DE2118437C3 - i-Isopropenyl-2-p-chlorobenzoylacetylene and process for its preparation - Google Patents
i-Isopropenyl-2-p-chlorobenzoylacetylene and process for its preparationInfo
- Publication number
- DE2118437C3 DE2118437C3 DE19712118437 DE2118437A DE2118437C3 DE 2118437 C3 DE2118437 C3 DE 2118437C3 DE 19712118437 DE19712118437 DE 19712118437 DE 2118437 A DE2118437 A DE 2118437A DE 2118437 C3 DE2118437 C3 DE 2118437C3
- Authority
- DE
- Germany
- Prior art keywords
- isopropenyl
- chlorobenzoylacetylene
- preparation
- compound
- added dropwise
- 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
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims 2
- 150000001875 compounds Chemical class 0.000 claims description 8
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000003385 bacteriostatic Effects 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 230000001408 fungistatic Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- YUKOSCZNCWZWJG-UHFFFAOYSA-N 4-methyl-1-phenylpent-4-en-2-yn-1-one Chemical group CC(=C)C#CC(=O)C1=CC=CC=C1 YUKOSCZNCWZWJG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N Bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 229940095731 Candida albicans Drugs 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940095076 benzaldehyde Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036633 rest Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
Description
In dem Hauptpatent ist die fungistatisch und bakteriostatiseh wirksame Acelylemerbindung 1-lsopropenyl-2-benzovlacetvlen beschrieben.In the main patent it is fungistatic and bacteriostatic acetyl binding 1-isopropenyl-2-benzovlacetylene described.
In dem Hauptpatent ist ferner ein Verfahren zur Herstellung dieser Verbindung beschrieben. Das Verfahren ist dadurch gekenn/eichnet. daß man die aus der 2-Isopropyl-aeetylen-Verbindung hergestellte Ciirgnardverbindung mit Benzaldehyd umsetzt und das Umsetzungsprodukl dann zu dem entsprechenden Keton oxydiert.The main patent also describes a process for producing this compound. The procedure is thereby identified / calibrated. that one prepared from the 2-isopropyl-aeetylene compound Ciirgnardverbindungen reacts with benzaldehyde and the implementation product then to the corresponding one Ketone oxidizes.
Bei der weiteren . lisbildung dieser Erfindung wurde gefunden, daß diese Verbindung ausgezeichnete fungi-Statische und baktcriostatisehe Eigenschaften hat. «venη der Phenyln-st in p-Stellung chloriert ist.At the other. In the formation of this invention, this compound was found to be excellent fungi-static and has bacteriostatic properties. «Venη the phenyln-st is chlorinated in the p-position.
Die neue Verbindung kann analog zu dem im Hauptfialcnt beschriebenen Verfahren hergestellt werden. Man setzt die aus dem 2-Isopropenvl-aeetvlen hergestellte Grignardvcrbindung mit p-Chlorben/aldehyd »im und oxydiert das Umsetzungsprodukt zu dem entsprechenden Keton.The new connection can be analogous to that in the main event described method are produced. One sets the one made from the 2-isopropene-aeetvlen Grignard compound with p-chlorobenzene / aldehyde and oxidizes the reaction product to the corresponding ketone.
3535
e 1 s ρ ι e 1e 1 s ρ ι e 1
12.15 g Magnesiunispane werden mit 50 ml wasserfreiem Tetrahydrofuran überschichtel. Unter Sliek- »toff werden 54 g Athylbromid in KK) ml wasserfreiem Tetrahydrofuran gelöst, derart zugetropft, daß die Temperatur zwischen 40 und 50 (.' bleibt. Anschließend kocht man den Ansatz 30 Minuten unter Rückfluß. Nach Abkühlen auf 20 C tropft man 53 ml Isopropeinlaeetslen. in 50ml wasserfreiem Tetrahvdrofuran gelöst, derart zu. daß die Temperatur nicht über 30 C steigt. Danach kocht man 30 Minuten am Rückfluß. Nach Abkühlen mit Eis-Kochsalz-Mischung auf 0 C tropft man 70.3 g 4-Chiorbenzaldehyd. in 150 ml wasserfreiem Tetrahydrofuran gelösi. zwischen 5 und 10 C hinzu und läßt 45 Minuten unter Rückfluß nachreagieren.12.15 g of Magnesiunispane are covered with 50 ml of anhydrous tetrahydrofuran. Under Sliek- 54 g of ethyl bromide in KK) ml of anhydrous Dissolved tetrahydrofuran, added dropwise in such a way that the temperature remains between 40 and 50 (. '. Subsequently the batch is refluxed for 30 minutes. After cooling to 20 ° C., 53 ml are added dropwise Isopropyl charges. in 50ml anhydrous tetrahydrofuran resolved so too. that the temperature does not rise above 30 C. Then cook for 30 minutes at reflux. After cooling to 0 ° C. with an ice-common salt mixture, 70.3 g of 4-chlorobenzaldehyde are added dropwise. gelösi in 150 ml of anhydrous tetrahydrofuran. between 5 and 10 C and allowed to react for 45 minutes under reflux.
Das erkaltete Reaktionsgemisch gießt man auf eine aus 150 g Ammoniumehlorid. 200 ml Wasser und 250 ti Eis" bestehende Mischung und rührt 1 Stunde. Nach Abtrennung der organischen Phase wäscht man diese mit Natriumsulfit. Soda und anschließend mit Wasser bis zur neutralen Reaktion. Nach Trocknen mit Natriumsulfat und Zugabe von 0.5°0 Hydrochinon fraktioniert man das Reaktionsprodukt im Hochvakuum.The cooled reaction mixture is poured onto a 150 g ammonium chloride. 200 ml of water and 250 ti ice "existing mixture and stir for 1 hour. After the organic phase has been separated off, it is washed with sodium sulfite. Soda and then with Water until neutral. After drying with sodium sulfate and addition of 0.5 ° 0 hydroquinone the reaction product is fractionated in a high vacuum.
Siedepunkt: 114 bis 116 C 0.03mm. Ausbeute: 53 υ = 49"0 der Theorie.Boiling point: 114 to 116 C 0.03mm. Yield: 53 υ = 49 "0 of theory.
Die Oxydation dieses Alkohols geschieht in der folgenden Weise: 20.6g Alkohol löst man in 6(1 ml Aceton und kühlt auf 0 C ab.This alcohol is oxidized as follows: Dissolve 20.6 g of alcohol in 6 (1 ml Acetone and cools to 0 C.
Nun stellt man eine Lösung vonNow we provide a solution for
7 g Chromtrioxyd.7 g chromium trioxide.
11.2 11 konzentrierter Schwefelsäure und
30 ml Wasser her.11.2 11 concentrated sulfuric acid and
30 ml of water.
die ebenfalls auf 0 C gekühlt wird.which is also cooled to 0 C.
Die Oxydationslösung tropft man innerhalb \on 2 Stunden zur Aceton-Lösung hinzu, wobei die Tempern ur 10 C nicht überschreiten soll. Die Nachreaktion erfolgt etwa 3 Stunden bei Raumtemperatur.The oxidation solution is added dropwise to the acetone solution within 2 hours, the tempering should not exceed 10 C. The subsequent reaction takes place for about 3 hours at room temperature.
Die Reakt'onsmischung extrahiert man mit Äther, wobei die organische Phase mit Wasser nachgewaschen und anschließend getrocknet wird. Nach Abdestillieien des Äthers fraktioniert man den Rückstand im Hochvakuum.The reaction mixture is extracted with ether, wherein the organic phase is washed with water and then dried. After distilling of the ether, the residue is fractionated in a high vacuum.
Man fängt die zwischen 105 und 110 C !1.04 mm siedende Fraktion auf. die nach Stehen durchkristallisiert. Schmelzpunkt 50 C. Ausbeute: 13.2g = 63",, der Theorie.You catch those between 105 and 110 C! 1.04 mm boiling fraction. which crystallizes after standing. Melting point 50 C. Yield: 13.2g = 63 ",, the theory.
Die so hergestellte Verbindung wurde nach dem im Hauptpatent beschriebenen Verfahren auf ihre fungistalische und baktcriostatische Wirksamkeit geprüft. Hierbei wurden die nachstehenden Ergebnisse erhalten:The connection so produced was according to the method described in the main patent on their fungistal and bacteriostatic effectiveness tested. Here, the following results were obtained receive:
Kein Wachstum.
I : I I ast totale llcmnuini:No growth.
I : II ast totale llcmnuini:
Kein ilen Knnirollen \er;jlen.hhaics WachstumNo ile tubercles \ er; jlen.hhaics growth
/um Nachweis des technischen Fortschrittes wurde 65 on( I) (in der Tabelle mit »B« bezeichnen verglichen,/ in order to demonstrate technical progress, 65 on (I) (denoted by "B" in the table) was compared,
die Wirkung des erlindungsgemäßen l-lsopropcnvl- Die Substanzen wurden im Verdünnunastest jeweilsthe effect of the isopropyl alcohol according to the invention. The substances were each tested in the dilution test
2-p-chlorbenzoylacetylcns (in der Tabelle mit »A« gegen zvsei Stämme geprüft, bezeichnet I mit dem bekannten l-Phen\l-hexadiin(2.4|-2-p-chlorobenzoylacetylcns (tested with "A" in the table against other strains, denotes I with the well-known l-phen \ l-hexadiyne (2.4 | -
21 184321 1843
7 I 7 I.
\ ettjünnuni!
1 : 3HKI I : Μ«»ι ·:5ιμΚλρ i.:5ülü«l i : 1 25« !KX! !; ft !K»! (KK' \ ettjünnuni!
1: 3HKI I: Μ «» ι ·: 5ιμΚλρ i.:5ülüri: 1 25 «! KX! !; ft! K »! (KK '
Candida albicansCandida albicans
A — — — — -■ τ r-rA - - - - - ■ τ r-r
Trich. mentagrophytesTrich. mentagrophytes
■J ; T■ J; T
- Kein \\',iL'hsium. - --- SchwjL'hes Wach^ium. - · - DculliL-hes Wachstum - -· - — Uniieiiemmlcs \V.ιι.·h^lum.- No \\ ', iL'hsium. - --- SchwjL'hes Wach ^ ium. - · - DculliL-hes growth - - · - - Uniieiiemmlcs \ V.ιι. · h ^ lum.
Die Tabelle zeigt die Überlegenheit der erfindungsüemiifkn Verbindung gegenüber der bekannten Verbindung.The table shows the superiority of the compound according to the invention over the known compound.
Claims (2)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712118437 DE2118437C3 (en) | 1971-04-16 | i-Isopropenyl-2-p-chlorobenzoylacetylene and process for its preparation | |
| CH626971A CH551355A (en) | 1971-04-16 | 1971-04-28 | PROCESS FOR THE PRODUCTION OF FUNGISTATICALLY AND BACTERIOSTATICALLY EFFECTIVE ACETYLENE COMPOUNDS. |
| CA112867A CA925101A (en) | 1970-05-30 | 1971-05-13 | Fungistatically and bacteriostatically effective acetylene compounds |
| ES391177A ES391177A1 (en) | 1970-05-30 | 1971-05-14 | Procedure for the preparation of acetylene compounds with fungistatic and bacteriostatic effect. (Machine-translation by Google Translate, not legally binding) |
| FR7117804A FR2100703A1 (en) | 1970-05-30 | 1971-05-17 | Acetylene deriv fungistat and bacteriostat for human pathogens |
| AT436671A AT315149B (en) | 1970-05-30 | 1971-05-19 | Process for the preparation of new ω-alkenylpropiolophenones |
| BE767684A BE767684A (en) | 1970-05-30 | 1971-05-26 | ACETYLENE DERIVATIVES WITH FUNGIST AND BACTERIOSTATIC EFFECT |
| US00147661A US3839455A (en) | 1971-04-16 | 1971-05-27 | Fungistatically and bacteriostatically active acetylene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712118437 DE2118437C3 (en) | 1971-04-16 | i-Isopropenyl-2-p-chlorobenzoylacetylene and process for its preparation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2118437A1 DE2118437A1 (en) | 1972-10-26 |
| DE2118437B2 DE2118437B2 (en) | 1975-06-12 |
| DE2118437C3 true DE2118437C3 (en) | 1976-01-22 |
Family
ID=
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