DE1024979B - Process for the preparation of cyclic phosphoric acid ester halides - Google Patents
Process for the preparation of cyclic phosphoric acid ester halidesInfo
- Publication number
- DE1024979B DE1024979B DEU3409A DEU0003409A DE1024979B DE 1024979 B DE1024979 B DE 1024979B DE U3409 A DEU3409 A DE U3409A DE U0003409 A DEU0003409 A DE U0003409A DE 1024979 B DE1024979 B DE 1024979B
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- acid ester
- phosphoric acid
- theoretical
- cyclic phosphoric
- 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
- -1 cyclic phosphoric acid ester halides Chemical class 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical class OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000014101 wine Nutrition 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
- C07F9/547—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)
- C07F9/657127—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) condensed with carbocyclic or heterocyclic rings or ring systems
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 cyclischen Phosphorsäureesterhalogeniden Es ist bereits vorgeschlagen worden, cyclischePhosphorsäureesterhalogenide durch Umsetzung von Phosphoroxyhalogeniden mit Alkandiolen bei Temperaturen vorzugsweise unter 50° herzustellen.Process for the preparation of cyclic phosphoric acid ester halides It has been proposed to use cyclic phosphoric acid ester halides Reaction of phosphorus oxyhalides with alkanediols at temperatures preferably under 50 °.
Es wurde nun gefunden, daß man zu bicyclischen Phosphorsäureesterhalogeniden gelangt, wenn man bei dem Verfahren zur Herstellung von cyclischen Phosphorsäureesterhalogeniden durch Umsetzung von Phosphoroxyhalogeniden mit Diolen bei einer Temperatur zwischen - 20 und + 60° die Phosphoroxyhalogenide mit 2-(1'-Oxyalkyl)-cyclohexanolen oder2-(1'-Oxyalkyl)-cyclopentanolen der allgemeinen Formel bzw. in der R Alkylgruppen oder Wasserstoffatome und Weine Alkylgruppe bedeutet, umsetzt.It has now been found that bicyclic phosphoric ester halides are obtained if, in the process for the preparation of cyclic phosphoric ester halides by reacting phosphorus oxyhalides with diols at a temperature between -20 and + 60 °, the phosphorus oxyhalides with 2- (1'-oxyalkyl) - cyclohexanols or 2- (1'-oxyalkyl) -cyclopentanols of the general formula respectively. in which R denotes alkyl groups or hydrogen atoms and wines denotes alkyl groups.
Den erhaltenen P-Halogen-2,4-dioxa-P-oxo-3-phosphabicyclo-(4,4,0)-decanen bzw. P-Halogen-2,4-dioxa-P-oxo-3-phosphabicyclo-(4,3,0)-nonanen kommt die allgemeine Formel bzw. in der Hal ein Halogenatom bedeutet, zu. Erfindungsgemäß sind als Ausgangsmaterialien z. B.The resulting P-halogen-2,4-dioxa-P-oxo-3-phosphabicyclo- (4,4,0) -decanes or P-halogen-2,4-dioxa-P-oxo-3-phosphabicyclo- ( 4,3,0) -nonanes comes the general formula respectively. in which Hal means a halogen atom, to. According to the invention are as starting materials such. B.
2-(1-Oxyäthyl)-cyclohexanol, 2-(1-Oxyäthyl)-3,3,5-trimethylcyclohexanol und 2-(1-Oxyäthyl)-3-methylcyclopentanol geeignet.2- (1-oxyethyl) cyclohexanol, 2- (1-oxyethyl) -3,3,5-trimethylcyclohexanol and 2- (1-oxyethyl) -3-methylcyclopentanol are suitable.
Vorzugsweise wird die Reaktion des Phosphoroxyhalogenides mit dem Cycloalkan-diol in Gegenwart eines den Halogenwasserstoff bindenden Mittels, wie tertiären Aminen, z. B. Pyridin, N,N-Dimethylanilin, Trimethylamin oder Tributylamin, durchgeführt. Die Umsetzung kann bei atmosphärischen oder bei verminderten Drücken durchgeführt werden und wird bei Temperaturen zwischen - 20 und + 60°, vorzugsweise bei solchen von 0 bis 25°, vorgenommen. Die Reaktion wird weiterhin vorteilhafterweise bei einem absoluten Druck von nicht mehr als 500 mm durchgeführt. Gegebenenfalls kann auch in Gegenwart eines inerten organischen Lösungsmittels umgesetzt werden.Preferably, the reaction of the phosphorus oxyhalide with the Cycloalkanediol in the presence of a hydrogen halide binding agent such as tertiary amines, e.g. B. pyridine, N, N-dimethylaniline, trimethylamine or tributylamine, carried out. The implementation can be at atmospheric or at diminished Pressures are carried out and is at temperatures between -20 and + 60 °, preferably in those from 0 to 25 °. The reaction becomes further advantageous carried out at an absolute pressure of not more than 500 mm. Possibly can also be reacted in the presence of an inert organic solvent.
Die rohen Verfahrensprodukte können durch Kristallisation oder durch Destillation im Hochvakuum, vorzugsweise unter Verwendung einer Destillationsanlage mit fallendem Film, gereinigt werden. In den Fällen, in denen das Rohprodukt in Wasser genügend unlöslich ist, kann die Reaktionsmischung mit Wasser gewaschen, das gewaschene Rohprodukt durch Vakuumdestillation vom Wasser befreit und so ein gereinigter Rückstand erhalten werden.The crude process products can by crystallization or by Distillation in a high vacuum, preferably using a distillation unit with falling film. In those cases where the crude product is in Water is sufficiently insoluble, the reaction mixture can be washed with water, the washed crude product freed from water by vacuum distillation and so a purified residue can be obtained.
Die neuen bicyclischen Verbindungen sind wertvolle Schädlingsbekämpfungsmittel. Sie dienen außerdem als Zwischenprodukte zur Herstellung von Schädlingsbekämpfungsmitteln, Weichmachern, Schmiermitteln, Öl-und Benzinzusätzen, oberflächenaktiven Mitteln und Textilhilfsmitteln.The new bicyclic compounds are valuable pesticides. They also serve as intermediate products in the manufacture of pesticides, Plasticizers, lubricants, oil and gasoline additives, surface active agents and textile auxiliaries.
Das erfindungsgemäße Verfahren wird durch die nachstehenden Beispiele näher erläutert. Beispiel 1 Zu 153 g (1 Mol) Phosphoroxychlorid, das bei einem absoluten Druck von 500 mm auf einer Reaktionstemperatur von 25° gehalten wird, werden während 35 Minuten 144 g (1 Mol) 2-(1'-Oxyäthyl)-cyclohexanol gegeben. Danach wird die Reaktionsmischung jeweils bei 25° eine weitere Stunde auf einem Druck von 500 mm, dann 1 Stunde auf 350 mm und schließlich 21/2 Stunden auf weniger als 1 mm gehalten. Das entstandene P-Chlor-2,4-dioxa-5-methyl-P-oxo-3-phosphabicyclo-[4,4, 0]-decan wird in Form eines hellorangegefärbten flüssigen Rückstandes erhalten, der folgende Eigenschaften besitzt: Äquivalentgewicht (durch Veresterung bestimmt) 218,7 (theoretisch 224,6); WD 1,4883.The process according to the invention is illustrated in more detail by the following examples. EXAMPLE 1 144 g (1 mol) of 2- (1'-oxyethyl) cyclohexanol are added over 35 minutes to 153 g (1 mol) of phosphorus oxychloride, which is kept at a reaction temperature of 25 ° at an absolute pressure of 500 mm. Thereafter, the reaction mixture is held at 25 ° for a further hour at a pressure of 500 mm, then for 1 hour at 350 mm and finally for 21/2 hours at less than 1 mm. The resulting P-chloro-2,4-dioxa-5-methyl-P-oxo-3-phosphabicyclo [4,4,0] decane is obtained in the form of a light orange-colored liquid residue which has the following properties: equivalent weight (determined by esterification) 218.7 (theoretical 224.6); WD 1.4883.
Analyse (Gewichtsprozent) Cl 15,36 (theoretisch 15,78) ; P 13,68 (theoretisch 13,80) ; C 43,11 (theoretisch 42,80) ; H 6,53 (theoretisch 6,28).Analysis (percent by weight) Cl 15.36 (theoretical 15.78); P 13.68 (theoretical 13.80); C 43.11 (theoretical 42.80); H 6.53 (theoretical 6.28).
Beispiel 2 153 g (1 Mol) Phosphoroxychlorid werden während 18 Minuten tropfenweise unter Rühren und Kühlen auf eine Temperatur von 25° zu einer Lösung von 186 g (1 Mol) 2-(1'-Oxyäthyl)-3,3,5-trimethylcyclohexanol in 150 g Benzol bei einem Druck von 500 mm gegeben. Nach der Zugabe werden Temperatur und Druck eine weitere Stunde aufrechterhalten. Dann wird die Reaktionsmischung 1 Stunde bei der gleichen Temperatur, jedoch 350 mm Druck, anschließend 1 Stunde bei weniger als 4 mm und schließlich bei 50° 1/2 Stunde und weniger als 1,5 mm Druck belassen. Es werden 261,5 g (theoretisch 266,7 g) eines braunen, flüssigen Rückstandes erhalten, der P -Chlor -2,4 - dioxa - P - oxo - 5, 7, 7, 9 - tetramethyl-3-phosphabicyclo-[4,4,0]-decan darstellt und folgende Eigenschaften besitzt: Reinheit (durch Verseifung bestimmt) 99,4 0/,; W = 1,4819.Example 2 153 g (1 mol) of phosphorus oxychloride are added dropwise over 18 minutes with stirring and cooling to a temperature of 25 ° to a solution of 186 g (1 mol) of 2- (1'-oxyethyl) -3,3,5-trimethylcyclohexanol given in 150 g of benzene at a pressure of 500 mm. After the addition, the temperature and pressure are maintained for a further hour. The reaction mixture is then left for 1 hour at the same temperature, but a pressure of 350 mm, then for 1 hour at less than 4 mm and finally at 50 ° for 1/2 hour and less than 1.5 mm of pressure. 261.5 g (theoretically 266.7 g) of a brown, liquid residue are obtained which contains P -chloro -2,4-dioxa-P-oxo-5, 7, 7, 9-tetramethyl-3-phosphabicyclo- [ 4,4,0] decane and has the following properties: purity (determined by saponification) 99.4 0 / ,; W = 1.4819.
Analyse (Gewichtsprozent) P 11,03 (theoretisch 11,62) ; C 49,40 (theoretisch 49,55); H 7,76 (theoretisch 7,56).Analysis (percent by weight) P 11.03 (theoretical 11.62); C 49.40 (theoretical 49.55); H 7.76 (theoretical 7.56).
Beispiel 3 144 g (1 Mol) 2-(1'-Oxyäthyl)-3-methylcyclopentanol werden während 27 Minuten unter Rühren tropfenweise zu 153 g (1 Mol) Phosphoroxychlorid gegeben. Während der Zugabe und einer weiteren Stunde wird die Reaktionsmischung auf 25° und 500 mm Druck gehalten. Die Reaktionsmischung wird dann bei 25° eine weitere Stunde bei einem Druck von 350 mm und dann 24 Stunden bei 2 mm belassen. Es werden 222,5 g (theoretisch 224,6 g) eines roten flüssigen Rückstandes erhalten, der P-Chlor-5, 7-dimethyl-2,4-dioxa-P-oxo-3-phosphabicy clo-'#4,3,0]-nonan darstellt. Die Verbindung besitzt folgende Eigenschaften: Äquivalentgewicht (durch Veresterung bestimmt) 215,1 (theoretisch 224,6) ; aaD 1,4768.Example 3 144 g (1 mol) of 2- (1'-oxyethyl) -3-methylcyclopentanol are added dropwise to 153 g (1 mol) of phosphorus oxychloride over 27 minutes with stirring. During the addition and for a further hour, the reaction mixture is kept at 25 ° and 500 mm pressure. The reaction mixture is then left at 25 ° for a further hour at a pressure of 350 mm and then for 24 hours at 2 mm. 222.5 g (theoretically 224.6 g) of a red liquid residue are obtained, the P-chloro-5, 7-dimethyl-2,4-dioxa-P-oxo-3-phosphabicy clo- '# 4,3 , 0] -nonane represents. The compound has the following properties: equivalent weight (determined by esterification) 215.1 (theoretical 224.6) ; aaD 1.4768.
Analyse (Gewichtsprozent) Cl 16,17 (theoretisch 15,78); P 13,84 (theoretisch 13,79) ; C 43,18 (theoretisch 42,81); H 6,68 (theoretisch 6,28).Analysis (percent by weight) Cl 16.17 (theoretical 15.78); P 13.84 (theoretical 13.79); C 43.18 (theoretical 42.81); H 6.68 (theoretical 6.28).
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1024979XA | 1954-07-08 | 1954-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1024979B true DE1024979B (en) | 1958-02-27 |
Family
ID=22290167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEU3409A Pending DE1024979B (en) | 1954-07-08 | 1955-06-28 | Process for the preparation of cyclic phosphoric acid ester halides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1024979B (en) |
-
1955
- 1955-06-28 DE DEU3409A patent/DE1024979B/en active Pending
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