DE727406C - Process for the preparation of acidic phosphoric acid esters of phenols - Google Patents
Process for the preparation of acidic phosphoric acid esters of phenolsInfo
- Publication number
- DE727406C DE727406C DER100064D DER0100064D DE727406C DE 727406 C DE727406 C DE 727406C DE R100064 D DER100064 D DE R100064D DE R0100064 D DER0100064 D DE R0100064D DE 727406 C DE727406 C DE 727406C
- Authority
- DE
- Germany
- Prior art keywords
- phenols
- phosphoric acid
- acid esters
- esters
- preparation
- 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
- 150000002989 phenols Chemical class 0.000 title claims description 19
- 230000002378 acidificating effect Effects 0.000 title claims description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 3
- -1 phosphorus halides Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 229910000147 aluminium phosphate Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- AFFXNOIULZQAML-UHFFFAOYSA-N 4-chloro-2-methyl-5-propan-2-ylphenol Chemical compound CC(C)C1=CC(O)=C(C)C=C1Cl AFFXNOIULZQAML-UHFFFAOYSA-N 0.000 description 2
- KFZXVMNBUMVKLN-UHFFFAOYSA-N 4-chloro-5-methyl-2-propan-2-ylphenol Chemical compound CC(C)C1=CC(Cl)=C(C)C=C1O KFZXVMNBUMVKLN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229940031956 chlorothymol Drugs 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940070805 p-chloro-m-cresol Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Verfahren zur Herstellung saurer Phosphorsäureester von Phenolen Die vorliegende Erfindung betrifft die Herstellung antibakterieller Verbindungen, und zwar handelt @es sich um ein Verfahren zur Herstellung saurer PhosphorsäuTeester von Phenolen, bei dem man alkyherte Phenole, die noch Halogen im Kern enthalten, mit Phosphorhalogeniden umsetzt und die entstehenden wasserunlöslichen Halogenide hydxolysiert oder neutrale Ester aus Halogen im Kern jenthaltenden alkylierten Phenolen und Phosphorsäure teilweise verseift.Process for the preparation of acidic phosphoric acid esters of phenols The present invention relates to the preparation of antibacterial compounds, and @it is a process for the production of acidic phosphoric acid esters of phenols, in which one uses alkylated phenols that still contain halogen in the nucleus, with phosphorus halides and the resulting water-insoluble halides hydroxolyzed or neutral esters of halogen in the nucleus j-containing alkylated phenols and phosphoric acid partially saponified.
Es -ist . bekannt, daß neutrale Ester.- organischer oder auch anorganischer Säuren mit Phenolen nur selten die Phenolwirkun,g vollständig, sondern häufiger in. mehr oder minder ,geschwächtem Zustande zeigen. So finden z. B. die Kohlensäureester und B@enzo,esäuxieester von Phenolen, wie Guajakol, praktische Verwendung für Desinfektionszwecke. Auch: das Chlorcarvacrolca;rbonat ist bereits zur Verwendung als antibakterielles Mittel vorgeschlagen. worden. Im Gegensatz hierzu ist aber .auch bekannt, da.ß saure Phenolester und deren Salze die physiologische Wirkung der Phenale auf die Kleinlebewesen nicht besitzen und daher als Desinfektionsmittel praktisch keine Verwendung finden. Es sei daran erinnert, daß der lebende Organismus Phenole durch Umwandlung in saure Phenolestcr bzw. deren Salze; zuentgiften vermag.It is . known that neutral esters - organic or inorganic Acids with phenols rarely have the phenol effect completely, but more frequently show in more or less weakened condition. So find z. B. the carbonic acid esters and B @ enzo, esäuxie esters of phenols such as guaiacol, practical use for disinfecting purposes. Also: the Chlorcarvacrolca; rbonat is already for use as an antibacterial Funds proposed. been. In contrast to this, it is also known that it is acidic Phenol esters and their salts affect the physiological effect of phenals on small organisms do not have and therefore find practically no use as a disinfectant. It should be remembered that the living organism converts phenols into acidic ones Phenol esters or their salts; able to detoxify.
Es zeigte sich nun überraschenderweise, daß es eine ganze Reihe saurer Ester der Phosphorsäure reit Phenolen gibt, die als solche oder in Form der Salze eine ,ganz ausgezeichnete .antibakterielle Wirkung zeigen.Surprisingly, it turned out to be a whole lot more acidic Phosphoric acid esters are phenols, as such or in the form of salts show a very excellent antibacterial effect.
Es sind zwar bereits saure Phosphorsäureester von- Phenolen bekannt. Für die Verwendung als Desinfektionsmittel haben diese aber entweder keine genügende Löslichkeit, oder sie erwiesen sich als nicht .ausreichend wirksam. Praktisch brauchbare Verbindungen dieser Art müssen nach der Erkenntnis des Erfinders bestimmte konstitutive Eigenarten zeigen. Diese Erkenntnis bildet den Gegenstand. der v erliegenden, Erfindung.Acid phosphoric acid esters of phenols are already known. For use as a disinfectant, however, these are either not sufficient Solubility, or they turned out to be insufficiently effective. Practically useful According to the knowledge of the inventor, compounds of this kind must have certain constitutive elements Show idiosyncrasies. This knowledge forms the object. of the present invention.
räch der vorliegenden Erfindung -erhält man solche ,antibakteriell höchst wirksamen sauren Ester bzw. deren Salze .durch Kombination von r Mol Phosphorsäure mit r oder 2 Molekülen eines Phenols, welches im Molekül mindestens eine Alkylgruppe und mindestens ein Halogenatom enthält. Zu solchen. Verbindungen kommt man am einfachsten, indem man Phosphorhalo;genide mit einem überschuß an den betreffenden Phenolen umsetzt und die entstehenden wasserunlöslichen Halogenide hydrolysiert oder die entsprechenden neutralen Ester teilweise verseift. Besonders brauchbare Ester erzielt man z. B. aus Chlorthymol und Chlorcarvacrol. Die chlorhaltigen Verbindungen dieser Art sind erheblich wirksamer ,als die bekannten halogenfreien z. B. der österreichischen Patentschrift 140 864.According to the present invention, antibacterial ones are obtained highly effective acidic esters or their salts by combining r moles of phosphoric acid with r or 2 molecules of a phenol which has at least one alkyl group in the molecule and contains at least one halogen atom. To such. Connections are easiest to come by by reacting phosphorus halides with an excess of the phenols in question and hydrolyzed the resulting water-insoluble halides or the corresponding neutral ester partially saponified. Particularly useful esters are obtained, for. B. from chlorothymol and chlorocarvacrol. The chlorine-containing compounds are of this type considerably more effective than the known halogen-free z. B. the Austrian Patent specification 140 864.
Die sekundären Phosphorsäureester der genannten Phenole zeichnen sich, abgesehen von ihrer starken Desinfektionswirkung, durch weitere technisch wichtige Eigenschaften ihrer Alkalisalze aus. Dia diese sowohl in Wasser als auch in Mitteln von Lipoidcharakter löslich sind, eignen sie sich sowohl zum Keimfreimachen freimachen von iväßri,gen als_ uch von nichtwäßri,gen Medien, wie Viietteri und ölen. Außerdem zeigen säe ganz ,ausgespro:chene lyotrope Eigenschaften und sind daher imstande, solche Stoffe, die in Wassier nicht oder nur schwer löslich sind, wasserlöslich zu machen, wenn man sie- als Lösungspartner verwendet. So lösen sich z. B. unlösliche Phenole in Wasser auf, wenn man sie mit deal genannten sekundären Phosphorsäureestersalzen mischt. Besonders wichtig ist hierbei, daß die Wirkung der Phenole durch die zugesetzten Lösungspartner nicht vermindert wird, wie es z. B. bei Verwendung von Seifen als Lösungspartner der Fall ist. Beispiele i. 1/2a Mol Trichlorthymolphosphorsäureester (Schmp. 84°) wird in Alkohol ,gelöst und nach Zugabe von. 1/2o MG' Kaliumhydroxyd i o Stunden lang zum Sieden erhitzt. Dann wird der Alkohol verdampft, der RÜckstand in Wasser aufgenommen und die Lösung vom ahgestaltenen Chlorthymol abgetrennt. Aus der Lösung scheidet man das bis-chlorthymolphosphorsaure Kalium durch Aussalzen mit Kaliumcarbonat .aus und nimmt -es in Äther auf. Beim Abdampfen des Äthers scheidet es sich als feste Masse aus und kann durch Kristallisieren aus Äther-Petroläther rein erhalten werden. Die freie Bis-Chlorthymalpho-sphorsäure ist in Wasser kaum löslich, ihr Schmelzpunkt liegt bei i34°.The secondary phosphoric acid esters of the phenols mentioned are characterized apart from their strong disinfecting effect, through others technically important properties of their alkali salts. Dia these both in water and are soluble in agents of lipoid character, they are suitable both for Germ-freeing, freeing of both aqueous and non-aqueous media, such as Viietteri and oils. In addition, seeds show very pronounced lyotropic properties and are therefore able to dissolve such substances, which are insoluble or only sparingly soluble in water are to be made water-soluble if they are used as a solution partner. So solve z. B. Insoluble phenols in water if you deal with them called secondary Mixing phosphoric ester salts. It is particularly important that the effect the phenols is not reduced by the added solution partner, as z. B. is the case when using soaps as a solution partner. Examples i. 1 / 2a Mol trichlorothymol phosphoric acid ester (melting point 84 °) is dissolved in alcohol and after Adding. 1 / 2o MG 'potassium hydroxide heated to the boil for 10 hours. Then it will be the alcohol evaporates, the residue taken up in water and the solution of the ahgestaltenen Separated chlorothymol. The bis-chlorothymolphosphoric acid is separated from the solution Potassium is extracted by salting out with potassium carbonate and takes it up in ether. At the Evaporation of the ether separates it as a solid mass and can crystallize can be obtained pure from ether-petroleum ether. The free bis-chlorothymalphosphoric acid is hardly soluble in water, its melting point is i34 °.
2. 309 5-Chlorcarvacrol und i 5 ,g Phosphoroxychlorid werden langsam auf 13o° erwärmt und 3 Stunden bei dieser Temperatur gehalten. - Der Gefäßinhalt wird dann einer fraktionierten Destillation unterworfen, wobei das Monochlorcarvacrolphosphorsäu:redichlorid bei o,6 mm bei 123 bis i25° und das Bis-Chlorcarvacrolphosphorsäuremonochlorid bei o,6 m,m bei i 9o bis i g--' destilliert. Die Ausbeute an Dichlorid beträgt z. B. 5 g, an Monochlorid z. B. 24,g.2. 309 of 5-chlorocarvacrol and 1.5 g of phosphorus oxychloride are slowly warmed to 130 ° and kept at this temperature for 3 hours. - The contents of the vessel are then subjected to a fractional distillation, the monochlorocarvacrolphosphoric acid: redichloride at 0.6 mm at 123 to i25 ° and the bis-chlorocarvacrolphosphoric acid monochloride at 0.6 m, m at i 9o to i g-- '. The yield of dichloride is z. B. 5 g, of monochloride z. B. 24, g.
Die Chloridee werden mit Wasser zersetzt, das Reaktionsprodukt in Soda ,gelöst, die Lösung ausgeäthert und mit Salzsäure gefüllt. Die Monochlo@rcarvacrolphosphorsäure fällt dabei direkt kristallinisch aus, sie zeigt den Schmp. i48°. Die Bis-ChlorcarvacrolphosphorsäuTe kristallisiert jedoch nicht, ihr Natriumsalz zeigt die Eigenschaft, in Äther löslich zu sein.The chlorides are decomposed with water, the reaction product in Soda, dissolved, the solution etherified and filled with hydrochloric acid. The monochlorocarvacrolphosphoric acid precipitates directly in crystalline form, it shows the melting point i48 °. The bis-chlorocarvacrolphosphoric acid does not crystallize, however, its sodium salt shows the property of being soluble in ether to be.
3. 56g p-Chlor-m-kresolwerden mit 38,59 Phosphoroxychlorid bei Gegenwart von wenig Aluminiumchlorid 3 Stunden zu schwachem Sieden erhitzt. Das Gemisch wird in Hochvakuum fraktioniert. Man.erhält iogMonochlorkresolphosphorsäuredichlorid (KP., --- 95 °) und 40g Bis-Chlorkresolphosphorsäuremonochlorid (KP.., = i70°). Durch Behandeln der Chloride mit heißem Wasser entsteht die Monochlorkresolphosphorsäure (Schmp. 13i°) bzw. die Bis-Chlorkresolphosphorsäure vom Schmp. i 16'. 3. 56 g of p-chloro-m-cresol are heated to a gentle boil for 3 hours with 38.59 phosphorus oxychloride in the presence of a little aluminum chloride. The mixture is fractionated in a high vacuum. One receives iog-monochlorocresol phosphoric acid dichloride (KP., --- 95 °) and 40g bis-chlorocresol phosphoric acid monochloride (KP .., = i70 °). Treatment of the chlorides with hot water produces monochlorocresol phosphoric acid (melting point 13 °) or bis-chlorocresol phosphoric acid with melting point i 16 '.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER100064D DE727406C (en) | 1935-10-31 | 1935-10-31 | Process for the preparation of acidic phosphoric acid esters of phenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER100064D DE727406C (en) | 1935-10-31 | 1935-10-31 | Process for the preparation of acidic phosphoric acid esters of phenols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE727406C true DE727406C (en) | 1942-11-02 |
Family
ID=7420288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER100064D Expired DE727406C (en) | 1935-10-31 | 1935-10-31 | Process for the preparation of acidic phosphoric acid esters of phenols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE727406C (en) |
-
1935
- 1935-10-31 DE DER100064D patent/DE727406C/en not_active Expired
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