DE596255C - Process for the preparation of ketones from citral - Google Patents
Process for the preparation of ketones from citralInfo
- Publication number
- DE596255C DE596255C DEG82275D DEG0082275D DE596255C DE 596255 C DE596255 C DE 596255C DE G82275 D DEG82275 D DE G82275D DE G0082275 D DEG0082275 D DE G0082275D DE 596255 C DE596255 C DE 596255C
- Authority
- DE
- Germany
- Prior art keywords
- citral
- acid
- ethyl
- ketones
- citralone
- 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
- 150000002576 ketones Chemical class 0.000 title claims description 14
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title claims description 11
- 229940043350 citral Drugs 0.000 title claims description 11
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YKNYRRVISWJDSR-UHFFFAOYSA-N methyl oxirane-2-carboxylate Chemical compound COC(=O)C1CO1 YKNYRRVISWJDSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 methyl glycidate ester Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 150000007659 semicarbazones Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- OTGHWLKHGCENJV-UHFFFAOYSA-N glycidic acid Chemical compound OC(=O)C1CO1 OTGHWLKHGCENJV-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NZZYVDKRZFWNRJ-UHFFFAOYSA-M 2-chloro-2-methylbutanoate Chemical compound CCC(C)(Cl)C([O-])=O NZZYVDKRZFWNRJ-UHFFFAOYSA-M 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- CSEUSVYSDPXJAP-UHFFFAOYSA-N 2-methyloxirane-2-carboxylic acid Chemical compound OC(=O)C1(C)CO1 CSEUSVYSDPXJAP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
-
- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
Description
Verfahren zur Darstellung von Ketonen aus Citral Die Erfindung betrifft ein Verfahren zur Darstellung neuer Ketone (Citralone) aus Citral.Process for the preparation of ketones from citral The invention relates to a process for the preparation of new ketones (citralone) from citral.
Dieses Verfahren beruht darauf, daß Citral, mit a-chlorpropionsaunem Äthyl vermischt, in Gegenwart eines Alkoholates, z. B. Natriumalkoholat, einen Methylglycidestererzeugt, dessen durch Verseifung gewonnene Säure C 02 abspaltet und sich in ein neues Keton umwandelt, das den Namen Citralon erhält.This process is based on the fact that citral, with a-chloropropionic acid Ethyl mixed in the presence of an alcoholate, e.g. B. Sodium alcoholate, which produces a methyl glycidate ester, its acid C 02 obtained by saponification splits off and converts into a new ketone converts, which is named Citralon.
Die Reaktion, die zur Bildung des Methylglycidesters führt, kann durch
folgende Formeln dargestellt werden:
D-as neue Keton, Citralon, besitzt einen angenehmen Geruch und kann daher in der Riechstoffindustrie verwendet werden oder als Ausgangsstoff für die Herstellung anderer Erzeugnisse dienen. Durch Einwirkung von Schwefelsäure von 6o0/0 oder Phosphorsäure von Soojo oder noch anderer Isomerisatibnsmittel auf das Keton wird dieses in sein Cycloisomer, das Cyclocitralon, übergeführt, dessen Siedepunkt bei 2 mm Quecksilberdruck 85° beträgt und dessen Semicarbazon bei 176 bis z77° schmilzt und einen sehr angenehmen Geruch besitzt.The new ketone, citralone, has a pleasant odor and can therefore used in the fragrance industry or as a raw material for Serve to manufacture other products. By exposure to sulfuric acid of 6o0 / 0 or phosphoric acid from Soojo or other isomerizing agents on the ketone this is converted into its cycloisomer, the cyclocitralone, its boiling point at 2 mm mercury pressure is 85 ° and its semicarbazone melts at 176 to z77 ° and has a very pleasant odor.
Es ist bekannt, daß, wenn man ein Alkaliinetallalkoholat auf ein Gemisch eines Aldehvds und Chloressigsäureester oder n-Chlorpropionsäureester einwirken läßt, man Glycidester erhält, und daß die entsprechenden Glycidsäuren sich beim Erhitzen in Aldehyde oder Ketone zersetzen.It is known that when you add an alkali metal alcoholate to a mixture an aldehyde and chloroacetic acid ester or n-chloropropionic acid ester act lets, one receives glycidic ester, and that the corresponding glycidic acids are at Heat decompose into aldehydes or ketones.
Diese Reaktionen können durch folgende Gleichungen veranschaulicht werden: Diese Reaktionen können aber nicht allgemein angewendet worden, weil entweder der Aldehyd sich in Gegenwart eines Alkalimetallalkoholates sofort polymerisiert oder verharzt oder weil bei Zersetzung der Glycidsäuren durch Erhitzen nur Harze undProdukte völliger Zersetzung erzeugt werden.These reactions can be illustrated by the following equations: However, these reactions cannot be used in general, because either the aldehyde polymerizes or resinifies immediately in the presence of an alkali metal alcoholate, or because when the glycidic acids decompose through heating, only resins and products of complete decomposition are produced.
Dies ist besonders der Fall, wenn diese Reaktion auf das Citral angewendet wird und dieses mit chloressigsaurem Äthyl in Gegenwart eines Alkalimetallalkoholates behandelt wird.This is especially the case when this reaction is applied to the citral and this with ethyl chloroacetate in the presence of an alkali metal alcoholate is treated.
Es wurde nun gefunden, daß Citral, mit o:-chlorpropionsaurem Athyl vermischt, in Gegenwart eines Alkoholates, z. B. Natriumalkoholat, einen Methylglycidester erzeugt, dessen durch Verseifung gewonnene Säure CO. abspaltet und sich in ein neues Keton umwandelt, das den Namen Citralon erhält.It has now been found that citral, mixed with o: -chlorpropionsaurem Ethyl, in the presence of an alcoholate, for. B. sodium alcoholate, a methyl glycidate is produced, the acid obtained by saponification CO. splits off and converts to a new ketone named citralone.
Das Citralon kann beispielsweise folgendermaßen hergestellt werden: In eine Mischung von 8,2oo kg Äthylca-chlorpropionat und 9,6oo kg Citral von 95 0i0 läßt man unter Umrühren eine Lösung von 4380 kg Natrium in 18 kg absolutem Alkohol einfließen. Die Ausflußgeschwindigkeit wird derart geregelt, daß die Temperatur der Mischung 25° nicht übersteigt. Die erhaltene Mischung wird dann während einiger Stunden sich selbst überlassen. Man neutralisiert den Alkaliüberschuß mit Essigsäure, gibt Wasser zu und destilliert den Alkohol ab. Der erkaltete Rückstand wird mit Wasser gewaschen, die ölige Schicht abgegossen und mit 24 kg ioo/oiger Ätznatronlauge während 3 bis 4 Stunden bei gewöhnlicher Temperatur geschüttelt. Man erhält dabei das Natriumsalz der Methylglycidsäure. Die Gesamtmasse wird hierauf mit einem Überschuß von 5o°/oiger Schwefelsäure behandelt, wobei die Methylglycidsäure frei wird. Die ölige, diese Säure enthaltende Schicht wird abgetrennt und durch diese so lange Wasserdampf hindurchgetrieben, als noch mit dem Wasser eine unlösliche Flüssigkeit übergeht. Durch diese Behandlung ist die Säure durch Abgabe von CO. in das Citralon übergeführt worden. Die ölige Flüssigkeit wird vom Wasser getrennt und durch Destillation iin Vakuum gereinigt. Bei 2 mm Ouecksilberdruck geht das Citralon zwischen 8o und ioo° C über und kann mittels seines Semicarbazons vollständig rein und farblos erhalten werden.For example, the citralone can be made as follows: In a mixture of 8.2oo kg of ethyl ca-chloropropionate and 9.6oo kg of citral of 95 A solution of 4380 kg of sodium in 18 kg of absolute alcohol is left with stirring flow in. The outflow rate is controlled in such a way that the temperature the mixture does not exceed 25 °. The mixture obtained is then during some Left to their own devices for hours. The excess alkali is neutralized with acetic acid, adds water and distills off the alcohol. The cooled residue is with Washed water, the oily layer poured off and with 24 kg 100% caustic soda solution shaken for 3 to 4 hours at ordinary temperature. One receives thereby the sodium salt of methyl glycidic acid. The total mass then becomes with an excess treated with 50% sulfuric acid, whereby the methylglycidic acid is free. the oily layer containing this acid is separated and through this for so long Water vapor drifted through it, when it was still an insoluble liquid with water transforms. As a result of this treatment, the acid is released from CO. into the citralone been convicted. The oily liquid is separated from the water and subjected to distillation cleaned in vacuum. At 2 mm The citralone goes through silver printing between 8o and 100 ° C above and can be completely pure thanks to its semicarbazone and can be obtained colorless.
Um nun dieses Citralon in Cyclocitralon überzuführen, kann man in folgender Weise verfahren: 5 kg Citralon und 2o kg So°/oige Phosphorsäure werden jedes getrennt auf eine zwischen o und 5 ° liegende Temperatur abgekühlt. Unter Umrühren wird sodann das Citralon in die Phosphorsäure gegossen, wobei die Temperatur von selbst auf ungefähr 5o° C steigt. Es wird während i Stunde weitergerührt, worauf das Gemisch in eisgekühltes Wasser gegossen wird. Man trennt das saure Wasser von der öligen Flüssigkeit, welche zuerst mit warmem Wasser und dann mit einer warmen Lösung von kohlensaurem Natrium im Überschuß gewaschen wird. Das rohe Cyclocitralon wird durch fraktionierte Destillation gereinigt. Zwischen 8o und 9o° C geht das Cyclocitralon über; mittels einer weiteren Destillation kann dieses noch besser gereinigt werden, und schließlich kann man das Cyclocitralon über sein Semicarbazon vollständig rein erhalten.In order to convert this citralone into cyclocitralone, one can in Proceed as follows: 5 kg of citralone and 20 kg of 50% phosphoric acid are added each cooled separately to a temperature between 0 and 5 °. Under Stirring, the citralone is then poured into the phosphoric acid, keeping the temperature rises by itself to about 50 ° C. Stirring is continued for an hour, after which the mixture is poured into ice-cold water. The acidic water is separated from the oily liquid, which is washed first with warm water and then with warm water Solution of carbonate of sodium in excess is washed. The crude cyclocitralone is purified by fractional distillation. It works between 8o and 9o ° C Cyclocitralone over; this can be done even better with a further distillation and finally you can get the cyclocitralone via its semicarbazone received completely pure.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG82275D DE596255C (en) | 1932-03-25 | 1932-03-25 | Process for the preparation of ketones from citral |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG82275D DE596255C (en) | 1932-03-25 | 1932-03-25 | Process for the preparation of ketones from citral |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE596255C true DE596255C (en) | 1934-05-11 |
Family
ID=7137522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG82275D Expired DE596255C (en) | 1932-03-25 | 1932-03-25 | Process for the preparation of ketones from citral |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE596255C (en) |
-
1932
- 1932-03-25 DE DEG82275D patent/DE596255C/en not_active Expired
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