DE108335C - - Google Patents
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- Publication number
- DE108335C DE108335C DENDAT108335D DE108335DA DE108335C DE 108335 C DE108335 C DE 108335C DE NDAT108335 D DENDAT108335 D DE NDAT108335D DE 108335D A DE108335D A DE 108335DA DE 108335 C DE108335 C DE 108335C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- cyclocitral
- parts
- citralidenecyanoacetic
- citral
- 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.)
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- 239000002253 acid Substances 0.000 claims description 17
- MLIREBYILWEBDM-UHFFFAOYSA-N Cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 9
- 229930007907 citral Natural products 0.000 claims description 8
- 229940043350 citral Drugs 0.000 claims description 8
- WTEVQBCEXWBHNA-YFHOEESVSA-N neral Chemical compound CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 230000000875 corresponding Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- QSMUFXXTSUEZJA-UHFFFAOYSA-N 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid Chemical compound O=C1N(CC=2C=CC=CC=2)C(C(=O)O)C(C(O)=O)N1CC1=CC=CC=C1 QSMUFXXTSUEZJA-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PSQYTAPXSHCGMF-BQYQJAHWSA-N beta-ionone Natural products CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- ZHYZQXUYZJNEHD-VQHVLOKHSA-N Geranic acid Chemical compound CC(C)=CCC\C(C)=C\C(O)=O ZHYZQXUYZJNEHD-VQHVLOKHSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229930008392 geranic acid Natural products 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NIKFYOSELWJIOF-UHFFFAOYSA-O Fuchsine Chemical compound Cl.C1=C(N)C(C)=CC(C(=C2C=CC(=[NH2+])C=C2)C=2C=CC(N)=CC=2)=C1 NIKFYOSELWJIOF-UHFFFAOYSA-O 0.000 description 1
- SFEOKXHPFMOVRM-BQYQJAHWSA-N Ionone Chemical compound CC(=O)\C=C\C1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-BQYQJAHWSA-N 0.000 description 1
- OJLMARCQPSGYNE-UXBLZVDNSA-N Isocitral Chemical compound CC(C)=CC\C=C(/C)CC=O OJLMARCQPSGYNE-UXBLZVDNSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229930002839 ionones Natural products 0.000 description 1
- 239000009758 isogeranic acid Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/42—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings with a six-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
PATENTAMT.PATENT OFFICE.
Im Patent 7308g ist gezeigt, dafs das Pseudojonon unter der Einwirkung von Säuren in eine isomere cyclische Verbindung, das Jonon, übergeht, und im Patent 75062 ist nachge7 wiesen, dafs die Glieder der Citral- (Geranial-) Reihe allgemeiner durch Säuren in cyclische Isomere umgewandelt werden, dafs man z. B. auf diesem Wege die Geraniumsäure in Isogeraniumsäure (cyclische Geraniumsäure) und ebenso Geraniumsäurenitnl in Isogeraniumsäurenitril (Cyclogeraniumsäurenitril) u. s. w. überführen kann. Eine gleiche Isomerisation des Citrals in Isocitral (Cyclocitral) ist bislang nicht gelungen.In Patent 7308g shown, the pseudoionone DAF under the action of acids in an isomeric cyclic compound, ionone, passes, and in patent 75062 is disclosed nachge 7, the members of the citral (geranial-) DAF number of general by acids in cyclic Isomers are converted, that z. B. in this way the geranic acid in isogeranic acid (cyclic geranic acid) and also geraniumsäurenitnl in isogeraniumsäurenitril (Cyclogeraniumsäurenitril) etc. can be converted. The same isomerization of citral into isocitral (cyclocitral) has not yet been successful.
Es wurde nun gefunden, dafs man zu dem Cyclocitral auf nachstehendem Umwege gelangen kann:It has now been found that cyclocitral can be obtained by the following detour can:
Citral wird mit Cyanessigsäure bezw. einem Salz oder Ester der Cyanessigsäure zu Citralidencyanessigsäure bezw. einem Salz oder Ester der Citralidencyanessigsäure conderisirt. Die Citralidencyanessigsäure bezw. das betreffende Derivat derselben wird nach dem durch das Patent 75062 geschützten Verfahren in die entsprechende isomere cyclische Verbindung umgewandelt und das dabei gewonnene Rohproduct direct bei ausreichend hoher Temperatur mit Alkalilauge bezw. Alkalilauge unter Zusatz eines gelinden Oxydationsmittels behandelt. Man kann aus dem Reactionsproduct durch fractionirte Destillation ein hochprocentiges Cyclocitral bereiten, indem man die bei 15 mm Druck zwischen 80 bis 1 io° siedende Fraction aussiedet.Citral is with cyanoacetic acid respectively. a salt or ester of cyanoacetic acid to citralidenecyanoacetic acid respectively conderized with a salt or ester of citralidenecyanoacetic acid. The citralidenecyanoacetic acid respectively. the derivative in question is the same after by the patent 75062 protected process into the corresponding isomeric cyclic compound converted and the resulting raw product directly at a sufficiently high temperature with alkali or Alkali treated with the addition of a mild oxidizing agent. A high percentage can be obtained from the reaction product by fractional distillation Prepare cyclocitral by pressing between 80 to 1 io ° at 15 mm boiling fraction.
Das so dargestellte Cyclocitral stellt eine wasserhelle Flüssigkeit dar. Cyclocitral ruft in der farblosen Auflösung von Rosanilin in wässeriger schwefliger Säure eine violette Färbung hervor, reducirt aus ammoniakalischer Silberlösung metallisches Silber und bildet ein krystallisirtes Semicarbazon von schwankendem Schmelzpunkt. Cyclocitral wird durch dieses Verhalten als Aldehyd charakterisirt.The cyclocitral represented in this way represents a water-white liquid. Cyclocitral calls in the colorless dissolution of rosaniline in aqueous sulphurous acid turns a violet color out, reduces metallic silver from ammoniacal silver solution and forms a crystallized semicarbazone of fluctuating melting point. Cyclocitral is made through this Behavior characterized as an aldehyde.
Cyclocitral soll zur Darstellung von ß-Jonon dienen. Die chemische -Natur des Cyclocitrals wird durch die in alkalischer Lösung eintretende Condensation von Cyclocitral mit Aceton, welche direct zu β-Jonon führt, in schärfster Weise gekennzeichnet.Cyclocitral is said to be used to represent ß-ionone. The chemical nature of cyclocitral is caused by the condensation of cyclocitral with in alkaline solution Acetone, which leads directly to β-ionone, is marked in the sharpest way.
Die Ausführung des Verfahrens ergiebt sich aus folgendem Beispiel:The execution of the procedure results from the following example:
100 Theile Cyanessigsäure, in 300 Theilen Wasser gelöst, werden mit der Lösung von 60 Theilen Natriumhydroxyd in 300 Theilen Wasser und sodann mit einer Mischung aus 180 Theilen Citral und 100 Theilen Alkohol versetzt. Nach kurzem Schütteln klärt sich die anfangs trübe Flüssigkeit unter Erwärmen. Beim Ansäuern scheidet sich die Citralidencyanessigsäure zunächst als OeI ab, welches allmälig krystallinisch erstarrt.100 parts of cyanoacetic acid, dissolved in 300 parts of water, are mixed with the solution of 60 parts of sodium hydroxide in 300 parts of water and then with a mixture of 180 parts citral and 100 parts alcohol are added. After a short shake it clears the initially cloudy liquid with warming. During acidification, the citralidenecyanoacetic acid separates initially as an OeI, which gradually solidifies in a crystalline manner.
Die erstarrte rohe Citralidencyanessigsäure wird durch circa 12 stündiges Kochen am Rückflufskühler mit einer Lösung von circa 80 Raumtheilen concentrirter Schwefelsäure in 600 Raumtheilen Wasser in die entsprechende cyclische Isomere umgewandelt. Man trennt gleichzeitig gebildete, neutral reagirende Nebenproducte durch Aufnahme der rohen Säure in Alkalilauge und Ausäthern der alkalischen Lösung-ab. Die aus der alkalischen Lösung durch Säuren gefällte cyclischeThe solidified crude citralidenecyanoacetic acid is boiled for about 12 hours Reflux condenser with a solution of about 80 parts by volume of concentrated sulfuric acid converted into the corresponding cyclic isomer in 600 parts by volume of water. Simultaneously formed, neutrally reacting ones are separated By-products from taking up the crude acid in alkali lye and etherifying the alkaline solution. The ones from the alkaline Cyclic solution precipitated by acids
Citralidencyanessigsäure bildet einen schwerflüssigen Syrup.Citralidenecyanacetic acid forms a heavy syrup.
Behufs Abspaltung von Cyclocitral aus dieser syrupösen Cyclocitralidencyanessigsäure löst man die rohe, aus 180 Theilen Citral gewonnene Säure in wenig Alkalilauge und behandelt die Lösung in einem Destillationsapparate mit einem starken Dampfstrom, indem man gleichzeitig eine Auflösung von 200 Theilen Kaliumhydrat in wenig Wasser hinzutropfen läfst. Das im Kühler condensirte OeI enthält das gebildete Cyclocitral. Die unter 15 mm Druck bei 80 bis ioo° siedende Fraction dieses Oeles bildet eine gelb gefärbte, leicht bewegliche Flüssigkeit.For the purpose of splitting off cyclocitral from this syrupy cyclocitralidenecyanoacetic acid, one dissolves the crude acid, obtained from 180 parts of citral, in a little alkali lye, and treats it Dissolve in a still with a strong stream of steam by simultaneously a solution of 200 parts of potassium hydrate in a little water is allowed to drop in. The im Cooler condensed oil contains the formed cyclocitral. Those under 15mm pressure at 80 A fraction of this oil boiling up to 100 ° forms a yellow-colored, easily mobile liquid.
Die Abspaltung von Cyclocitral aus Cyclo-/ citralidencyanessigsäure kann auch in der Weise geschehen, dafs man die aus 180 Theilen Citral gewonnene Cyclocitralidencyanessigsäure mit einer Auflösung von 300 Theilen Kaliumhydrat in 300 Theilen Wasser und etwa 300 Theilen Xylol 10 bis 12 Stunden am Rückflufskühler kocht, die abgetrennte Xylolschicht trocknet und im Vacuum fractionirt, indem man als Cyclocitral die unter 15 mm Druck zwischen 80 bis iio° übergehende Fraction sammelt.The elimination of cyclocitral from cyclo- / Citralidenecyanoacetic acid can also be done in such a way that one consists of 180 parts Cyclocitralidenecyanoacetic acid obtained from citral has a dissolution of 300 parts of potassium hydrate in 300 parts of water and about 300 parts of xylene 10 to 12 hours am The reflux condenser boils, the separated xylene layer dries and fractionates in a vacuum by using as cyclocitral the less than 15 mm Pressure between 80 to 10 ° passing fraction collects.
Um die Abspaltung von Cyclocitral zu erleichtern , kann man in dem einen wie im anderen Falle kleine Mengen eines gelinde wirkenden . Oxydationsmittels., <z. B. Bleisuperoxyd, :Mangan'superoxyd, ' Bariumsuperoxyd, Natrium'superoxyd etc. hinzufügen. '■. In order to facilitate the cleavage of cyclocitral, small amounts of a mild one can be used in one case as in the other. Oxidizing agent., <Z. , As lead peroxide: Add Mangan'superoxyd etc., 'Bariumsuperoxyd, Natrium'superoxyd. '■.
An Stelle von freier Cyanessigsäure kann man bei dem vorstehend beschriebenen Verfahren auch ein lösliches Salz der Cyanessigsäure oder einen ihrer Ester anwenden. Wenn man Ester der Cyanessigsäure benutzt, so mufs die alkalische Flüssigkeit schliefslich erhitzt werden, bis die darauf schwimmenden Ester der Citralidencyanessigsäure und der Cyanessigsäure verseift sind und eine klare Lösung entstanden ist.Instead of free cyanoacetic acid, one can use the method described above also use a soluble salt of cyanoacetic acid or one of its esters. if If esters of cyanoacetic acid are used, the alkaline liquid must finally be heated until the floating esters of citralidenecyanoacetic acid and cyanoacetic acid are saponified and a clear solution has arisen.
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