Corporation | Fluorescence detection method capable of making measurement under external light |
-
0
- DE DENDAT245491D patent/DE245491C/de active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1021843B (en) * | 1953-09-14 | 1958-01-02 | Rheinpreussen Ag | Process for the preparation of the allophanate of 1-AEthynylcyclohexanols- (1) |
| DE959458C (en) * | 1954-07-13 | 1957-03-07 | Rheinpreussen Ag | Process for the preparation of allophanates of ª ‡ -Aethynyl carbinols |
| US6664113B2 (en) | 2001-04-23 | 2003-12-16 | Tosoh Corporation | Fluorescence detection method capable of making measurement under external light |
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