DE556145C - Process for the preparation of organic phosphorus compounds - Google Patents
Process for the preparation of organic phosphorus compoundsInfo
- Publication number
- DE556145C DE556145C DE1930556145D DE556145DD DE556145C DE 556145 C DE556145 C DE 556145C DE 1930556145 D DE1930556145 D DE 1930556145D DE 556145D D DE556145D D DE 556145DD DE 556145 C DE556145 C DE 556145C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- phosphorus compounds
- organic phosphorus
- phenol
- phosphorus oxychloride
- 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
- 150000002903 organophosphorus compounds Chemical class 0.000 title claims description 3
- 238000000034 method Methods 0.000 title description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic amino acid esters Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002357 guanidines Chemical class 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- UUOIRJWYUOKWPV-UHFFFAOYSA-N (diaminomethylideneamino) dihydrogen phosphate Chemical compound NC(N)=NOP(O)(O)=O UUOIRJWYUOKWPV-UHFFFAOYSA-N 0.000 description 1
- ZSIAANIILFGLQH-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 ZSIAANIILFGLQH-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- RCHVMFNYFYQEMB-UHFFFAOYSA-N ctk0h8384 Chemical class NPCl RCHVMFNYFYQEMB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- HIPLEPXPNLWKCQ-UHFFFAOYSA-N fosfocreatinine Chemical compound CN1CC(=O)N=C1NP(O)(O)=O HIPLEPXPNLWKCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
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 Darstellung organischer Phosphorverbindungen Bekanntlich entsteht bei der Einwirkung von Phosphoroxychlorid auf Phenol eine Verbindung, die bei geeigneter Behandlung mit Ammoniak in den Diphenylester. der Aminophosphorsäure übergeht. Bei dieser Reaktion tritt als Zwischenprodukt ein halogenierter Phosphorsäureester auf, dessen Halogen später mit Ammoniak reagiert. Es ist auch die Herstellung von Aminoderivaten des Phosphorsäurediphenylesters durch Umsetzen von Benzylamin bzw. Piperidin mit Diphenylphosphorsäurechlorid bekannt.Process for preparing organic phosphorus compounds is known The action of phosphorus oxychloride on phenol creates a compound that with suitable treatment with ammonia into the diphenyl ester. of aminophosphoric acid transforms. A halogenated phosphoric acid ester occurs as an intermediate in this reaction whose halogen later reacts with ammonia. It is also the making of Amino derivatives of the phosphoric acid diphenyl ester by reacting benzylamine or Piperidine known with diphenylphosphoric acid chloride.
Diese Umsetzung läßt sich auch auf aliphatische Amine übertragen;. Man erhält auf diese Weise Diarylester von Aminophosphorsäuren, die bereits auf anderem Wege, nämlich durch Umsetzen von Aminochlorphosphinen mit Phenolen, erhalten worden sind. Auf Aminosäuren ließ sich die Reaktion jedoch nicht übertragen.This conversion can also be applied to aliphatic amines. In this way, diaryl esters of aminophosphoric acids which are already on other way, namely by reacting aminochlorophosphines with phenols obtained have been. However, the reaction could not be transferred to amino acids.
Es wurde nun gefunden, daß man auch phosphory lierte Aminosäuren erhalten kann, wenn man Aminosäureester mit dem Einwirkungsprodukt von Phosphoroxychlorid auf ein Phenol zur Reaktion bringt und das Reaktionsprodukt verseift. Ebenso lassen sich auch Guanidine mit dem Einwirkungsprodukt von Phosphoroxychlorid mit Phenol zur Reaktion bringen. Die auf diese Weise erhältlichen aliphatisch substituierten Aminophosphorsäuren sind deshalb von besonderer Wichtigkeit, weil sie ihrer Konstitution nach Stoffen nahestehen, die wie die Kreatininphosphorsäure im Muskelstoffwechsel eine große Rolle spielen. Das Verfahren ist deshalb für die Synthese solcher Naturstoffe von großer Bedeutung.It has now been found that phosphorylated amino acids are also obtained can, if one amino acid esters with the action product of phosphorus oxychloride reacts on a phenol and saponifies the reaction product. Likewise let also guanidines with the action product of phosphorus oxychloride with phenol to react. The aliphatically substituted ones obtainable in this way Aminophosphoric acids are of particular importance because of their constitution are related to substances like creatinine phosphoric acid in muscle metabolism play a major role. The process is therefore suitable for the synthesis of such natural products of great importance.
Beispiel r Läßt man auf 2 Mol Phenol i Mol Phosphoroxychlorid unter Erwärmen am Rückfiußkühler so lange einwirken, bis keine Salzsäure mehr entweicht, verdünnt das Reaktionsgemisch nach Abkühlen mit etwa Zoo ccm absolutem Alkohol und setzt unter Kühlung eine alkoholische Lösung von 2,1 Mol Glykolläthylester hinzu, so scheidet sich beim Eingießen in Wasser die Verbindung (CQH50)2 #PO # N14 # CII2.# COOCEHS als öl ab, welche nach Ausäthern im Exsikkator nach einiger Zeit kristallisiert. Umkristallisiert aus Äther zeigt sie den Schmelzpunkt 760. Example r If 1 mole of phosphorus oxychloride is allowed to act on 2 moles of phenol while heating on a reflux condenser until no more hydrochloric acid escapes, the reaction mixture is diluted after cooling with about zoo cc of absolute alcohol and an alcoholic solution of 2.1 moles of glycol ethyl ester is added with cooling , the compound (CQH50) 2 #PO # N14 # CII2. # COOCEHS separates out as an oil when it is poured into water, which crystallizes after some time after etherification in the desiccator. Recrystallized from ether, it has a melting point of 760.
Beispiele 3i g Phosphoroxychlorid werden mit 38 g Phenol erhitzt, bis keine Salzsäure mehr entweicht. Das Reaktionsgemisch wird nach Abkühlen mit Äthanol verdünnt und mit einer alkoholischen Lösung von Guanidin neutralisiert. Beim Eingießen in Wasser fällt ein 01 aus, das nach Abtrennung im Vakuumexsikkator nach einiger Zeit kristallisiert. Umkristallisiert aus Benzol zeigt der erhaltene Guanidinophosphorsäurediphenylester (C,H50)2 # PO # NH # CNH NH2 den Schmelzpunkt i18°. Beim Verseifen erhält man die Guanidinophosphorsäure. De= Ester ist löslich in Äthanol, Methanol, Aceton, Chloroform, Essigäther, schwerer in Benzol, Toluol, unlöslich 'in.Wasser und Petroläther.EXAMPLES 31 g of phosphorus oxychloride are heated with 38 g of phenol until no more hydrochloric acid escapes. After cooling, the reaction mixture is diluted with ethanol and neutralized with an alcoholic solution of guanidine. When pouring in water 01 falls out, which crystallizes after separation in a vacuum after some time. Recrystallized from benzene, the diphenyl guanidinophosphate (C, H50) 2 # PO # NH # CNH NH2 obtained has a melting point of 18 °. The guanidinophosphoric acid is obtained during saponification. De = ester is soluble in ethanol, methanol, acetone, chloroform, acetic ether, more difficult in benzene, toluene, insoluble in water and petroleum ether.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE556145T | 1930-01-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE556145C true DE556145C (en) | 1932-08-03 |
Family
ID=6564666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1930556145D Expired DE556145C (en) | 1930-01-22 | 1930-01-22 | Process for the preparation of organic phosphorus compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE556145C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2995596A (en) * | 1956-09-01 | 1961-08-08 | Benckiser Gmbh Joh A | Production of phosphoric aciddialkylester-amines |
-
1930
- 1930-01-22 DE DE1930556145D patent/DE556145C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2995596A (en) * | 1956-09-01 | 1961-08-08 | Benckiser Gmbh Joh A | Production of phosphoric aciddialkylester-amines |
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