DE1093789B - Process for the preparation of bis-dialkylphosphoryl sulfoxides - Google Patents
Process for the preparation of bis-dialkylphosphoryl sulfoxidesInfo
- Publication number
- DE1093789B DE1093789B DEF25189A DEF0025189A DE1093789B DE 1093789 B DE1093789 B DE 1093789B DE F25189 A DEF25189 A DE F25189A DE F0025189 A DEF0025189 A DE F0025189A DE 1093789 B DE1093789 B DE 1093789B
- Authority
- DE
- Germany
- Prior art keywords
- bis
- dialkylphosphoryl
- sulfoxides
- preparation
- sodium
- 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
- 150000003462 sulfoxides Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 7
- WCTKUENARPWTAY-UHFFFAOYSA-N ac1l9mss Chemical class OS(Cl)=O WCTKUENARPWTAY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 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 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- BYMVZHORNHZYPQ-UHFFFAOYSA-N sodium;diethyl phosphite Chemical compound [Na+].CCOP([O-])OCC BYMVZHORNHZYPQ-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SMBCCRRPZMKSML-UHFFFAOYSA-N 1-chlorosulfinyloxybutane Chemical compound CCCCOS(Cl)=O SMBCCRRPZMKSML-UHFFFAOYSA-N 0.000 description 1
- XHPBLHAZMLPNTF-UHFFFAOYSA-N 1-chlorosulfinyloxypropane Chemical compound CCCOS(Cl)=O XHPBLHAZMLPNTF-UHFFFAOYSA-N 0.000 description 1
- RDPAIXGJGMTFIJ-UHFFFAOYSA-N C(C)P(=O)(CC)S(=O)P(=O)(CC)CC Chemical compound C(C)P(=O)(CC)S(=O)P(=O)(CC)CC RDPAIXGJGMTFIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- DNTYXOAEBUZAJC-UHFFFAOYSA-N chlorosulfinyloxyethane Chemical compound CCOS(Cl)=O DNTYXOAEBUZAJC-UHFFFAOYSA-N 0.000 description 1
- -1 phosphoryl sulfoxides Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 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
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1658—Esters of thiopolyphosphoric acids or anhydrides
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 Bis-dialkylphosphoryl-sulfoxyden Zusatz zur Patentanmeldung F 25188 IVb /120 (Auslegesdlrift 1 085870) Gegenstand der Patentanmeldung F25188IVb/12c ist ein Verfahren zur Herstellung von Bis-dialkylphosphoryl-sulfoxyden, das dadurch gekennzeichnet ist, daß Dialkylaminosulfinsäurechloride mit 2 Mol eines 0,0 -Dialkylphosphites in geeigneten Lösemitteln zur Reaktion gebracht werden. Process for the preparation of bis-dialkylphosphoryl-sulfoxydene additive Patent application F 25188 IVb / 120 (Auslegesdlrift 1 085870) is the subject of the patent application F25188IVb / 12c is a process for the production of bis-dialkylphosphoryl sulfoxides, which is characterized in that dialkylaminosulfinic acid chlorides with 2 moles of one 0.0 dialkyl phosphites can be reacted in suitable solvents.
Es wurde gefunden, daß diese Bis-dialkylphosphorylsulfoxyde auch durch Umsetzung von Chlorsulfinsäureestern mit O,O-Dialkylphosphiten bzw. deren Salzen erhalten werden können. Die Reaktion kann durch folgendes Formelschema erläutert werden: Während nach den Angaben der USA.-Patentschrift 2 508 364 die Bis-dialkylphosphoryl-sulfoxyde durch Umsetzung von Trialkylphosphiten mit Thionylchlorid erhalten werden, gelingt es erfindungsgemäß, die erheblich leichter zugänglichen O,O-Dialkylphosphite bzw. deren Salze zu verwenden.It has been found that these bis-dialkylphosphoryl sulfoxides can also be obtained by reacting chlorosulfinic acid esters with O, O-dialkyl phosphites or their salts. The reaction can be explained by the following equation: While according to the information in US Pat. No. 2,508,364 the bis-dialkylphosphoryl sulfoxides are obtained by reacting trialkyl phosphites with thionyl chloride, it is possible according to the invention to use the considerably more easily accessible O, O-dialkyl phosphites or their salts.
Auch aus der bekannten Umsetzung von O,O-Dialkylphosphiten mit Dialkylaminosulfensäurechloriden (vgl. deutsche Patentschrift 820 001) konnte nicht geschlossen werden, daß auf die erfindungsgemäße, technisch einfache Weise, nämlich durch Umsetzung von Chlorsulfinsäureestern mit Dialkylphosphiten, Bis-dialkylphosphorylsulfoxyde gebildet werden. Also from the known reaction of O, O-dialkyl phosphites with dialkylaminosulfenic acid chlorides (see. German Patent 820 001) could not be concluded that on the technically simple manner according to the invention, namely by reacting chlorosulfinic acid esters be formed with dialkyl phosphites, bis-dialkyl phosphoryl sulfoxides.
Die folgenden Beispiele mögen das Verfahren der vorliegenden Erfindung erläutern: Beispiel 1 In üblicher Weise stellt man aus O,O-Diäthylphosphit (71 g; 1/2 Mol) in 200 ccm wasserfreiem Benzol und 11,5 g pulverförmigem Natrium eine Anschlämmung des Natriumsalzes des O,O-Diäthylphosphits her. Zu dieser Anschlämmung gibt man 80 g (1/2 Mol) Chlorsulfinsäureäthylester (Kp.62 = 52"C). Man hält die Temperatur bei 600 C 112 Stunde und saugt dann das abgeschiedene Natriumchlorid ab. Beim Fraktionieren werden 20 g Bisdiäthylphosphoryl-sulfoxyd vom Kpso,ol = 68 bis 70"C erhalten. Ausbeute 24°/o der Theorie.The following examples may illustrate the method of the present invention: Example 1 In the usual way, a slurry of the sodium salt of O, O-diethyl phosphite is prepared from O, O-diethyl phosphite (71 g; 1/2 mol) in 200 cc of anhydrous benzene and 11.5 g of powdered sodium. 80 g (1/2 mol) of ethyl chlorosulfinate (boiling point 62 = 52 ° C.) are added to this slurry. The temperature is maintained at 600 ° C. for 112 hours and the sodium chloride which has separated out is then filtered off with suction. 20 g of bisdiethylphosphoryl sulfoxide are removed during fractionation Kpso, ol = 68 to 70 "C obtained. Yield 24% of theory.
Beispiel 2 Wie im Beispiel 1 stellt man aus 71 g O,O-Diäthylphosphit und 11,5 g Natrium in Benzol eine Anschlämmung des Natrium-O,O-diäthylphosphits her. Zu dieser Anschlämmung gibt man bei 60"C 71 g Chlorsulfinsäuren-propylester (Kp.lg = 43°C). Man erwärmt noch 1 Stunde bei 60 bis 700 C, kühlt dann auf Zimmertemperatur ab und saugt das entstandene Natriumchlorid ab.Example 2 As in Example 1, a slurry of sodium O, O-diethyl phosphite is prepared from 71 g of O, O-diethyl phosphite and 11.5 g of sodium in benzene. 71 g of chlorosulfinic acid propyl ester (bp = 43 ° C.) are added to this slurry at 60 "C. The mixture is heated for a further 1 hour at 60 to 700 ° C., then cooled to room temperature and the sodium chloride formed is filtered off with suction.
Beim Fraktionieren erhält man 40 g Bis-diäthylphosphoryl-sulfoxyd vom Kp.o,ol = 66 bis 70"C. Ausbeute 50 0/, der Theorie. Beispiel 3 Wie in den Beispielen 1 und 2 wird aus 71 g O,O-Diäthylphosphit und 11,5 g Natrium in Benzol eine Anschlämmung von Natrium-O ,O-diäthylphosphit hergestellt. Auf diese Anschlämmung läßt man bei 60°C unter Rühren 78 g Chlorsulfinsäure-n-butylester (Kp.10 = 570 C) einwirken. Man erwärmt noch 1 Stunde bei 70 bis 75°C und arbeitet dann wie im Beispiel 1 und 2 auf. Es werden 40 g Bisaiäthylphosphoryl-sulfoxyd vom Kp.0,01 = 67 bis 70°C erhalten. Ausbeute 50°/0 der Theorie.Fractionation gives 40 g of bis-diethylphosphoryl sulfoxide with a boiling point of 66 to 70 ° C. Yield 50%, theoretical. Example 3 As in Examples 1 and 2, a slurry of sodium O, O-diethyl phosphite is prepared from 71 g of O, O-diethyl phosphite and 11.5 g of sodium in benzene. 78 g of n-butyl chlorosulfinate (boiling point 10 = 570 ° C.) are allowed to act on this suspension at 60 ° C. with stirring. The mixture is heated at 70 to 75 ° C. for a further hour and then worked up as in Examples 1 and 2. There are 40 g of Bisaiäthylphosphoryl-sulfoxide with a boiling point of 0.01 = 67 to 70 ° C. Yield 50% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF25189A DE1093789B (en) | 1958-03-06 | 1958-03-06 | Process for the preparation of bis-dialkylphosphoryl sulfoxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF25189A DE1093789B (en) | 1958-03-06 | 1958-03-06 | Process for the preparation of bis-dialkylphosphoryl sulfoxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1093789B true DE1093789B (en) | 1960-12-01 |
Family
ID=7091523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF25189A Pending DE1093789B (en) | 1958-03-06 | 1958-03-06 | Process for the preparation of bis-dialkylphosphoryl sulfoxides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1093789B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE820001C (en) * | 1949-09-07 | 1951-11-08 | Bayer Ag | Process for the preparation of thiopyrophosphoric acid esters |
-
1958
- 1958-03-06 DE DEF25189A patent/DE1093789B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE820001C (en) * | 1949-09-07 | 1951-11-08 | Bayer Ag | Process for the preparation of thiopyrophosphoric acid esters |
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