DE266520C - - Google Patents
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- Publication number
- DE266520C DE266520C DENDAT266520D DE266520DA DE266520C DE 266520 C DE266520 C DE 266520C DE NDAT266520 D DENDAT266520 D DE NDAT266520D DE 266520D A DE266520D A DE 266520DA DE 266520 C DE266520 C DE 266520C
- Authority
- DE
- Germany
- Prior art keywords
- sodium
- methylcyclohexanone
- oxalester
- ester
- oxalate
- 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
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- 150000002576 ketones Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- -1 m - methylcyclohexanone oxalate Chemical compound 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- USMNOWBWPHYOEA-XKSSXDPKSA-N Isothujone Natural products O=C([C@H]1C)C[C@@]2(C(C)C)[C@@H]1C2 USMNOWBWPHYOEA-XKSSXDPKSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000001264 neutralization Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003388 sodium compounds Chemical class 0.000 description 4
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 3
- KPJPHPFMCOKUMW-UHFFFAOYSA-N iodomethane Chemical group I[CH2] KPJPHPFMCOKUMW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N Methyl iodide Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KNSPBSQWRKKAPI-UHFFFAOYSA-N 2,2-dimethylcyclohexan-1-one Chemical compound CC1(C)CCCCC1=O KNSPBSQWRKKAPI-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Hexanone Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N Ethyl iodide Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- IDVPSOYNHUMTLJ-UHFFFAOYSA-N oxalic acid;propan-2-one Chemical compound CC(C)=O.OC(=O)C(O)=O IDVPSOYNHUMTLJ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
-M 266520-KLASSE 12 o. GRUPPE -M 266520-CLASS 12 or GROUP
Dr. KARL BLENDERMANN in BREMEN.Dr. KARL BLENDERMANN in BREMEN.
Verfahren zur Darstellung von alkylierten Ketonen.Process for the preparation of alkylated ketones.
Patentiert im Deutschen Reiche vom 25. April 1912 ab.Patented in the German Empire on April 25, 1912.
Die bekannte Darstellung von alkylierten Ketonen über die Oxalesterkondensationsprodukte beruht auf folgenden Reaktionen:The well-known representation of alkylated ketones via the oxalester condensation products is based on the following reactions:
ι. ι Mol. Keton reagiert mit ι Mol. Oxalester bei Anwesenheit von Natriumäthylat unter Austritt eines Moleküls Alkohol wie folgt: 40ι. ι Mol. Ketone reacts with ι Mol. Oxalester in the presence of sodium ethylate A molecule of alcohol escapes as follows: 40
-CH-CO- -CH2-CO- + C2H5OOC -COOC2H5 = C2H5OH -f -CH-CO- -CH 2 -CO- + C 2 H 5 OOC -COOC 2 H 5 = C 2 H 5 OH -f
CO-CO2C2H6. 2. Abspaltung von CO wie folgt: CO-CO 2 C 2 H 6 . 2. Separation of CO as follows:
45 -CH-CO- -CH-CO- 45 -CH-CO- -CH-CO-
= CO -f · CO-CO2C2H5 CO2C2H5. = CO- f • CO-CO 2 C 2 H 5 CO 2 C 2 H 5 .
3. Substitution des beweglichen ff-Atomes durch Na mittels Natriumalkoholat, ferner 50 Ersatz des 2V«-Atomes durch Halogenalkyl wie folgt:3. Substitution of the mobile ff atom by Na using sodium alcoholate, furthermore replacement of the 2V «atom by haloalkyl as follows:
-CNa-CO- .CR-CO--CNa-CO- .CR-CO-
+ Hal. R= - +Na Hal.+ Hal. R = - + Na Hal.
CO2C2H5 CO 2 C 2 H 5
CO2C2H5 CO 2 C 2 H 5
4· Verseifung der Estergruppe unter gleichzeitiger Kohlendioxydabspaltung:4 Saponification of the ester group with simultaneous elimination of carbon dioxide:
-CR-CO--CR-CO-
+ H2O =·. . C HR - CO · + C2H5O H + CO2. + H 2 O = ·. . C HR - CO + C 2 H 5 OH + CO 2 .
CO2C2H5 CO 2 C 2 H 5
Praktisch ausgeführt verlief der Vorgang z. B. bei der Darstellung des ρ - Dimethylcyclohexanon aus dem m-Methylcyclohexanon folgendermaßen:In practice, the process went z. B. in the representation of ρ - dimethylcyclohexanone from m-methylcyclohexanone as follows:
Molekulare Mengen des m-Methylcyclohexanon wurden mit molekularen Mengen Oxalester
zusammengebracht und mit Hilfe berechneter Mengen 20 prozentiger Lösung von Natrium
und Alkohol zu dem Natriumsalz des
m - Methylcyclohexanonoxalesters kondensiert.
Diese NatriumverbindungMolecular amounts of m-methylcyclohexanone were brought together with molecular amounts of oxalic ester and with the help of calculated amounts of 20 percent solution of sodium and alcohol to the sodium salt of
m - methylcyclohexanone oxalate condensed.
This sodium compound
CH2 CO CH 2 CO
CH11-CHCH 11 -CH
CH9 CH 9 CH,CH,
wurde durch verdünnte Schwefelsäure in den Methylhexanonoxalesterwas converted into the methylhexanone oxalate by dilute sulfuric acid
CH9 CH 9
C ^2C ^ 2
COCO
"2"2
-CO9C9H-CO 9 C 9 H
umgewandelt. Durch Destillation erhielt man unter CO-Austritt den Methylcyclohexanoncarbonester: converted. The methylcyclohexanone carbon ester was obtained by distillation with the escape of CO:
CH0 CH 0
COCO
CH3-CHCH 3 -CH
, C O9 C9 He., CO 9 C 9 He.
CH2 CH 2
CH2.CH 2 .
Dieser Carbonester wurde wieder mit der molekularen Menge 20 prozentiger Natriumalkoholatlösung versetzt und der so entstandenen Natriumverbindung des CarbonestersThis carbon ester was again with the molecular amount of 20 percent sodium alcoholate solution added and the resulting sodium compound of the carbon ester
CJi,CJi,
COCO
CH.-CHCH.-CH
CO9C9HCO 9 C 9 H
CH9 CH 9
CH9 CH 9
Jodmethyl hinzugefügt. Man erhielt nun den Dimethylcyclohexanoncarbonester,Iodomethyl added. The dimethylcyclohexanone carbon ester was now obtained,
/CO2C2 H5 / CO 2 C 2 H 5
XX
CH,CH,
CH3-CH CH,CH 3 -CH CH,
der mittels Natronlauge zum ρ - Dimethylcyclohexanon verseift wurde,which was saponified to ρ - dimethylcyclohexanone using sodium hydroxide solution,
CJi,CJi,
CH3-CHCH 3 -CH
CH9.CH 9 .
COCO
CH-CH^CH-CH ^
CH2.CH 2 .
Es wurde gefunden, daß man dieses Verfahren wesentlich vereinfachen kann.It has been found that this process can be simplified considerably.
In ein Gemisch molekularer Mengen eines Ketons wird unter starker Abkühlung die molekulare Menge 20 prozentiger Lösung von Natrium mit Alkohol eingetragen. Die sich bildende Natrium verbindung des Oxalesters des betreffenden Ketons wird mit Halogenalkyl in geringem Überschuß versetzt und bis zur neutralen Reaktion auf dem Wasserbade am Rückflußkühler erhitzt. Darauf wird der Oxalester mit verdünnter Natronlauge auf dem Wasserbade verseift und das substituierte Keton mit Wasserdampf übergeblasen.In a mixture of molecular amounts of a ketone, the molecular amount of 20 percent solution of sodium with alcohol entered. Which Forming sodium compound of the oxalate of the ketone in question is with haloalkyl added in a slight excess and put on the water bath until a neutral reaction heated on the reflux condenser. The oxalester is then applied with dilute sodium hydroxide solution saponified the water bath and blown over the substituted ketone with steam.
ι kg m-Methylcyclohexanon wird mit 1,25 kg Oxalester gemischt. Zu dem stark gekühlten Gemisch läßt man eine kalte Lösung von 200 g Natrium in 4000 ecm abs. Alkohol zufließen. Es bildet sich die Verbindungι kg of m-methylcyclohexanone is 1.25 kg Oxalester mixed. A cold solution of 200 g sodium in 4000 ecm abs. Alcohol flow. The connection is formed
CH9 CH 9
CH3-CHCH 3 -CH
C H9 CH 9
COCO
C<
CH2. C <
CH 2 .
OC-CO9C9H.OC-CO 9 C 9 H.
Diese Natriumverbindung versetzt man mit !30O S Jodmethyl und erhitzt am Rückflußkühler einige Stunden bis zur neutralen Reaktion. Es entsteht:This sodium compound is mixed with! 3 0 O S methyl iodide and heated at reflux for several hours until a neutral reaction. The result is:
CH9 CH 9
CH,CH,
3'3 '
CH9 CH 9
COCO
CH9.CH 9 .
,OCCO2C2H5 CH„, OCCO 2 C 2 H 5 CH "
Nach Verseifen des Oxalesters mit verdünnter Natronlauge erhält man das Dimethylcyclohexanon in größerer Ausbeute wie bei den bisher bekannten umständlichen Methoden. In analoger Weise lassen sich Äthyljodid, Benzylchlorid und andere Halogenkohlenwasserstoffe in Ketone einführen.After saponifying the oxalate with dilute sodium hydroxide solution, dimethylcyclohexanone is obtained in greater yield than with the previously known cumbersome methods. Ethyl iodide, Introduce benzyl chloride and other halogenated hydrocarbons into ketones.
Das vorliegende Verfahren stellt gegenüber der bisher bekannten Methode einen bedeutenden Fortschritt dar, welcher es für die Technik ungemein geeignet macht, da die gesamten unter 1 bis 4 oben beschriebenen Reaktionen in einem Gefäß ohne Isolierung der Zwischenprodukte vorgenommen werden.The present process is an important one compared to the previously known method Progress, which makes it immensely suitable for technology as the whole under 1 to 4 reactions described above in a vessel without isolation of the Intermediate products are made.
Methyläthylketon aus Aceton. Ein Gemisch molekularer Mengen Aceton und Oxalester wird stark abgekühlt, und zu dieser Mischung wird ebenfalls stark abgekühltes 20 prozentiges Natriumäthylat in berechneter Menge hinzugegeben. Es fällt das Natriumsalz des Acetonoxalesters CH3 - CO - CHNa - CO - CO2C2H5 aus. Das abfiltrierte und getrocknete Natriumsalz wird mit einem geringen Überschuß von Methyljodid bis zur neutralen Reaktion auf dem Wasserbade erhitzt. Der Oxalesterrest wird mit Alkali abgespalten und das gewonnene Methyläthylketon vom Sdp. 81 ° abdestilliert. Methyl ethyl ketone from acetone. A mixture of molecular amounts of acetone and oxalate is strongly cooled, and to this mixture, likewise strongly cooled 20 percent sodium ethylate is added in a calculated amount. The sodium salt of the acetone oxalate CH 3 - CO - CHNa - CO - CO 2 C 2 H 5 precipitates. The filtered and dried sodium salt is heated with a small excess of methyl iodide until a neutral reaction on the water bath. The oxal ester residue is split off with alkali and the methyl ethyl ketone obtained, boiling point 81 °, is distilled off.
Beispiel 3. ■Example 3. ■
Methylisothujon aus Isothujon. C H3 C H3 Methyl isothujone from isothujone. CH 3 CH 3
CH3-CCH 3 -C
CO -CH -CH-CO -CH -CH- CH3-CCH 3 -C
\ C H / \ CH /
C3H7 C 3 H 7
Molekulare Mengen von Isothujon und Oxalester werden mit der berechneten Menge ■co Molecular amounts of isothujone and oxal ester are calculated with the calculated amount ■ co
■ C H2 ■ CH 2
C3 H7. C 3 H 7 .
mit einem geringen Überschuß von Jodmethyl Rückflußkühler auf dem Wasserbade biswith a small excess of iodomethyl reflux condenser on the water bath up to
20 prozentigen Natriumalkohölats eine Stunde j zur neutralen Reaktion erhitzt. Der ent20 percent sodium alcoholate heated for one hour to a neutral reaction. The ent
lang am Rückflußkühler auf dem Wasserbade erhitzt. Darauf wird die Hauptmenge des Alkohols abdestilliert und das Reaktionsgemisch standene Methylisothujonoxalester wird mit Alkali verseift. Es entsteht dabei Methylisothujon. long heated on the reflux condenser on the water bath. The bulk of the Alcohol is distilled off and the reaction mixture stood Methylisothujonoxalester with Saponified alkali. This produces methyl isothujone.
Beispiel 4.
i^-Dimethylcyclohexanon^ · aus o-Methylcyclohexanon.Example 4.
i ^ -Dimethylcyclohexanone ^ · from o-methylcyclohexanone.
C H9 CH 9 CH2 CH 2
CH-CH^CH-CH ^
CHCH
CH,CH,
Zu einer stark gekühlten Mischung molekularer Mengen von o-Methylcyclohexanon und oxalsaurem Äthyl läßt man eine ebenfalls unter o° abgekühlte berechnete Menge 2oprozentigen Natriummethylats hinzufließen. Von diesem Reaktionsgemisch wird die Hauptmenge des Methylalkohols abdestilliert und der Rückstand mit einem Überschuß von Jodmethyl bis zur neutralen Reaktion am Rückflußkühler erhitzt. Bei der Verseifung erhält man das 1,3 - Dimethylcyclo-To a strongly cooled mixture of molecular amounts of o-methylcyclohexanone and Ethyl oxalic acid is allowed to give a calculated amount of 2%, also cooled to below 0 ° Add sodium methylate. Most of the methyl alcohol is distilled off from this reaction mixture and the residue is heated with an excess of iodomethyl until a neutral reaction on the reflux condenser. At the saponification the 1,3 - dimethylcyclo-
CH9 CH 9
hexanon - 2, das mit Wasserdämpfen flüchtig ist.hexanone - 2, which is volatile with water vapors.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE266520C true DE266520C (en) |
Family
ID=523652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT266520D Active DE266520C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE266520C (en) |
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