DE1079022B - Process for the preparation of trialkyl phosphites - Google Patents
Process for the preparation of trialkyl phosphitesInfo
- Publication number
- DE1079022B DE1079022B DEF26322A DEF0026322A DE1079022B DE 1079022 B DE1079022 B DE 1079022B DE F26322 A DEF26322 A DE F26322A DE F0026322 A DEF0026322 A DE F0026322A DE 1079022 B DE1079022 B DE 1079022B
- Authority
- DE
- Germany
- Prior art keywords
- trialkyl phosphites
- boiling point
- preparation
- amine
- reaction
- 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
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 2
- 238000009835 boiling Methods 0.000 claims description 8
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 amine hydrochloride Chemical class 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 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
- C07F9/141—Esters of phosphorous 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
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Trialkylphosphiten Es ist bekannt, daß man Trialkylphosphite durch Umsetzung von Phosphortrichlorid mit den entsprechenden Alkoholen erhalten kann. Dabei ist die Anwesenheit eines Säurebinders erforderlich, da sonst unter Abspaltung eines Alkylhalogenides Dialkylphosphite entstehen. Als Säurebinder werden unter anderem tertiäre aliphatische Amine und Anilin vorgeschlagen. Bei allen diesen Verfahren ist eine intensive Kühlung erforderlich, welche sich nachteilig auf die Wirtschaftlichkeit der Verfahren auswirkt. Ein besonderes Problem besteht in der Abtrennung des als Nebenprodukt gebildeten Aminhydrochlorids vor dem Reaktionsprodukt. Eine Abtrennung durch Filtration ist verlustreich, da das Reaktionsprodukt nicht vollständig aus dem Filterkuchen entfernt werden kann.Process for the preparation of trialkyl phosphites It is known that trialkyl phosphites by reacting phosphorus trichloride with the corresponding Alcohols can get. The presence of an acid binder is required, otherwise dialkyl phosphites are formed with elimination of an alkyl halide. as Acid binders include tertiary aliphatic amines and aniline. In all of these processes, intensive cooling is required, which is has a detrimental effect on the economic viability of the process. A particular problem consists in the separation of the amine hydrochloride formed as a by-product the reaction product. A separation by filtration is lossy, since that Reaction product cannot be completely removed from the filter cake.
Wird das Reaktionsprodukt durch Destillation von dem Aminhydrochlorid abgetrennt, so sind ebenfalls Verluste nicht zu vermeiden, da Aminhydrochloride bei höheren Temperaturen aus Trialkylphosphiten Alkylhalogenide abspalten.The reaction product is obtained by distillation from the amine hydrochloride separated, losses cannot be avoided either, since amine hydrochlorides split off alkyl halides from trialkyl phosphites at higher temperatures.
Es wurde nun gefunden, daß man Trialkylphosphite in praktisch quantitativer Ausbeute durch Umsetzung von Phosphorigsäuretri- (dialkyl)-amiden mit Alkoholen erhalten kann, wobei das während der Reaktion frei gesetzte sekundäre Amin einen tieferen Siedepunkt als der verwendete Alkohol haben muß und wobei man bei Temperaturen oberhalb des Siedepunktes dieses frei werdenden Amins arbeitet. Verwendet man als sekundäres Amin Dimethylamin, so liegt der Siedepunkt des Amins stets unter dem Siedepunkt des Alkohols. Aus diesem Grunde wird Dimethylamin vorzugsweise benutzt. Die als Ausgangsstoffe verwendeten Phosphorigsäuretri-(dialkyl)-amide können nach bekannten Verfahren durch Umsetzung von Phosphortrichlorid mit sekundären Aminen hergestellt werden. It has now been found that trialkyl phosphites are practically quantitative Yield from reaction of phosphorous acid tri- (dialkyl) amides with alcohols can be obtained, the secondary amine released during the reaction must have a lower boiling point than the alcohol used and at which temperature works above the boiling point of this liberated amine. Used as a secondary amine dimethylamine, the boiling point of the amine is always below Boiling point of alcohol. For this reason, dimethylamine is preferably used. The Phosphorigsäuretri- (dialkyl) amides used as starting materials can after known processes by reacting phosphorus trichloride with secondary amines getting produced.
Beispiel 1 1,0 Mol Phosphorigsäuretri-(dimethyl)-amid wird bei etwa 900 C langsam mit 3,0 Mol Methanol versetzt, wobei Dimethylamin entweicht. Das Gemisch wird anschließend so lange im Siedezustand gehalten, bis die Gasentwicklung beendet ist. Der Rückstand besteht aus praktisch reinem Trimethylphosphit (Kp. 450 C/60 Torr). Die Ausbeute an Trimethylphosphit und zurückgewonnenem Dimethylamin sind quantitativ. Example 1 1.0 mole of phosphorous acid tri- (dimethyl) amide is used at about At 900 ° C., 3.0 mol of methanol are slowly added, with dimethylamine escaping. The mixture is then kept in the boiling state until the evolution of gas has ended is. The residue consists of practically pure trimethyl phosphite (bp 450 C / 60 Torr). The yield of trimethyl phosphite and recovered dimethylamine are quantitatively.
Die Herstellung der als Ausgangsmaterial verwendeten Phosphorigsäuretri-(dialkyl) -amide erfolgt in bekannter Weise durch Umsatz von Phosphortrichlorid mit dem entsprechenden sekundären Amin in Gegenwart eines inerten Lösungsmittels. Dabei wird die Zugabe der Reaktionskomponenten so geleitet, daß das Lösungsmittel am Rückfluß siedet. Nach beendeter Reaktion wird das gebildete Dialkylammoniumchlorid durch Extraktion mit Wasser entfernt, die resultierende organische Phase getrocknet und das Reaktionsprodukt z. B. durch Destillation gewonnen. The production of the phosphorous acid tri- (dialkyl) used as starting material -amide takes place in a known manner by reacting phosphorus trichloride with the corresponding secondary amine in Presence of an inert solvent. Thereby the addition the reaction components passed so that the solvent boils under reflux. After the reaction has ended, the dialkylammonium chloride formed is extracted by extraction removed with water, dried the resulting organic phase and the reaction product z. B. obtained by distillation.
Aus der wäßrigen Salzlösung läßt sich in bekannter Weise das sekundäre Amin wiedergewinnen.The secondary can be extracted from the aqueous salt solution in a known manner Recover Amin.
Beispiel 2 1,0 Mol Phosphorigsäuretri- (dimethyl) -amid und 3,0 Mol Äthanol werden auf die im Beispiel 1 beschriebene Weise zur Reaktion gebracht. Die Ausbeuten an Triäthylphosphit (Kp. 630 C/23 Torr) und zurückgewonnenem Dimethylamin sind quantitativ. Example 2 1.0 mol of phosphorous acid tri- (dimethyl) amide and 3.0 mol Ethanol are reacted in the manner described in Example 1. the Yields of triethyl phosphite (b.p. 630 C / 23 Torr) and recovered dimethylamine are quantitative.
Beispiel 3 1,0 Mol Phosphorigsäuretri-(dimethyl)-amid und 3,0 Mol 2-Athylhexanol werden auf die im Beispiel 1 beschriebene Weise zur Reaktion gebracht. Die Ausbcuten an Tri-(2-äthylhexyl)-phosphit (Kp. 1530 CX 1 Torr) und zurückgewonnenem Dimethylamin sind quantitativ. Example 3 1.0 mol of phosphorous acid tri- (dimethyl) amide and 3.0 mol 2-Ethylhexanol are reacted in the manner described in Example 1. The yields of tri- (2-ethylhexyl) phosphite (boiling point 1530 CX 1 Torr) and recovered Dimethylamine are quantitative.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF26322A DE1079022B (en) | 1958-08-05 | 1958-08-05 | Process for the preparation of trialkyl phosphites |
| CH7530459A CH401942A (en) | 1958-08-05 | 1959-07-03 | Process for the preparation of monomeric neutral esters of phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF26322A DE1079022B (en) | 1958-08-05 | 1958-08-05 | Process for the preparation of trialkyl phosphites |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1079022B true DE1079022B (en) | 1960-04-07 |
Family
ID=7091979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF26322A Pending DE1079022B (en) | 1958-08-05 | 1958-08-05 | Process for the preparation of trialkyl phosphites |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH401942A (en) |
| DE (1) | DE1079022B (en) |
-
1958
- 1958-08-05 DE DEF26322A patent/DE1079022B/en active Pending
-
1959
- 1959-07-03 CH CH7530459A patent/CH401942A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH401942A (en) | 1965-11-15 |
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