DE1024945B - Process for the production of chlorine-containing phosphoric acid esters - Google Patents
Process for the production of chlorine-containing phosphoric acid estersInfo
- Publication number
- DE1024945B DE1024945B DEN11549A DEN0011549A DE1024945B DE 1024945 B DE1024945 B DE 1024945B DE N11549 A DEN11549 A DE N11549A DE N0011549 A DEN0011549 A DE N0011549A DE 1024945 B DE1024945 B DE 1024945B
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- phosphoric acid
- chlorine
- hydrogen
- production
- 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
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 10
- 239000000460 chlorine Substances 0.000 title claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052801 chlorine Inorganic materials 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000005111 carboxyalkoxy group Chemical group 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 19
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 6
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4018—Esters of cycloaliphatic acids
-
- 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
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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 von chlorhaltigen Phosphorsäureestern Es ist bekannt, daß Dialkylphosphite mit Ketonen im Sinne folgender Reaktionsgleichung unter Entstehung von 0,0-Dialkyl-oxyalkylphosphonsäureestern reagieren, wobei katalytische Zusätze, wie z. ß. Piperidin oder Alkalimetallalkoholate, die Reaktion beschleunigen können: Die auf diesem Wege erhaltenen Verbindungen zeigen keine bemerkenswerten biologischen Eigenschaften.Process for the preparation of chlorine-containing phosphoric acid esters It is known that dialkyl phosphites react with ketones in the sense of the following reaction equation to form 0,0-dialkyl-oxyalkylphosphonic acid esters, with catalytic additives such. ß. Piperidine or alkali metal alcoholates, which can accelerate the reaction: The compounds obtained in this way do not show any remarkable biological properties.
Es wurde gefunden, daß die Umsetzung von Dialkylphosphiten mit in a-Stellung zur Carbonylgruppe einfach oder mehrfach halogenierten Ketonen in analoger Weise zu 0,0-Dialkyl-a-oxy-ß-halogenphosphonsäureestern bzw. den entsprechenden Di- oder Trihalogenderivaten führt, aus welchen leicht Halogenwasserstoff durch übliche Methoden (Reaktion mit anorganischen oder organischen Basen, Erhitzen in Gegenwart von Katalysatoren usw.) abgespalten werden kann. Hierbei lagern sich die Phosphonsäureester in olefinische Doppelbindungen enthaltende Phosphorsäureester um. Dieser neue Reaktionsweg macht auf einfach durchführbare Weise eine Klasse von Verbindungen zugänglich, die biologische hochwirksame Substanzen enthält. Die so hergestellten 0,0-Dialkylphosphorsäureester mit einer ungesättigten, aliphatischen, cycloaliphatischen oder gemischt aliphatisch-aromati- Die Symbole bedeuten: R1 und R2 gleiche oder verschiedene aliphatische Alkylreste mit 1 bis 4 C-Atomen; R3 Wasserstoff oder Halogen; R4 Wasserstoff, Halogen, scheu Estergruppe zeigen teilweise bereits insektizide Eigenschaften. Sie werden jedoch zu insektizid hochwirksamen Verbindungen, wenn man sie zusätzlich chloriert, wobei sich in üblicher Weise ein Molekül Chlor quantitativ an die - C = C-Doppelbindung anlagert. Diese Halogenierung kann in bekannter Weise durch Jod, Pyridin und andere katalytisch wirkende Zusätze beschleunigt werden.It has been found that the reaction of dialkyl phosphites with ketones which are singly or multiply halogenated in α-position to the carbonyl group leads in an analogous manner to 0,0-dialkyl-α-oxy-β-halophosphonic esters or the corresponding di- or trihalogen derivatives, from which hydrogen halide can easily be split off by conventional methods (reaction with inorganic or organic bases, heating in the presence of catalysts, etc.). Here, the phosphonic acid esters rearrange themselves into phosphoric acid esters containing olefinic double bonds. This new pathway makes a class of compounds accessible in a simple manner, which contains biologically potent substances. The 0,0-dialkyl phosphoric acid esters produced in this way with an unsaturated, aliphatic, cycloaliphatic or mixed aliphatic-aromatic The symbols mean: R1 and R2 are identical or different aliphatic alkyl radicals with 1 to 4 carbon atoms; R3 is hydrogen or halogen; R4 hydrogen, halogen, shy ester groups already show insecticidal properties in some cases. However, they become highly insecticidal compounds if they are additionally chlorinated, with one molecule of chlorine being quantitatively added to the - C =C double bond in the usual way. This halogenation can be accelerated in a known manner by iodine, pyridine and other catalytically active additives.
Die Reaktionsstufen werden durch folgende Formulierungen gekennzeichnet Alliyl, Cycloalkyl, Carboxyalkyl, Carboxyalkoxy oder Alkaryl, wobei die jeweiligen Phenylgruppen auch substituiert sein können; R5 Alkyl, Halogenalkyl, Cycloalkyl, Alkaryl, Aryl oder Aralkyl, wobei die Phenylgruppen auch substituiert sein können.The reaction stages are characterized by the following formulations Alliyl, cycloalkyl, carboxyalkyl, carboxyalkoxy or alkaryl, the respective Phenyl groups can also be substituted; R5 alkyl, haloalkyl, cycloalkyl, Alkaryl, Aryl or aralkyl, where the phenyl groups can also be substituted.
Führt man die Reaktion in entsprechender Weise mit in a-Stellung einfach oder doppelt halogenieiten Ringketonen durch, so ergibt sich analog folgende Formulierung z. B. der Umsetzung von Dimethylphosphit mit a,a-Dichlorcyclohezanon : w Beispiel 1 11,0g Dimethylphosphit mischt man mit 12,7g a,a-Dichloraceton (asymmetrisches Dichloraceton) und erwärmt 18 Stunden auf Wasserbadtemperatur. Das erhaltene ölige Phosphonat der Zusammensetzung C,H"04PC12 löst man im 3fachen Volumen absolutem Methanol, gibt unter äußerer Kühlung eine Lösung von 2,3 g metallischem Natrium in 50 ccm absolutem Methanol zu, läßt 10 Stunden bei Zimmertemperatur stehen, saugt ausgefallenes Natriumchlorid ab und erhält als Eindampfrückstand den dünnflüssigen Phosphorsäureester der Zusammensetzung C5 Hl, 04 P Cl, der durch Destillation bei 3 mm 98 bis 102' gereinigt werden kann. Man verdünnt dieses Produkt mit einem inerten Lösungsmittel, z. B. Tetrachlorkohlenstoff, und leitet trockenes Chlorgas ein, wobei die Verbindung die stöchiometrische Menge C12 aufnimmt. Der Rückstand nach Abdampfen des Lösungsmittels ist ein gelbliches Öl der Zusammensetzung C5H1o04PC13 mit einer Dichte d20 1,478.If the reaction is carried out in a corresponding manner with ring ketones that are singly or doubly halogenated in the a-position, the following formulation results, for example, in FIG. B. the reaction of dimethyl phosphite with a, a-dichlorocyclohezanone: w Example 1 11.0 g of dimethyl phosphite are mixed with 12.7 g of α , α-dichloroacetone (asymmetric dichloroacetone) and heated to water bath temperature for 18 hours. The oily phosphonate obtained of the composition C, H "04PC12 is dissolved in 3 times the volume of absolute methanol, a solution of 2.3 g of metallic sodium in 50 cc of absolute methanol is added with external cooling, left to stand for 10 hours at room temperature, and precipitated sodium chloride is filtered off with suction The residue obtained from evaporation is the low-viscosity phosphoric acid ester of the composition C5 Hl, 04 P Cl, which can be purified by distillation at 3 mm 98 to 102 °. This product is diluted with an inert solvent, e.g. carbon tetrachloride, and dry chlorine gas is introduced , the compound taking up the stoichiometric amount of C12. The residue after evaporation of the solvent is a yellowish oil of the composition C5H1004PC13 with a density d20 1.478.
Beispiel 2 11,0g Dimethylphosphit mischt man mit 12,7g a,ä -Dichloraceton (symmetrisches Dichloraceton), gibt S Tropfen Piperidin zu und erwärmt 12 Stunden auf etwa 100°. Die weitere Aufarbeitung geschieht wie im Beispiel 1, wobei wiederum aus dem Phosphonat der Zusammensetzung C,H"0,PC12 durch Chlorwasserstoffabspaltung ein Phosphorsäureester der Bruttoformel C5 Hlp 04 P Cl entsteht, der bei 1,5 mm 95 bis 98' siedet. Durch Chlorierung wird hieraus die Verbindung der Zusammensetzung C5 H1104 P C13 erhalten.Example 2 11.0 g of dimethyl phosphite are mixed with 12.7 g of α , α-dichloroacetone (symmetrical dichloroacetone), 5 drops of piperidine are added and the mixture is heated to about 100 ° for 12 hours. The further work-up is carried out as in Example 1, with the phosphonate of the composition C, H "0, PC12 being split into a phosphoric acid ester of the gross formula C5 Hlp 04 P Cl which boils at 1.5 mm from 95 to 98 '. By chlorination the compound with the composition C5 H1104 P C13 is obtained therefrom.
Beispiel 3 11,0 g Dimethylphosphit mischt man mit 10,65 g a-Chloracetessigester, gibt 5 Tropfen Piperidin zu und erwärmt 18 Stunden auf 90 bis 100'. Das entstandene Phosphonat der Zusammensetzung C,H"06PC1 lagert man unter Chlorwasserstoffabspaltung mittels N atriummethylat (aus 2,3 g metallischem Natrium), wie im Beispiel 1 beschrieben, in den Phosphorsäureester der Zusammensetzung C$ H15 0 , P um, der einen Siedepunkt vcn 129 bis 132' bei 1 mm zeigt. Die Verbindung nimmt die stöchiometrische Menge Chlorgas auf, wobei ein öliges Produkt der Zusammensetzung C"H"05PC12 entsteht.Example 3 11.0 g of dimethyl phosphite are mixed with 10.65 g of a-chloroacetoacetic ester, add 5 drops of piperidine and heat to 90 to 100 'for 18 hours. The resulting Phosphonate of the composition C, H "06PC1 is stored with elimination of hydrogen chloride by means of sodium methylate (from 2.3 g of metallic sodium), as described in Example 1, in the phosphoric acid ester of the composition C $ H15 0, P um, which has a boiling point shows vcn 129 to 132 'at 1 mm. The compound takes the stoichiometric amount Chlorine gas, with an oily product of the composition C "H" 05PC12 is formed.
Beispiel 4 11,0g Dimethylphosphit mischt man mit 16,7g a,a-Dichlorcycloliexanon und erwärmt 6 Stunden auf 80'. Man löst das entstandene Phosphonat der Zusammensetzung C8 H1504 P Cl, in 50 ccm absolutem Alkohol, gibt unter Kühlung portionsweise eine Lösung von 5,6 g Kaliumhydroxyd in 100 ccm absolutem Alkohol zu, läßt 10 Stunden bei Raumtemperatur stehen, entfernt das ausgeschiedene Kaliumchlorid durch Filtration, dampft das Lösungsmittel ab, filtriert nochmals und erhält so den Phosphorsäureester der Bruttoformel C,H"04PC1, der bei 3 mm 138 bis 142° unter leichter Zersetzung siedet. Die Verbindung nimmt beim Einleiten von trockenem Chlorgas die berechnete Menge C12 auf, wobei ein öliges Produkt der Zusammensetzung C., H1404 P C13 entsteht. Beispiel 5 11,0 g Dimethylphosphit mischt man mit 18,9 g c),(»-Dichloracetophenon, gibt 5 Tropfen Piperidin zu und erwärmt 12 Stunden auf 100 bis 110°. Das entstandene Phosphonat der Zusammensetzung C1oH1s04PC12 lagert man, wie im Beispiel l beschrieben, durch Natriummethylatlösung (aus 2,3 g metallischem Natrium) unter Chlorwasserstoffabspaltung in den Phosphorsäureester C1pH"0,PC1 um, der bei 1 mm 148 bis 151' unter leichter Zersetzung siedet. Die Verbindung nimmt beim Einleiten von trockenem Chlorgas die berechnete Menge CIZ auf, wobei ein öliges Produkt der Zusammensetzung Cio H12 04 P C13 entsteht.Example 4 11.0 g of dimethyl phosphite are mixed with 16.7 g of α , α-dichlorocycloliexanone and heated to 80 ° for 6 hours. The resulting phosphonate of the composition C8 H1504 P Cl is dissolved in 50 cc of absolute alcohol, a solution of 5.6 g of potassium hydroxide in 100 cc of absolute alcohol is added in portions with cooling, left to stand for 10 hours at room temperature, the precipitated potassium chloride is removed by filtration , the solvent evaporates, filtered again and thus receives the phosphoric acid ester of the gross formula C, H "04PC1, which boils at 3 mm 138 to 142 ° with slight decomposition. When dry chlorine gas is introduced, the compound absorbs the calculated amount of C12, whereby a oily product of composition C., H1404 P C13 is formed. EXAMPLE 5 11.0 g of dimethyl phosphite are mixed with 18.9 g of (»- dichloroacetophenone, 5 drops of piperidine are added and the mixture is heated to 100 to 110 ° for 12 hours Phosphonate of the composition C1oH1s04PC12 is stored, as described in Example 1, by sodium methylate solution (from 2.3 g of metallic sodium) with elimination of hydrogen chloride in the phosph Oräurester C1pH "0, PC1 um, which boils at 1 mm 148 to 151 'with slight decomposition. When dry chlorine gas is introduced, the compound absorbs the calculated amount of CIZ, an oily product with the composition Cio H12 04 P C13 being formed.
Beispiel 6 13,8 g Diäthylphosphit mischt man mit 25,8 g (),(,),e),p-Tetrachloracetophenon und erwärmt nach Zugabe von 5 Tropfen Piperidin 24 Stunden auf 100 bis 110'. Das entstandene Phosphonat der Zusammensetzung C12 Hl;, 04 P C14 löst man in 50 ccm absolutem Alkohol, gibt eine Lösung von 2,3 g metallischem Natrium in 100 ccm absolutem Alkohol zu und läßt 24 Stunden bei Zimmertemperatur stehen. Der nach Aufarbeiten in beschriebener Weise erhaltene Phosphorsäureester der Zusammensetzung C"H"04PC13 hat einen Siedepunkt von 181 bis 184° bei 1 mm. Die Verbindung nimmt die stöchiometrische Menge Chlorgas auf, wobei ein dicköliger Ester der Zusammensetzung C12H1404PC15 entsteht.Example 6 13.8 g of diethyl phosphite are mixed with 25.8 g of (), (,), e), p-tetrachloroacetophenone and after adding 5 drops of piperidine, heated to 100 to 110 'for 24 hours. That The resulting phosphonate of the composition C12 Hl ;, 04 P C14 is dissolved in 50 ccm absolute alcohol, gives a solution of 2.3 g of metallic sodium in 100 cc of absolute Add alcohol and leave to stand at room temperature for 24 hours. The one after working up in Phosphoric acid esters of the composition obtained in the manner described C "H" 04PC13 has a boiling point of 181 to 184 ° at 1 mm. The connection takes the stoichiometric amount of chlorine gas based on a thick oil ester of the composition C12H1404PC15 is created.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEN11549A DE1024945B (en) | 1955-12-06 | 1955-12-06 | Process for the production of chlorine-containing phosphoric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEN11549A DE1024945B (en) | 1955-12-06 | 1955-12-06 | Process for the production of chlorine-containing phosphoric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1024945B true DE1024945B (en) | 1958-02-27 |
Family
ID=7339436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEN11549A Pending DE1024945B (en) | 1955-12-06 | 1955-12-06 | Process for the production of chlorine-containing phosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1024945B (en) |
-
1955
- 1955-12-06 DE DEN11549A patent/DE1024945B/en active Pending
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