DE289800C - - Google Patents
Info
- Publication number
- DE289800C DE289800C DENDAT289800D DE289800DA DE289800C DE 289800 C DE289800 C DE 289800C DE NDAT289800 D DENDAT289800 D DE NDAT289800D DE 289800D A DE289800D A DE 289800DA DE 289800 C DE289800 C DE 289800C
- Authority
- DE
- Germany
- Prior art keywords
- acetylene
- parts
- hydrocarbons
- alkali
- colorless
- 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
Links
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- ODZPKZBBUMBTMG-UHFFFAOYSA-N Sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 5
- BGTOWKSIORTVQH-UHFFFAOYSA-N Cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N Propargyl alcohol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- MCDBPYGPPCWBMI-UHFFFAOYSA-N CC(=O)CC.[Na] Chemical compound CC(=O)CC.[Na] MCDBPYGPPCWBMI-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-M Sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N 3-Pentanone Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- GOSMJZCNDBTAED-UHFFFAOYSA-N [Na].C1CCCC1 Chemical compound [Na].C1CCCC1 GOSMJZCNDBTAED-UHFFFAOYSA-N 0.000 description 1
- -1 acetylene alcohol Chemical compound 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- PRZPVJOTGOLXRT-UHFFFAOYSA-N cyclohexanone;sodium Chemical compound [Na].O=C1CCCCC1 PRZPVJOTGOLXRT-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- KUSDZIGWHCGGQJ-UHFFFAOYSA-N pentan-3-one;sodium Chemical compound [Na].CCC(=O)CC KUSDZIGWHCGGQJ-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 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
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Description
KAISERLICHES Λ IMPERIAL Λ
PATENTSCHRIFTPATENT LETTERING
~ M 289800 KLASSE 12 o. GRUPPE ~ M 289800 CLASS 12 or GROUP
FARBENFABRIKEN vorm. FRIEDR. BAYER .& CO. in LEVERKUSEN b. CÖLN a. Rh.FARBENFABRIKEN vorm. FRIEDR. BAYER. & CO. in LEVERKUSEN b. CÖLN a. Rh.
Verfahren zur Darstellung der Oxyalkylderivate von Kohlenwasserstoffen.Process for the preparation of the oxyalkyl derivatives of hydrocarbons.
Zusatz zum Patent 280226*).Addition to patent 280226 *).
Patentiert im Deutschen Reiche vom 30. November 1913 ab. Längste Dauer: 8. September 1928.Patented in the German Empire on November 30, 1913. Longest duration: September 8, 1928.
Durch das Hauptpatent 280226 und seine beiden Zusätze 284764 und 286920 ist ein Verfahren zur Einführung der Oxyisopropylgruppe in organische Verbindungen geschützt. Es wurde nun gefunden, daß ebenso wie 30 Acetonalkali auch die Alkaliverbindungen der Homologen des Acetons, wie Methyläthylketonnatrium Through the main patent 280226 and its two additions 284764 and 286920 is a Process for introducing the oxyisopropyl group into organic compounds. It has now been found that just like acetone alkali, the alkali compounds of Homologues of acetone, such as sodium methylethylketone
CH,CH,
CH3-CH = CCH 3 -CH = C
die Alkaliverbindungen hydroaromatischer oder anderer cyklischer Ketone, die die Atomgrup-the alkali compounds of hydroaromatic or other cyclic ketones that form the atomic group
CH3 CH 3
O Na,Oh well
pierung — C H2 — CO-— enthalten, sich mit 40 Kohlenwasserstoffen vereinigen lassen, z. B.pation - CH 2 - CO- contain, can be combined with 40 hydrocarbons, z. B.
CH,CH,
CH,- CH = C + CH = CH=: CH3-CH2-C-C=CH.CH, - CH = C + CH = CH =: CH 3 -CH 2 -CC = CH.
I
• .,, ' O — NaI.
•. ,, 'O - Well
An Stelle der Alkaliketone kann man auch die Ketone in Gegenwart von Alkalimetall oder Alkaliamiden anwenden.Instead of the alkali ketones, one can also use the ketones in the presence of alkali metal or use alkali amides.
OHOH
Kondensation von Methyläthylketonnatrium mit Acetylen zu 3-MethylpentinolCondensation of sodium methylethylketone with acetylene to give 3-methylpentinol
CH3 CH 3
CH3-CH2-C-C:CH 3 -CH 2 -CC:
I-OH I-OH
CH.CH.
40 Teile fein geriebenes Natriumamid werden etwa mit 500 Teilen absolutem Äther übergössen. In die auf — 20 ° abgekühlte Mischung tropft man unter Rühren 72 Teile trockenesApproximately 500 parts of absolute ether are poured over 40 parts of finely ground sodium amide. 72 parts of dry material are added dropwise with stirring into the mixture, which has been cooled to -20 °
*) Frühere Zusatzpatente 284764 und 286920.*) Former additional patents 284764 and 286920.
Methyläthylketon, wobei das Natriumamid allmählich in Lösung geht und leitet alsdann durch die Lösung, indem man ihre Temperatur dauernd auf —20 bis —15 ° hält, einen langsamen Strom gereinigten und getrockneten Acetylens. Nach etwa 10 stündiger Einwirkung wird die Lösung unter starkem Rühren in überschüssige, mit Eis gekühlte verdünnte Essigsäure gegossen, die ätherische Schicht abgehoben und die wässerige Lösung wiederholt mit Äther ausgeschüttelt. Die vereinigten ätherischen, mit Pottaschelösung entsäuerten und über Kaliumkarbonat getrockneten Lösungen hinterlassen nach dem Abdestillieren des Äthers an der Kolonne das 3-MethyI-pentinol als nahezu farbloses Öl, das durch ein- bzw. zweimalige Destillation gereinigt wird. 3 -Methylpentinol ist ein farbloses, leicht bewegliches wasserlösliches öl von eigentürrilichem Geruch, das bei 120 bis 121° siedet. Es bildet ein farbloses explosibles Silbersalz und ein gelbes Kupferoxydulsalz.Methyl ethyl ketone, the sodium amide gradually going into solution and then conducting through the solution, by keeping its temperature permanently at -20 to -15 °, a slow one Stream of purified and dried acetylene. After about 10 hours of exposure the solution is diluted with vigorous stirring in excess, cooled with ice Poured acetic acid, lifted the ethereal layer and repeated the aqueous solution shaken out with ether. The combined essential, deacidified with potash solution and solutions dried over potassium carbonate leave behind after distillation of the ether on the column, the 3-MethyI-pentinol as an almost colorless oil, which by is purified once or twice distillation. 3 -Methylpentinol is a colorless, light Mobile, water-soluble oil with a peculiar odor, boiling at 120 to 121 °. It forms a colorless explosive silver salt and a yellow copper oxide salt.
Kondensation von Diäthylketonnatrium mit Acetylen zu 3-ÄthylpentinolCondensation of diethyl ketone sodium with acetylene to form 3-ethylpentinol
C H„ — C H,C H "- C H,
I CH3-CH2-C C = CH.I CH 3 -CH 2 -C C = CH.
OHOH
40 Teile fein geriebenes Natriumamid werden mit etwa 500 Teilen absolutem Äther Übergossen und das Gemisch unter Abkühlen unter o° mit reinem trockenen Acetylen gesättigt. Unter fortgesetztem Einleiten von Acetylen läßt man langsam 86 Teile trockenes Diäthylketon zutropfen und verarbeitet darauf die Lösung genau so weiter, wie es im Beispiel 1 beschrieben ist.About 500 parts of absolute ether are poured over 40 parts of finely ground sodium amide and the mixture is saturated with pure dry acetylene while cooling below 0 °. With continued introduction of acetylene, 86 parts of dry diethyl ketone are slowly added dropwise and then processed continue the solution exactly as described in example 1.
3-Äthylpentinol ist ein farbloses, leicht bewegliches öl, das sich etwas schwieriger in Wasser löst als das in Beispiel 1 beschriebene3-Ethylpentinol is a colorless, easily mobile oil that is a little more difficult to get into Water dissolves than that described in Example 1
C H, — C H, ' C — O NaCH, - CH, ' C - O Na
• C H2 — C H• CH 2 - CH
mit Acetylen zu dem Acetylencarbinolwith acetylene to the acetylene carbinol
C H2 — C H2v CH 2 - CH 2v
ι )ccι) cc
CH2-CH2 ICH 2 -CH 2 I.
OH = CH.OH = CH.
nächst niedere homologe Carbinol. Es siedet bei 135 bis 137 ° und bildet ein farbloses Silber- und ein gelbgefärbtes Kupferoxydulsalz. next lower homologous carbinol. It boils at 135 to 137 ° and forms a colorless one Silver and a yellow colored copper oxide salt.
Die gleiche Verbindung läßt sich auch erhalten, indem man statt des Natriumämids 23 Teile Natrium oder 40 Teile Kalium in Drahtform oder in Scheiben geschnitten verwendet und im übrigen so verfährt, wie oben angegeben. Beispiel 3.The same compound can also be obtained by using instead of sodium amide 23 parts sodium or 40 parts potassium used in wire form or sliced and otherwise proceed as indicated above. Example 3.
Kondensation von CyklopentannatriumCondensation of Cyclopentane Sodium
40 Teile fein zerriebenes Natriumamid werden mit 1000 Teilen absolutem Äther übergössen und das Gemisch unter o° mit trockenem Acetylen gesättigt. Unter fortgesetztem Einleiten von Acetylen werden langsam 84 Teile Cyklopentanon hinzugetropft und die dünnbreiige Reaktionsflüssigkeit alsdann so, wie im Beispiel 1 beschrieben, weiter verarbeitet.40 parts of finely ground sodium amide are poured over with 1000 parts of absolute ether and the mixture is saturated with dry acetylene below 0 °. With continued initiation of acetylene, 84 parts of cyclopentanone are slowly added dropwise and the thin pulpy reaction liquid then as described in Example 1, processed further.
Das rohe, von Äther befreite Reaktionsprodukt stellt ein Gemenge von unverändertem Cyklopentanon, hochsiedenden Kondensationsprodukten des Cyklopentanons und den oben formulierten Acetylenalkohol dar. Durch wiederholte fraktionierte Destillation läßt sich der letztere daraus leicht rein abscheiden. Derselbe bildet ein farbloses, in Wasser schwer lösliches öl vom Siedepunkt 155 bis 160°; er bildet ein farbloses Silbersalz und ein gelbgefärbtes Kupferoxydulsalz. The crude reaction product, freed from ether, is a mixture of unchanged cyclopentanone, high-boiling condensation products of cyclopentanone and the above formulated acetylene alcohol. Repeated fractional distillation can be the latter can easily be separated from it. It forms a colorless one, heavy in water soluble oil from boiling point 155 to 160 °; it forms a colorless silver salt and a yellow-colored copper oxide salt.
Beispiel 4.
Kondensation von CyklohexanonnatriumExample 4.
Condensation of cyclohexanone sodium
C H2 — CH,CH 2 - CH,
CH2(^ ^C-ONaCH 2 (^ ^ C-ONa
C H2 — C H2 CH 2 - CH 2
mit Acetylen zu dem Acetylencarbinolwith acetylene to the acetylene carbinol
C HC H
2 ν. 2 ν.
C H2 — C H2 Q, — C ξξξ C H.CH 2 - CH 2 Q, - C ξξξ C H.
CH2-CH2 ICH 2 -CH 2 I.
.. /j/ j
Zur Darstellung dieses Carbinols verfährt man so, wie es im Beispiel 3 beschrieben ist, indem man hier an Stelle des Cyklopentanons 100 Teile Cyklohexanon zu dem Reaktionsgemisch unter Durchleiten von Acetylen tropft. Die Vereinigung der beiden Komponenten vollzieht sich glatt. Bei der weiteren Verarbeitung wird so gut wie kein Cyklohexanon zurückgewonnen, sondern das Acetylencarbinol von obiger Formel sogleich rein erhalten. Es bildet eine farblose Kristallmasse, die unter 6 mm Druck bei 61 bis 62° siedet.To prepare this carbinol, the procedure is as described in Example 3, by adding 100 parts of cyclohexanone to the reaction mixture in place of the cyclopentanone drops while passing acetylene through. The union of the two components takes place smoothly. During further processing As good as no cyclohexanone is recovered, but the acetylene carbinol Immediately obtained pure from the above formula. It forms a colorless crystal mass, which boils at 61 to 62 ° under 6 mm pressure.
Claims (1)
Weitere Ausbildung des durch das Hauptpatent 280226 und seine beiden Zusätze 284764 und 286920 geschützten Verfahrens zur Einführung der Oxyisopropylgruppe in Kohlenwasserstoffe, dadurch gekennzeichnet, daß man hier zwecks Einführung homologer Gruppen in Kohlenwasserstoffe die Homologen des Acetons in Form ihrer ätherlöslichen Alkaliverbindungen oder die Homologen des Acetons selbst in Gegenwart von Alkalimetall oder Alkaliamiden auf Kohlenwasserstoffe einwirken läßt.Patent claim:
Further development of the process for introducing the oxyisopropyl group into hydrocarbons, which is protected by the main patent 280226 and its two additions 284764 and 286920, characterized in that the homologues of acetone in the form of their ether-soluble alkali compounds or the homologues of acetone itself are used here for the purpose of introducing homologous groups into hydrocarbons can act on hydrocarbons in the presence of alkali metal or alkali amides.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE289800C true DE289800C (en) | 1900-01-01 |
Family
ID=544804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT289800D Expired DE289800C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE289800C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE740988C (en) * | 1938-01-21 | 1943-11-02 | Ig Farbenindustrie Ag | Process for the preparation of alcohols of the acetylene series |
-
0
- DE DENDAT289800D patent/DE289800C/de not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE740988C (en) * | 1938-01-21 | 1943-11-02 | Ig Farbenindustrie Ag | Process for the preparation of alcohols of the acetylene series |
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