DE1082895B - Process for the preparation of peroxyphosphoric acid esters - Google Patents
Process for the preparation of peroxyphosphoric acid estersInfo
- Publication number
- DE1082895B DE1082895B DED30486A DED0030486A DE1082895B DE 1082895 B DE1082895 B DE 1082895B DE D30486 A DED30486 A DE D30486A DE D0030486 A DED0030486 A DE D0030486A DE 1082895 B DE1082895 B DE 1082895B
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- parts
- preparation
- peroxyphosphoric
- pyridine
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 5
- 150000004971 peroxyphosphoric acids Chemical class 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- -1 cycloalkyl radical Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 150000002432 hydroperoxides Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000005840 aryl radicals Chemical group 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- MPNNOLHYOHFJKL-UHFFFAOYSA-K peroxyphosphate Chemical compound [O-]OP([O-])([O-])=O MPNNOLHYOHFJKL-UHFFFAOYSA-K 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical group [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BNDUYVNXBZYPMZ-UHFFFAOYSA-N 1-[chloro-(4-methylphenoxy)phosphoryl]oxy-4-methylbenzene Chemical compound C1=CC(C)=CC=C1OP(Cl)(=O)OC1=CC=C(C)C=C1 BNDUYVNXBZYPMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NGFFLHMFSINFGB-UHFFFAOYSA-N [chloro(methoxy)phosphoryl]oxymethane Chemical compound COP(Cl)(=O)OC NGFFLHMFSINFGB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- PLWUSUOYTVTTNH-UHFFFAOYSA-M sodium;2-methyl-2-oxidooxypropane Chemical compound [Na+].CC(C)(C)O[O-] PLWUSUOYTVTTNH-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Verfahren zur Herstellung von Peroxyphosphorsäureestern Perester der Phosphorsäure (Peroxyphosphorsäureester) sind bisher noch nicht bekannt. Es wurde gefunden, daß man Perester der Phosphorsäure der allgemeinen Formel in welcher R ein Alkyl-, Aralkyl-, Cycloalkyl- oder Arylrest und R' ein Alkyl-, Aralkyl- oder Cycloalkylrest ist, erhalten kann, wenn man Phosphorsäureesterchloride der Formel - in geeigneter Weise mit Hydroperoxyden R'OOH zur Umsetzung bringt. Hierzu kann z. B. das Esterchlorid mit dem Alkalisalz des Hydroperoxydes in einem indifferenten Lösungsmittel zur Reaktion gebracht werden, wobei sich Alkalichlorid abscheidet. Dies wird abfiltriert und der Perphosphorsäureester aus der Lösung isoliert: Eine weitere Möglichkeit besteht im Umsatz des Phosphorsäureesterchlorides mit dem freien Alkylhydroperoxyd in Gegenwart eines Salzsäure bindenden Mittels, z. B. Pyridin: Die Peroxyphosphorsäureester sind teils angenehm riechende, flüssige Verbindungen, von denen die mit niedriger Kohlenstoffzahl im Vakuum destillierbar sind, teilweise kristalline, feste Verbindungen. Bei Zimmertemperatur sind sie weitgehend beständig. Sie zersetzen sich beim Überhitzen auf etwa 100"C lebhaft, sind aber nicht explosiv. Sie sind sehr hydrolyseempfindlich. In Wasser gehen sie schnell in Lösung, wobei die Peroxygruppe eine ionische Aufspaltung erfährt. Auch durch Alkalien werden die Peroxyphosphorsäureester rasch gespalten.Process for the preparation of peroxyphosphoric acid esters Peresters of phosphoric acid (peroxyphosphoric acid esters) are not yet known. It has been found that peresters of phosphoric acid of the general formula in which R is an alkyl, aralkyl, cycloalkyl or aryl radical and R 'is an alkyl, aralkyl or cycloalkyl radical, can be obtained if phosphoric acid ester chlorides of the formula - Bringing the reaction with hydroperoxides R'OOH in a suitable manner. For this purpose, z. B. the ester chloride can be reacted with the alkali salt of the hydroperoxide in an inert solvent, with alkali chloride separating out. This is filtered off and the perphosphoric acid ester is isolated from the solution: Another possibility is to react the phosphoric acid ester chloride with the free alkyl hydroperoxide in the presence of a hydrochloric acid binding agent, e.g. B. Pyridine: The peroxyphosphoric acid esters are partly pleasant-smelling, liquid compounds, of which those with a low carbon number can be distilled in vacuo, partly crystalline, solid compounds. They are largely stable at room temperature. They decompose vigorously on overheating to about 100 "C, but are not explosive. They are very sensitive to hydrolysis. They quickly dissolve in water, with the peroxy group undergoing ionic splitting. The peroxyphosphoric acid esters are also split rapidly by alkalis.
Peroxyphosphorsäureester vermögen die Polymerisation von Vinylverbindungen einzuleiten. Der dabei frei werdende Phosphorsäureesterrest verbleibt im Polymerisat und kann dessen Eigenschaften günstig beeinflussen. Peroxyphosphoric acid esters are capable of polymerizing vinyl compounds initiate. The phosphoric acid ester residue released remains in the polymer and can influence its properties favorably.
Beispiel 1 Diäthyl-(O-O-) -tert. -butyl-peroxyphosphat (C2H50)2P(O) OOC(CH3)3 In eine unter Kühlung bereitete Lösung von 8,62 Teilen Diäthylchlorophosphat in 20 Teilen trockenem Pyridin läßt man unter Eis-Kochsalz-Kühlung eine Lösung von 6,75 Teilen tert.-Butylhydroperoxyd in 10 Teilen getrocknetem Pyridin allmählich eintropfen. Die sofort auftretendeAbscheidungvon Pyridinhydrochlorid erreicht nach mehrstündigem Stehen bei Zimmertemperatur ihr Maximum. Nach dem Verdünnen mit etwa 50 Teilen Benzol wird der Niederschlag abfiltriert und das Filtrat nach mehrmaligem Ausschütteln mit gekühlter 2 n-H2 04, 50l,iger NaHCO3-Lösung, schließlich mit Eiswasser gewaschen. Dann wird getrocknet und vom Lösungsmittel befreit. Wenn aus dem dabei erhaltenen öligen Rückstand die bei 1 Torr bis etwa 25"C flüchtigen Anteile abgetrieben sind, verbleiben 9,5 Teile. Peroxyphosphat (= 84°/o der Theorie), das mit Kp. 3,10-3 = 53 bis 54°C destillierbar ist. Es ist eine angenehm riechende, farblose und bei Zimmertemperatur weitgehend beständige Flüssigkeit. Example 1 Diethyl (O-O-) -tert. -butyl peroxyphosphate (C2H50) 2P (O) OOC (CH3) 3 In a solution of 8.62 parts of diethyl chlorophosphate prepared with cooling a solution of is allowed in 20 parts of dry pyridine while cooling with ice and sodium chloride 6.75 parts of tert-butyl hydroperoxide in 10 parts of dried pyridine gradually a drop. The instantaneous deposition of pyridine hydrochloride reaches after standing for several hours at room temperature its maximum. After diluting with about 50 parts of benzene, the precipitate is filtered off and the filtrate after several times Shake out with cooled 2N H2 04, 50l, NaHCO3 solution, finally with ice water washed. It is then dried and freed from the solvent. If from that The oily residue obtained, which is volatile at 1 torr to about 25 ° C., is driven off 9.5 parts remain. Peroxyphosphate (= 84% of theory), which has a boiling point of 3.10-3 = 53 to 54 ° C can be distilled. It is a pleasant smelling, colorless and at Liquid largely stable at room temperature.
Beispiel 2 Das Peroxyphosphat des Beispiels 1 wird auch erhalten, wenn man zu einer ätherischen Suspension von Natriumtert.-butylperoxyd eine ätherische Lösung des Chlorophosphats im Mengenverhältnis des Beispiels 1 unter Kühlung mit Eiswasser allmählich zutropfen läßt, vom ausgeschiedenen NaCl abfiltriert und die ätherische Lösung im Vakuum unter Feuchtigkeitsausschluß eindampft. Example 2 The peroxyphosphate of Example 1 is also obtained if one turns to an ethereal suspension of sodium tert-butyl peroxide an essential Solution of the chlorophosphate in the quantitative ratio of Example 1 below cooling gradually added dropwise with ice water, filtered off from the precipitated NaCl and the ethereal solution evaporates in vacuo with exclusion of moisture.
Beispiel 3 Dimethyl- (O-O-)-tert.-butyl-peroxyphosphat (CH3O)2P(O) OOC(CH3)3 Werden entsprechend der Arbeitsweise gemäß Beispiel 1 2,2 Teile Dimethylchlorophosphat in 10 Teilen Pyridin mit 2,1 Teilen tert.-Butyl-hydroperoxyd in 5 Teilen Pyridin zur Umsetzung gebracht und analog aufgearbeitet, dann erhält man 1,3 Teile (= 430/, der Theorie) eines zunächst öligen Peroxyphosphates, das bei tieferen Temperaturen fest wird und nach dem Umkristallisieren aus Benzin einen F. = 24 bis 25"C besitzt. Example 3 Dimethyl (O-O -) - tert-butyl peroxyphosphate (CH3O) 2P (O) OOC (CH3) 3 are 2.2 parts of dimethyl chlorophosphate in accordance with the procedure of Example 1 in 10 parts of pyridine with 2.1 parts of tert-butyl hydroperoxide in 5 parts of pyridine brought to implementation and worked up analogously, then 1.3 parts are obtained (= 430 /, theory) of an initially oily peroxyphosphate, which at lower temperatures becomes solid and has an F. = 24 to 25 "C after recrystallization from gasoline.
Beispiel 4 Ditoluyl-(O-O-) -tert.-butyl-peroxyphosphat (CH3. C6H4O)2P(O) OoC(cH2)3 Werden entsprechend der Arbeitsweise gemäß Beispiell 4,5 Teile Di-p-toluylchlorophosphat (Kp.101 = 160 bis 1650C in 10 Teilen Pyridin mit 2,1 Teilen tert.-Butylhydroperoxyd in 5 Teilen Pyridin zur Umsetzung gebracht und nach dem Verdünnen mit Benzol das entstandene Pyridinhydrochlorid abfiltriert, so erhält man nach dem Ausschütteln des überschüssigen Pyridins eine benzolische Lösung des Peroxyphosphates, das beim Abdampfen des Lösungsmittels im Vakuum als farblose Flüssigkeit hinterbleibt. Example 4 Ditoluyl- (O-O-) -tert-butyl-peroxyphosphate (CH3. C6H4O) 2P (O) OoC (cH2) 3 become 4.5 parts of di-p-toluyl chlorophosphate according to the procedure according to example (Bp 101 = 160 to 1650C in 10 parts of pyridine with 2.1 parts of tert-butyl hydroperoxide brought in 5 parts of pyridine to react and after diluting with benzene that The resulting pyridine hydrochloride is filtered off, so one obtains after shaking out of the excess pyridine a benzene solution of the peroxyphosphate, which with Evaporation of the solvent in vacuo remains as a colorless liquid.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED30486A DE1082895B (en) | 1959-04-21 | 1959-04-21 | Process for the preparation of peroxyphosphoric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED30486A DE1082895B (en) | 1959-04-21 | 1959-04-21 | Process for the preparation of peroxyphosphoric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1082895B true DE1082895B (en) | 1960-06-09 |
Family
ID=7040519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED30486A Pending DE1082895B (en) | 1959-04-21 | 1959-04-21 | Process for the preparation of peroxyphosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1082895B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1518740B1 (en) * | 1965-01-08 | 1972-06-29 | Peroxid Chemie Gmbh | Process for the preparation of percarboxylic acid tert-butyl esters |
| US20240018173A1 (en) * | 2022-07-15 | 2024-01-18 | Entegris, Inc. | Process for preparing phosphonate esters |
-
1959
- 1959-04-21 DE DED30486A patent/DE1082895B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1518740B1 (en) * | 1965-01-08 | 1972-06-29 | Peroxid Chemie Gmbh | Process for the preparation of percarboxylic acid tert-butyl esters |
| US20240018173A1 (en) * | 2022-07-15 | 2024-01-18 | Entegris, Inc. | Process for preparing phosphonate esters |
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