DE94132C - - Google Patents
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- Publication number
- DE94132C DE94132C DENDAT94132D DE94132DA DE94132C DE 94132 C DE94132 C DE 94132C DE NDAT94132 D DENDAT94132 D DE NDAT94132D DE 94132D A DE94132D A DE 94132DA DE 94132 C DE94132 C DE 94132C
- Authority
- DE
- Germany
- Prior art keywords
- ester
- acetoacetic ester
- piperidine
- condensed
- mixed
- 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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- 230000005494 condensation Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N Ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N Salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Diethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- -1 benzoyl acetic ester Chemical compound 0.000 description 4
- 229940043350 citral Drugs 0.000 description 4
- 229930007907 citral Natural products 0.000 description 4
- WTEVQBCEXWBHNA-YFHOEESVSA-N neral Chemical compound CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LPBMPRKJYKSRLL-UHFFFAOYSA-N 3-benzoylchromen-2-one Chemical compound C=1C2=CC=CC=C2OC(=O)C=1C(=O)C1=CC=CC=C1 LPBMPRKJYKSRLL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N Acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N Benzyl cyanide Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229940095076 benzaldehyde Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VFOKYTYWXOYPOX-UHFFFAOYSA-N 2,3-diphenylprop-2-enenitrile Chemical compound C=1C=CC=CC=1C(C#N)=CC1=CC=CC=C1 VFOKYTYWXOYPOX-UHFFFAOYSA-N 0.000 description 1
- ACMLKANOGIVEPB-UHFFFAOYSA-N 2-oxochromene-3-carboxylic acid Chemical compound C1=CC=C2OC(=O)C(C(=O)O)=CC2=C1 ACMLKANOGIVEPB-UHFFFAOYSA-N 0.000 description 1
- CSPIFKKOBWYOEX-UHFFFAOYSA-N 3-acetylchromen-2-one Chemical compound C1=CC=C2OC(=O)C(C(=O)C)=CC2=C1 CSPIFKKOBWYOEX-UHFFFAOYSA-N 0.000 description 1
- LFTSEWVYWLTBRV-UHFFFAOYSA-N [C].C1=CC=C2OC(=O)C=CC2=C1 Chemical class [C].C1=CC=C2OC(=O)C=CC2=C1 LFTSEWVYWLTBRV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002002 slurry 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
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
Dr. E. KNOEVENAGEL in HEIDELBERG.Dr. E. KNOEVENAGEL in HEIDELBERG.
Patentirt im Deutschen Reiche vom 33. Juli 1895 ab.Patented in the German Empire on July 33, 1895.
Nach dem D. R. P. Nr. 74885 über Darstellung des Methylendiacetessigesters und seiner Homologen und den Mittheilungen des Erfinders in den Annalen der Chemie, Band 281, Seite 25, läfst sich 1 Mol. eines Aldehyds mit 2 Mol. Acetessigesters — oder eines Körpers vom Typus des Acetessigesters— durch primäre oder secundä're organische Basen condensiren.According to the D. R. P. No. 74885 on the preparation of methylenediacetoacetic ester and its Homologues and the inventor's communications in the Annals of Chemistry, Volume 281, Page 25, 1 mole of an aldehyde can be mixed with 2 moles of acetoacetic ester - or a body of Acetoacetic ester type - condensed by primary or secondary organic bases.
Ein genaueres Studium der Reaction hat ergeben, dafs diese Condensationen in der Weise erfolgen, dafs sich zunächst 1 Mol. des Aldehyds mit ι Mol. des Acetessigesters — oder ähnlicher Körper — unter Bildung ungesättigter Körper vereinigt, an welche sich erst in secundärer Reaction ein zweites Molecül des Körpers vom Typus des Acetessigesters unter Auflösung der Kohlenstoffdoppelbindung anlagert.A closer study of the reaction has shown that these condensations are in this way take place, that initially 1 mol. of the aldehyde with ι mol. of the acetoacetic ester - or similar Bodies - united with the formation of unsaturated bodies, which only become secondary Reaction of a second molecule of the body of the acetoacetic ester type with dissolution the carbon double bond accumulates.
Erfinder hat nun gefunden, dafs sich diese Reaction in ihrer ersten Phase ganz allgemein und leicht fixiren läfst, wenn man gleiche Molecule irgend eines Aldehyds und Acetessigester ■—· oder andere Körper, welche wie der Acetessigester eine Methylengruppe zwischen negativen Radicalen enthalten —■ mit primären oder secundären Basen zusammenbringt.Inventor has now found that this reaction is quite general in its first phase and can be easily fixed if the same molecules of any aldehyde and acetoacetic ester are used ■ - · or other bodies which, like the acetoacetic ester, have a methylene group between contain negative radicals - ■ brings together with primary or secondary bases.
Die hier in Frage stehenden Condensationen wurden früher schon zum Theil auf anderen Wegen erreicht durch Condensation mittelst gasförmiger Salzsäure oder mittelst Essigsäureanhydrid und in einigen wenigen Fällen auch durch Natriumacetat oder durch Natriumalkoholat. Durch das hier beschriebene Verfahren wird eine besondere technische Wirkung dadurch erreicht, dafs es umfangreicherer Anwendbarkeit fähig ist, und dafs es in weitaus den meisten Fällen einfacher durchzuführen ist und quantitativer verläuft, als die schon bekannten Condensationsverfahren.The condensations in question here have already been partly applied to others Because it is achieved by condensation by means of gaseous hydrochloric acid or by means of acetic anhydride and in a few cases also by sodium acetate or by sodium alcoholate. The method described here achieves a special technical effect in that it can be used more extensively capable, and that in by far most cases it is easier to do and runs more quantitatively than the already known condensation processes.
A. Condensationen mittelst primärer
Base.A. Condensations by means of primary
Base.
Citrylidenmalonester: 1600 g Malonester werden mit 1520g Citral gemengt und mit 30 bis 50 g Aethylamin condensirt. Das Condensationsproduct wird nach Entfernung des Aethylamins durch Waschen mit verdünnter Säure und Wasser im Vacuum destillirt. Es geht Citrylidenmalonester vom S. P. 203 ° C. bei 15 mm Druck über.Citrylidene malonic ester: 1600 g of malonic ester are mixed with 1520 g of citral and condensed with 30 to 50 g of ethylamine. That Condensation product is after removal of the ethylamine by washing with dilute Acid and water distilled in a vacuum. It is citrylidene malonic ester from S.P. 203 ° C. at 15mm print over.
Acety lcumarin: 1300 g Acetessigester werden mit 1220 g Salicylaldehyd und mit 30 bis 50 g Aethylamin versetzt. Man erhält an Stelle des zuerst gebildeten Salicylidenacetessigesters unter gleichzeitiger Alkoholabspaltung Acetcumarin, das nach dem Umkrystallisiren aus Wasser bei 1200 C. schmilzt.Acety lcoumarin: 1300 g of acetoacetic ester are mixed with 1220 g of salicylaldehyde and 30 to 50 g of ethylamine. Instead obtained Salicylidenacetessigesters the first-formed with simultaneous elimination of alcohol Acetcumarin which melts after recrystallization from water at 120 0 C..
Benzoylcumarin: 1920 g Benzoylessigester werden mit 1220 g Salicylaldehyd gemengt und durch Zusatz von ca. 100 g Anilin condensirt. Es entsteht ein in Wasser unlöslicher Krystallbrei, dem das Anilin durch Zusatz von verdünnter Salzsäure und Auswaschen mit Wasser entzogen wird. Nach dem Umkrystallisiren aus Alkohol schmilzt der KörperBenzoylcoumarin: 1920 g of benzoyl acetic ester are mixed with 1220 g of salicylaldehyde and condensed by adding about 100 g of aniline. The result is one that is insoluble in water Crystalline pulp, to which the aniline is added by adding dilute hydrochloric acid and washing it out is removed with water. After recrystallization from alcohol, the body melts
(2. Auflage, ausgegeben am X2. Juli iSgg.J(2nd edition, issued on July 2nd in connection with J.
bei Γ300 C. Er erweist sich als Benzoylcumarin, welches aus dem primär gebildeten Salicylidenbenzoylessigester durch sofortige Abspaltung von Alkohol entsteht.at Γ30 0 C. It proves Benzoylcumarin which arises from the primary formed Salicylidenbenzoylessigester by immediate elimination of alcohol.
B. Condensationen mittelst secundärer Base.B. Condensations by means of a secondary base.
Aethylidenacetessigester: 1300 g Acetessigester werden mit 440 g Acetaldehyd gemengt und ca. 20 g Piperidin (oder eine andere secundäre Base) unter starker Kühlung hinzugegeben. Nach Beendigung der Condensation wird das Piperidin durch Waschen mit Säure und Wasser entfernt und das OeI der Destillation am besten im Vacuum unterworfen. Der Aethylidenacetessigester geht bei 20 mm Druck zwischen 105 und io8° C. über.Ethylidene acetoacetic ester: 1300 g of acetoacetic ester are mixed with 440 g of acetaldehyde and about 20 g of piperidine (or another secondary base) were added with strong cooling. After the condensation has ended, the piperidine is removed by washing with acid and water and the oil is removed from the distillation best subjected to vacuum. The Aethylidenacetoessigester goes at 20 mm pressure between 105 and io8 ° C. above.
Citrylidenacetessigester: 1300 g Acetessigester werden mit 1520 g Citral gemengt gemäfs dem durch das Patent Nr. 7308g geschützten Verfahren, und unter starker Kühlung mit 20 g Piperidin versetzt. Das Reactionsgemisch wird wie sonst von Piperidin befreit und der Vacuumdestillation unterworfen. Es destillirt reiner Citrylidenacetessigester unter 20 mm Druck bei 1950C.Citrylidenacetoacetic ester: 1300 g of acetoacetic ester are mixed with 1520 g of citral in accordance with the process protected by patent no. 7308g, and 20 g of piperidine are added with strong cooling. The reaction mixture is freed from piperidine as usual and subjected to vacuum distillation. It distils pure Citrylidenacetessigester under 20 mm pressure at 195 0 C.
Citrylidenmalonester: 1600 g Malonester werden mit 1520g Citral gemengt und in der Kälte mit 20 g Piperidin condensirt. Die Verarbeitung geschieht wie sonst. Es entsteht Citrylidenmalonester vom S. P. 1940 C. bei 9 mm Druck.Citrylidene malonic ester: 1600 g of malonic ester are mixed with 1520 g of citral and condensed in the cold with 20 g of piperidine. The processing is done as usual. It arises from Citrylidenmalonester SP 194 0 C. at 9 mm pressure.
Citrylidenacetylaceton: 1000 g Acetylaceton werden mit 1520 g Citral durch 20 g Piperidin bei starker Kälte condensirt. Das gebildete Citrylidenacetylaceton siedet bei 1830C. unter 9 mm Druck.Citrylidene acetylacetone: 1000 g of acetylacetone are condensed with 1520 g of citral by 20 g of piperidine in extremely cold conditions. The Citrylidenacetylaceton formed boils at 183 0 C. 9 mm pressure.
Benzylidenacetessigester: 1300 g Acetessigester und 1060 g Benzaldehyd erstarren durch Zusatz von ca. 20 g Piperidin bei starker Kälte unter Wasseraus.tritt zu einem harten Krystallkuchen von Benzylidenacetessigester. F. P. 60 bis 61 ° C.Benzylidene acetoacetic ester: 1300 g acetoacetic ester and 1060 g of benzaldehyde solidify by adding about 20 g of piperidine at strong Cold under water emerges into a hard crystal cake of benzylidene acetoacetic ester. F. P. 60 to 61 ° C.
Acetylcumarin: 1300 g Acetessigester werden mit 1220 g Salicylaldehyd und ca. 20 g Piperidin in der Kälte condensirt. Nach kurzer Zeit erstarrt das Gemisch zu einem harten^ Krystallbrei. Man erhält an Stelle des Salicylidenacetessigesters unter gleichzeitiger. Abspaltung von Alkohol Acetcumarin vom F. P. 1200 C.Acetylcoumarin: 1300 g acetoacetic ester are condensed in the cold with 1220 g salicylaldehyde and approx. 20 g piperidine. After a short time the mixture solidifies to a hard crystalline slurry. Instead of the salicylidene acetoacetic ester, one obtains at the same time. Cleavage of alcohol acetcoumarin from the FP 120 0 C.
Cumarincarbonsäureester: 1600g Malonester werden mit 1220 g Salicylaldehyd gemengt und durch 20 g Piperidin zur Condensation gebracht. Man erhält unter gleichzeitiger Alkoholabspaltung Cumarincarbonester vom F. P. 940C.Coumarin carboxylic acid ester: 1600 g of malonic ester are mixed with 1220 g of salicylaldehyde and condensed with 20 g of piperidine. With simultaneous elimination of alcohol, coumarin carbon esters from FP 94 0 C are obtained.
Benzylidenbenzylcyanid (α - Phenyl zimmtsäurenitril): 1170 g Benzylcyanid und 1060 g Benzaldehyd werden mit ca. 50 g Piperidin in der Kälte condensirt. Es entsteht Bencylidenbenzylcyanid von 86° C. Schmelzpunkt. Benzylidene benzyl cyanide (α - phenyl zinnamic acid nitrile): 1170 g benzyl cyanide and 1060 g of benzaldehyde are condensed in the cold with about 50 g of piperidine. It arises Bencylidene benzyl cyanide of 86 ° C. Melting point.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE94132C true DE94132C (en) |
Family
ID=365505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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Country Status (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0729936A1 (en) * | 1995-03-03 | 1996-09-04 | Societe Civile Bioprojet | Process for the synthesis of alpha substituted acrylic acids and their application |
-
0
- DE DENDAT94132D patent/DE94132C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0729936A1 (en) * | 1995-03-03 | 1996-09-04 | Societe Civile Bioprojet | Process for the synthesis of alpha substituted acrylic acids and their application |
| FR2731219A1 (en) * | 1995-03-03 | 1996-09-06 | Bioprojet Soc Civ | PROCESS FOR THE SYNTHESIS OF ALPHA-SUBSTITUTED ACRYLIC ACIDS AND THEIR APPLICATION |
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