DE1923103B2 - O, O-DIALKYL-O- (3-OXO-2-ALKYL-1CYCLOPENTENYL) -PHOSPHATE, PROCESS FOR THE PREPARATION AND AGENTS CONTAINING THESE - Google Patents

O, O-DIALKYL-O- (3-OXO-2-ALKYL-1CYCLOPENTENYL) -PHOSPHATE, PROCESS FOR THE PREPARATION AND AGENTS CONTAINING THESE

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Publication number
DE1923103B2
DE1923103B2 DE19691923103 DE1923103A DE1923103B2 DE 1923103 B2 DE1923103 B2 DE 1923103B2 DE 19691923103 DE19691923103 DE 19691923103 DE 1923103 A DE1923103 A DE 1923103A DE 1923103 B2 DE1923103 B2 DE 1923103B2
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Prior art keywords
oxo
phosphate
alkyl
methyl
dialkyl
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DE19691923103
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DE1923103A1 (en
Inventor
Daniel Dr Montrouge Perronnet Jacques Pans Bertin, (Frankreich)
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Sanofi Aventis France
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Roussel Uclaf SA
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • 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
    • C07F9/117—Esters of phosphoric acids with cycloaliphatic alcohols
    • 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
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • 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
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/177—Esters of thiophosphoric acids with cycloaliphatic alcohols
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
    • C07F9/657118—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

(D(D

in der R1 C,-C4-Alkyl und R2 Methyl. Äthyl oder i-Propyl darstellt.in which R 1 is C, -C 4 -alkyl and R 2 is methyl. Represents ethyl or i-propyl.

2.0,O-Dimethyl-O-(3-oxo-2-methyl-cyclopenten-1 -yl)-phosphat.2.0, O-dimethyl-O- (3-oxo-2-methyl-cyclopentene-1 -yl) phosphate.

3.0,O - Diäthyl - O - (3 - oxo - 2 - methyl - cyclopenten-l-yl)-phosphat. 3.0, O - diethyl - O - (3 - oxo - 2 - methyl - cyclopenten-l-yl) phosphate.

4. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß man ein Phosphorsäurehalogenid der Formel in der Hai ein Brom- oder Chloratom bedeutet, in Gegenwart eines basischen Mittels mit einem Cyclopentanderivat der allgemeinen Formel4. Process for making the compounds according to claim 1, characterized in that a phosphoric acid halide of the formula in which Hai means a bromine or chlorine atom, in the presence of a basic agent with a cyclopentane derivative the general formula

(III)(III)

P —HaiP - shark

(H)(H)

R1OR 1 O

in der Hai ein Brom- oder Chloratom bedeutet, in Gegenwart eines basischen Mittels mit einem Cyclopentanderivat der allgemeinen Formelin which Hai means a bromine or chlorine atom, in the presence of a basic agent with a Cyclopentane derivative of the general formula

R2 OR 2 O

V-/V- /

an)at)

umsetzt.implements.

5. Pestizides Mittel, enthaltend mindestens eine Verbindung nach Anspruch 1 als Wirkstoff.5. A pesticidal agent containing at least one compound according to claim 1 as an active ingredient.

Die Erfindung betrifft O,O-Dialkyl-O-(3-oxo-2-alkyl-l-cyclo-pentenyl)-phosphate der allgemeinen Formel IThe invention relates to O, O-dialkyl-O- (3-oxo-2-alkyl-1-cyclo-pentenyl) phosphates of the general formula I.

R1O OR 1 OO

\t
P-O \ t
PO

R1OR 1 O

R2 OR 2 O

(D(D

in der R1 C,-C4-Alkyl und R2 Methyl, Äthyl oder i-Propyl darstellt.in which R 1 is C, -C 4 -alkyl and R 2 is methyl, ethyl or i-propyl.

Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung dieser Verbindungen (dargestellt im Reakiionsschema 1), das dadurch gekennzeichnet ist, daß umsetzt.The invention also relates to a process for the preparation of these compounds (shown in the reaction scheme 1), which is characterized in that converts.

Gegenstand der Erfindung sind ferner pestizide Mi^-I. die als Wirkstoff mindestens eine dieser Ye: bindungen enthalten.The invention also relates to pesticidal Mi ^ -I. which as an active ingredient at least one of these Ye: bindings included.

Die Insektiziden Eigenschaften der erfindunustie-The insecticidal properties of the invention

mäßen Verbindungen können durch Versuche mii Calandra granaria (schwarzer Kornwurm! Blattlau-.Appropriate connections can be made by experiments Calandra granaria (black corn worm! Aphid.

Fliege und Schabe gezeigt werden und ihre akariziden Eigenschaften durch Tests mit Tetranychus.Fly and cockroach are shown and their acaricides Properties by testing with Tetranychus.

Die pestiziden Zusammensetzungen, die die erfindungsgemäßen Verbindungen enthalten, können na mentlich in Form von Pudern, Granulaten. Suspcn sionen. Emulsionen oder Lösungen vorliegen. Die Gebrauchsdosen der erfindungsgemäßen Verbindungen sind in Abhängigkeit von den zu vernichtenden Tierarten, den zu behandelnden Pflanzen, den klimatischen Bedingungen zu variieren. Sie können namentlich mit Wasser, Alkohol, Kohlenwasserstoffen oder anderen organischen Lösungsmitteln, Mineralölen. tierischen oder pflanzlichen ölen oder mit Pudern, wie Ta'k, Tonerden. Silicaten, Kieselgur und mit anionischen, kationischen oder nichtionischen oberflächenaktiven Mitteln vermischt werden. Sie können ebenfalls einem oder mehreren pestiziden Wirkstoffen und Substanzen mit einer Wirkung auf das Pflanzenwachstum beigemischt werden.The pesticidal compositions containing the compounds of the invention can na mostly in the form of powders, granules. Suspensions. Emulsions or solutions are present. the Usage doses of the compounds according to the invention are dependent on those to be destroyed Animal species, the plants to be treated, the climatic Conditions to vary. You can name with water, alcohol, hydrocarbons or other organic solvents, mineral oils. animal or vegetable oils or with powders, like Ta'k, clays. Silicates, kieselguhr and with anionic, cationic or nonionic surfactants are mixed. You can also one or more pesticidal active ingredients and substances with an effect on plant growth be mixed in.

Die Kondensation des Phosphor .,äurehalogenids(II) mit dem Cyclopentanderivat (111) wird vorteilhafterweiöe in Gegenwart eines basischen Mittels, insbesondere in Gegenwart einer tertiären Base, wie Pyridin oder Triäthylamin, in einem organischen Lösungsmittel, wie Tetrahydrofuran oder Benzol, durchgeführt.The condensation of phosphorus, acid halide (II) with the cyclopentane derivative (111) is advantageously in the presence of a basic agent, especially in the presence of a tertiary base such as Pyridine or triethylamine, in an organic solvent such as tetrahydrofuran or benzene, carried out.

Die erfindungsgevnäßen Verbindungen I können auch durch eine Umsetzung von der Art der »Perkow«- Reaktion gemäß dem Reaktionsschema 2 erhalten werden, indem man ein Trialkylphosphit mit einem 2-R2-2-Hal-cyclopenlan-l,3-dion umsetzt, wobei Hai ein Chlor- oder Bromatom darstellt.The compounds I according to the invention can also be obtained by a reaction of the "Perkow" type reaction according to reaction scheme 2, by reacting a trialkyl phosphite with a 2-R 2 -2-halocyclopenlan-1,3-dione, with Hai represents a chlorine or bromine atom.

Die in 2-Stellung durch einen Alkylrest substituierten Cyclopentandione können beispielsweise nach dem in der belgischen Patentschrift 647 U79 beschriebenen Verfahren hergestellt werden.Those substituted in the 2-position by an alkyl radical Cyclopentanediones can, for example, according to that described in Belgian patent specification 647 U79 Process are produced.

Die Halogenide von Phosphorsäure-O,O-diestern(I I) können unlerAnwendungderin Houben-W e y I, Methoden der Organischen Chemie, Bd. 12/2, Aufl. 1964, S. 274 bis 297 und insbesondere S. 290 bis 292, beschriebenen Methoden, insbesondere durch Einwirkung eines Halogenisierungsmittels, wie Chlor, Sulfurylchlorid, auf einen passend gewählten Phos-The halides of phosphoric acid O, O-diesters (I. I) can be used by Houben-W e y I, Methods of Organic Chemistry, Vol. 12/2, Aufl. 1964, pp. 274 to 297 and in particular pp. 290 to 292, methods described, in particular by the action of a halogenating agent such as chlorine, Sulfuryl chloride, on a suitably selected phosphor

phorsäure-O,O-diester oder durch Einwirkung von Phosphoroxychlorid auf einen passenden Alkohol oder auch durch Einwirkung von Sulfurylchlorid auf ein Alkylphosphit, das in situ im Reaktionsmilieu gebildet werden kann, hergestellt werden.phosphoric acid-O, O-diester or by the action of Phosphorus oxychloride on a suitable alcohol or by the action of sulfuryl chloride an alkyl phosphite which can be formed in situ in the reaction medium can be prepared.

Herstellung von Ο,Ο-DimethylchlorphosphatProduction of Ο, Ο-dimethyl chlorophosphate

In 67 g Sulfurylchlorid trägt man bei 0=C unter Stickstoffatmosphäre eine Mischung aus 62 g Trimethylphosphit und 70 ecm Petroläther (Siedepunkt 35 bis 70DC) ein und rührt 17 Stunden lang bei Raumtemperatur. Nach der Entfernung der flüchtigen Anteile durch Destillation unter vermindertem Druck rektifiziert man im Vakuum und erhält 55 g O,O-Dimethyi-chlorphosphat. Siedepunkt = 26° C unter (J. 1 Tcirr:«-: = 1,4120.In 67 g of sulfuryl chloride, a mixture of 62 g of trimethyl phosphite and 70 cc of petroleum ether contributes = 0 C under a nitrogen atmosphere (b.p. 35 to 70 D C) and stirred for 17 hours at room temperature. After the volatile components have been removed by distillation under reduced pressure, rectification is carried out in vacuo and 55 g of O, O-dimethylchlorophosphate are obtained. Boiling point = 26 ° C below (J. 1 Tcirr: «-: = 1.4120.

Analyse: C2H6ClO3P = 144.52.Analysis: C 2 H 6 ClO 3 P = 144.52.

Berechnet ... C 16.63. H 4.16. Cl 24.55. P 21.42%: gefunden C 16.9. H 4.2. Cl 24.3, P 21.6%.Calculated ... C 16.63. H 4.16. Cl 24.55. P 21.42%: found C 16.9. H 4.2. Cl 24.3, P 21.6%.

Auf analoge Weise erhält man. ausgehend von 125 g Tri-n-butylphosphit. 106.5 g O.O-Di-n-butylchlorphosphat. Siedepunkt = 90 C unter 0.1 Torr: n:-- = 1.4320.In an analogous way one obtains. starting from 125 g of tri-n-butyl phosphite. 106.5 g of OO-di-n-butyl chlorophosphate. Boiling point = 90 C below 0.1 Torr: n : - = 1.4320.

Diese Verbindungen :!nd identich mit denen, die von R. A. Mclvor. G. D. McCa-thy. G. A. Grant. Can. Journ. Chem.. 34,18' 9 (1956). auf einem anderen Wege erhalten wurden.These connections:! Nd identical to those who by R. A. Mclvor. G. D. McCa-thy. G. A. Grant. Can. Journ. Chem. 34, 18'9 (1956). on one other ways were obtained.

Beispiel 1example 1

0.0-Dimethyl-0-(3-oxo-2-methyl-cyclopenten-l-yl)-phosphat (I mit R1 = R2 = CH,)0.0-dimethyl-0- (3-oxo-2-methyl-cyclopenten-l-yl) phosphate (I with R 1 = R 2 = CH,)

In einer Mischung aus 250 ecm Tetrahydrofuran und 42 ecm Triäthylamin löst man unter Stickstoffatmosphäre 33.6 g 2-Meihyl-cycIopentan-l,3-dion und trägt in diese Lösung 43,2 g O.O-Dimethylchlorphosphat ein. Die Temperatur der Reaktionsmischung steigt auf 6OC. Man läßt sie auf 25° C absinken, entfernt durch Filtrieren die gebildeten unlöslichen Anteile, engt im ter vermindertem Druck zur Trockne ein, löst den Rückstand in Chloroform, wäscht die Chloroformlösung, trocknet sie, engt sie unter vermindertem Druck zur Trockne ein, rektifiziert den Rückstand und erhält 38,5 g O.O-Dimethyl-O-P-oxo^-methyl-cyclopenten-1-yl)-phosphat. Siedepunkt = 1200C unter 0,1 Torr; ηΐ = 1,4770.33.6 g of 2-methylcyclopentane-1,3-dione are dissolved in a mixture of 250 ecm of tetrahydrofuran and 42 ecm of triethylamine under a nitrogen atmosphere and 43.2 g of OO-dimethylchlorophosphate are introduced into this solution. The temperature of the reaction mixture rises to 60 ° C. It is allowed to drop to 25 ° C., the insoluble fractions formed are removed by filtration, evaporated to dryness under reduced pressure, the residue is dissolved in chloroform, the chloroform solution is washed, dried, concentrated to dryness under reduced pressure, and the rectified Residue and receives 38.5 g of OO-dimethyl-OP-oxo ^ -methyl-cyclopenten-1-yl) phosphate. Boiling point = 120 ° C. below 0.1 torr; ηΐ = 1.4770.

Analyse: C8H13O5P = 220,2.Analysis: C 8 H 13 O 5 P = 220.2.

Berechne! ... C 43,64, H 5,96, P 14,07%;Calculate! ... C 43.64, H 5.96, P 14.07%;

gefunden .... C 43,4, H 6,1, P 14.2%. J5 found .... C 43.4, H 6.1, P 14.2%. J5

Beispiel 2Example 2

O,O-Diäthyl-O-(3-oxo-2-methyl-cyclopenten-1 -yl)-phosphat (I mit R, = C2H5, R2 = CH3)O, O-diethyl-O- (3-oxo-2-methyl-cyclopenten-1 -yl) -phosphate (I with R, = C 2 H 5 , R 2 = CH 3 )

In 100 ecm Tetrahydrofuran trägt man unter Stickstoffatomosphäre 10 g2-Methyl-cydopentän-l,3-dion, 9,9 g Triäthylamin und dann eine Mischung aus 15,0 g Ο,Ο-Diäthyl-chlorphosphat und 40 ecm Tetrahydrofuran ein. Man rührt 1O Minuten lang bei Raumtem- peratur, entfernt den gebildeten Niederschlag durch Filtrieren, engt unter vermindertem Druck zur Trockne ein in Gegenwart einer geringen Menge Natriumcarbonat, rektifiziert und erhält 14 g O,O-DiäthyI-O-(3-oxo-2-methyl-cyclopenten-l-yl)-phosphat, Siedepunkt = 1200C unter 0,1 Torr:n|' = 1,4691.In 100 ecm of tetrahydrofuran, under a nitrogen atmosphere, 10 g of 2-methylcydopentene-1,3-dione, 9.9 g of triethylamine and then a mixture of 15.0 g of Ο, Ο-diethyl chlorophosphate and 40 ecm of tetrahydrofuran are introduced. The mixture is stirred 1 O min at room temperature, the precipitate formed is removed by filtration and concentrated, rectified in the presence of a small amount of sodium carbonate under reduced pressure to dryness to obtain 14 g of O, O-DiäthyI-O- (3-oxo- 2-methyl-cyclopenten-l-yl) phosphate, boiling point = 120 ° C. below 0.1 Torr: n | ' = 1.4691.

Analyse: C10H17O5P = 248,22.Analysis: C 10 H 17 O 5 P = 248.22.

Berechnet ... C 48,39. H 6,90, P 12,50%;
gefunden .... C 48,0, H 6,9, P 12.4%.Calculated ... C 48.39. H 6.90, P 12.50%;
found .... C 48.0, H 6.9, P 12.4%.

ao Das Ο,Ο-Diäthyl-chlorphosphat stellt man nach der Methode von '.. C. Poshkus und J. E. Her weh, Am. Soc, 7«. 6127 (1957), her.ao The Ο, Ο-diethyl chlorophosphate is produced according to the Method by '.. C. Poshkus and J. E. Her weh, Am. Soc, 7 ". 6127 (1957), her.

In Analogie zu den Beispielen 1 und 2 werden hergestellt: In analogy to Examples 1 and 2, the following are produced:

0.0-Diisopropyl-0-(3-oxo-2-methyl-cyclopentenl-yl)-phosphat(ImitR, = i-Propyl,R2 = CH3)durch Einwirkung von Ο,Ο-Diisopropylchlorphosphat (hergestellt unter Anwendung der Methode von A. H. Ford-Moor <-. et coll., J. Chem. Soc.. 1953, 1776) auf 2-Methyl-cyclopentan-l,3-dion; Ausbeute: 85%; Siedepunkt = 125° C bei 0,05 Torr; n? = 1,4655.0.0-Diisopropyl-0- (3-oxo-2-methyl-cyclopentenl-yl) phosphate (ImitR, = i-propyl, R 2 = CH 3 ) by the action of Ο, Ο-diisopropyl chlorophosphate (prepared using the method of AH Ford-Moor <-. Et coll., J. Chem. Soc. 1953, 1776) on 2-methyl-cyclopentane-1,3-dione; Yield: 85%; Boiling point = 125 ° C at 0.05 torr; n? = 1.4655.

O,O-Di-n-butyl-O-(3-oxo-2-methyl-cyclopentanl-yl)-phosphat (I mit R1 = η-Butyl, R2 = CH3) durch Einwirkung von Ο,Ο-Di-n-butyl-chlorphosphat auf 2-Methyl-cyclopentan-l,3-dion; Ausbeute: 64%, Siedepunkt = 115° C bei 0,02 Torr; nf = i,<670.O, O-di-n-butyl-O- (3-oxo-2-methyl-cyclopentanl-yl) phosphate (I with R 1 = η-butyl, R 2 = CH 3 ) by the action of Ο, Ο- Di-n-butyl chlorophosphate on 2-methyl-cyclopentane-1,3-dione; Yield: 64%, boiling point = 115 ° C. at 0.02 torr; nf = i, <670.

Analyse: C14H25O5P = 304,32.Analysis: C 14 H 25 O 5 P = 304.32.

Berechnet ... C 55,25, H 8,28, P 10,18%;Calculated ... C 55.25, H 8.28, P 10.18%;

gefunden .... C 55,0, H &,4, P 10,5%.found .... C 55.0, H &, 4, P 10.5%.

0.0-Diäthyl-0-(3-oxo-2-äthyl-cyclopenten-l-yl)-phosphat (I mit R1 = R2 = C2H5) durch Einwirkung von Ο,Ο-Diäthyl-chlorphosphat (hergestellt unter Anwendung des Verfahrens von A. C. Poshkus und J.E. H er weh, Am. Soc., 79, 6127 [1957]) auf 2-Äthyl-cyclopentan-l,3-dion; Ausbeute· 85%, Siedepunkt = 85° C bei 10"4 Torr.0.0-diethyl-0- (3-oxo-2-ethyl-cyclopenten-l-yl) phosphate (I with R 1 = R 2 = C 2 H 5 ) by the action of Ο, Ο-diethyl chlorophosphate (manufactured under Application of the method of AC Poshkus and JE H er weh, Am. Soc., 79, 6127 [1957]) on 2-ethyl-cyclopentane-1,3-dione; Yield · 85%, boiling point = 85 ° C at 10 " 4 torr.

O,O-Diäthyl-O-(3-oxo-2-isopropyl-cyclopentenl-yl)-phosphat (I mit R1 = C2H5, R2 = i-Propyl) durch Einwirkung von Ο,Ο-Diäthyl-chlorphosphat (hergestellt unter Anwendung des Verfahrens von A. C. Poshkus und J. E. H e r w e h, Am. Soc., 79,6127 [ 1957]) auf 2-Isopropyl-cyclopentan-1,3-dion; Ausbeute: 75%; Siedepunkt = 93°C bei 10~4 Torr; n'i = 1,4649.O, O-diethyl-O- (3-oxo-2-isopropyl-cyclopentenl-yl) phosphate (I with R 1 = C 2 H 5 , R 2 = i-propyl) by the action of Ο, Ο-diethyl chlorophosphate (prepared using the method of AC Poshkus and JE H Erweh, Am. Soc., 79,6127 [1957]) to 2-isopropyl-cyclopentane-1,3-dione; Yield: 75%; Boiling point = 93 ° C at 10 ~ 4 torr; n'i = 1.4649.

SchemaScheme

R,R,

,V — Hai + , V - shark +

R1OR 1 O

R,o ,„R, o, "

HaI-HHaI-H

mit Hai = Chlor oder Bromwith Hai = chlorine or bromine

R1O..R 1 O ..

R1O-P R1OR 1 OP R 1 O

I 923103I 923103

Schema 2Scheme 2

HalHal

R|0\ ? R | 0 \?

P-O R1OPO R 1 O

+ R1HaI + R 1 HaI

Claims (1)

Patentansprüche: man ein Phosphorsäurehalogenid der FormelClaims: a phosphoric acid halide of the formula 1. ©,O-Dialkyl-O-ß-oxo^-alkyl-l-cyclopentenyl)-phosphate der allgemeinen Formel 1 Hai1. ©, O-Dialkyl-O-ß-oxo ^ -alkyl-1-cyclopentenyl) phosphate the general formula 1 shark R1OR 1 O
DE19691923103 1968-05-14 1969-05-06 O, O-DIALKYL-O- (3-OXO-2-ALKYL-1CYCLOPENTENYL) -PHOSPHATE, PROCESS FOR THE PREPARATION AND AGENTS CONTAINING THESE Pending DE1923103B2 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR151734 1968-05-14

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DE1923103A1 DE1923103A1 (en) 1969-11-20
DE1923103B2 true DE1923103B2 (en) 1973-02-22

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BE (1) BE732940A (en)
CH (1) CH511894A (en)
DE (1) DE1923103B2 (en)
ES (1) ES367168A1 (en)
FR (1) FR1584530A (en)
GB (1) GB1233843A (en)
IL (1) IL32009A0 (en)
NL (1) NL6907242A (en)
OA (1) OA03320A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025584A (en) * 1974-08-15 1977-05-24 Hoffmann-La Roche Inc. 1-Acetyl-3(4)-(dihydrocarbylphosphoryloxy)-cyclohex-3-enes
US4088645A (en) * 1975-10-02 1978-05-09 Hoffmann-La Roche Inc. O,O-Dialkylphosphoryloxy-2,3,5,8-tetrahydro-1H-s-triazolo[1,2a]pyridazine-1,3-diones
US4409153A (en) * 1980-03-28 1983-10-11 Union Carbide Corporation O-(2-Aryl-3-oxo-1-cyclohexenyl) phosphates

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GB1233843A (en) 1971-06-03
OA03320A (en) 1970-12-15
CH511894A (en) 1971-08-31
FR1584530A (en) 1969-12-26
BE732940A (en) 1969-11-12
ES367168A1 (en) 1971-04-01
DE1923103A1 (en) 1969-11-20
NL6907242A (en) 1969-11-18
IL32009A0 (en) 1969-06-25

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