DE937946C - Process for the preparation of tertiary esters of phosphorous acid - Google Patents
Process for the preparation of tertiary esters of phosphorous acidInfo
- Publication number
- DE937946C DE937946C DEF10530A DEF0010530A DE937946C DE 937946 C DE937946 C DE 937946C DE F10530 A DEF10530 A DE F10530A DE F0010530 A DEF0010530 A DE F0010530A DE 937946 C DE937946 C DE 937946C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- phosphorous acid
- tertiary
- tertiary esters
- neutralization
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 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 title claims description 3
- 150000008027 tertiary esters Chemical class 0.000 title claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SGXIEZNAOCVSKO-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl formate Chemical compound C1CC2C(OC=O)CC1C2 SGXIEZNAOCVSKO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- -1 phosphorus halide Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000008028 secondary esters Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-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
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without 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
AUSGEGEBEN AM 19. JANUAR 1956ISSUED JANUARY 19, 1956
F 10530 IVb 1120F 10530 IVb 1120
Die Herstellung tertiärer aliphatischer Ester der phosphorigen Säure aus Phosphortrihalogenid und dem betreffenden Alkohol gelang bekanntlich bisher allgemein nur bei gleichzeitiger Anwesenheit eines Säurebinders zur Beseitigung des neben dem Ester entstehenden Chlorwasserstoffs. Es ist auch schon vorgeschlagen worden, und zwar zur Darstellung vonTriamylphosphit oder aromatischen Estern, die Reaktion ohne Säurebinder in einer kontinuierlich arbeitenden Apparatur mit Entgasungskolonne für den Chlorwasserstoff ablaufen zu lassen, jedoch führt diese Arbeitsweise bei Veresterung der niederen Alkohole nur bis zu den sekundären Estern. Etwa entstehender tertiärer Ester würde unter den hier herrschenden Bedingungen mit dem reichlich vorhandenen Chlorwasserstoff zu Alkylhalogenid und sauren Estern reagieren.The preparation of tertiary aliphatic esters of phosphorous acid from phosphorus trihalide and As is well known, the alcohol in question has generally only succeeded in the simultaneous presence of one Acid binder to remove the hydrogen chloride formed in addition to the ester. It's also beautiful has been proposed for the preparation of triamyl phosphite or aromatic esters, the Reaction without acid binders in a continuously operating apparatus with a degassing column for to allow the hydrogen chloride to run off, but this procedure leads to the esterification of the lower Alcohols only up to the secondary esters. Any resulting tertiary ester would be among the conditions prevailing here with the abundant hydrogen chloride to form alkyl halide and acid esters react.
Als Säurebinder, die den bei der Veresterungsreaktion sich bildenden Chlorwasserstoff im Augenblick seiner Entstehung unschädlich machen, waren bisher nur solche Stoffe brauchbar, die weder aktiven Wasserstoff enthalten noch bei der Neutralisation Wasser bilden, weil sonst an der Phosphor-Halogen-Bindung störende Konkurrenzreaktionen eintreten. Es kamen somit praktisch nur die betreffenden Alkoholate oder tertiäre Basen (z.B.Pyridin) in Frage, also verhältnismäßig kostspielige Stoffe. Da Alkoholate in reinem Zustand nur schwer herzustellen und zu handhaben sind, werden sie zum vorliegenden Zweck praktisch aus-As an acid binder, the hydrogen chloride formed during the esterification reaction at the moment To render its origin harmless, so far only substances that are neither still contain active hydrogen during the neutralization form water, otherwise at the Competing reactions that interfere with phosphorus-halogen bonds occur. So practically only came the alcoholates or tertiary bases concerned (e.g. pyridine) in question, i.e. relatively expensive ones Fabrics. Since alcoholates are difficult to manufacture and handle in their pure state, are they practically designed for the present purpose
schließlich in alkoholischer Lösung eingesetzt. Dies bedingt eine erhebliche Verdünnung des Reaktionsgemisches und macht umfangreiche Rückgewinnungsprozesse unumgänglich. Tertiäre Basen weisen neben ihrer Giftigkeit den Nachteil auf, daß _ sie von den niederen Trialkylphosphiten nicht sehr leicht vollständig zu trennen sind.finally used in alcoholic solution. This requires a considerable dilution of the reaction mixture and makes extensive recovery processes unavoidable. In addition to their toxicity, tertiary bases have the disadvantage that _ they are not very easy to completely separate from the lower trialkyl phosphites.
Demgegenüber wurde nunmehr ein Weg gefunden, der es erlaubt, die Neutralisation mit Ammoniak vorzunehmen. Es konnte nämlich festgestellt werden, daß tertiäre Phosphite bei Temperaturen unter —20° gegen Halogenwasserstoff beständig sind. Anderseits verläuft die hier erwünschte Veresterungsreaktion zwischen Phosphorhalogenid und Alkohol jedoch auch bei diesen Temperaturen noch augenblicklich. Damit ergibt sich' die Möglichkeit, die Veresterung des Alkohols zu Ende zu führen, bevor der entstandene Chlorwasserstoff neutralisiert ist; nur muß die Temperatur des Reaktionsgemisches bis zur vollständigen Neutralisation ununterbrochen tiefer als — 2O° gehalten werden, weil man andernfalls, wenigstens von den niederen Alkoholen, nur saure Ester erhält. Da das System bei dieser Arbeitsweise, zur Zeit der Neutralisation keine Phosphor-Halogen-Bindungen mehr enthält, können auch Basen mit aktivem Wasserstoff, insbesondere Ammoniak, als Säurebinder verwandt werden. Der Vorzug des Verfahrens liegt neben dem geringen Preis des Ammoniaks und der Leichtigkeit seiner Handhabung unter anderem darin, daß eine Verdünnung des Reaktionsgemisches nur insoweit erforderlich ist, als dies die Handhabung des heterogenen System bei der Neutralisation erfordert.In contrast, a way has now been found that allows neutralization with ammonia to undertake. It was found that tertiary phosphites at temperatures are resistant to hydrogen halide below -20 °. On the other hand, the one that is desired here runs Esterification reaction between phosphorus halide and alcohol, however, also at these temperatures still instantly. This gives the possibility of esterifying the alcohol To end before the hydrogen chloride formed is neutralized; just have to be the temperature of the reaction mixture until complete neutralization is continuously lower than - 20 °, because otherwise, at least of the lower alcohols, one would only be acidic Ester receives. Since the system does not work in this way at the time of neutralization, there are no phosphorus-halogen bonds contains more, bases with active hydrogen, especially ammonia, can also be used as acid binders. Of the The advantage of the process lies in addition to the low price of ammonia and its ease Handling includes the fact that a dilution of the reaction mixture is only necessary to the extent that it is necessary is than the handling of the heterogeneous system in the neutralization requires.
Außerdem genügt eine einmalige Wasserabscheidung zur vollständigen Abtrennung des Esters.In addition, a single separation of water is sufficient for complete separation of the ester.
In einem Rundkolben mit Rührer werden 520 ecm wasserfreies Äthanol vorgelegt und bei —25 ° unter Rühren mit 137,5 g Phosphortrichlorid versetzt. Anschließend wird bei der gleichen Temperatur durch Einleiten von gasförmigem Ammoniak neutralisiert. Von Beginn der Eintragung des Phosphortrichlorids bis zur Beendigung der Neutralisation müssen Erwärmungen über —-20° durchgehend vermieden werden. Die Neutralität am Ende des Prozesses kann z. B. am Umschlag von Methylorange erkannt werden, das dem Reaktionsgemisch in fester Form zugesetzt wurde. Durch Extraktion mit 11 Wasser wird der Ester abgetrennt. Hierbei "darf der pH-Wert der wäßrigen Phase den Wert S nicht unterschreiten. Das gewonnene Triäthylphosphit kann erforderlichenfalls durch Destillation im Wasserstrahlvakuum gereinigt werden (Kp. 10 Torr 450). Ausbeute an Reindestillat 133 g = 80%.520 ecm of anhydrous ethanol are placed in a round-bottom flask with a stirrer and 137.5 g of phosphorus trichloride are added at -25 ° while stirring. It is then neutralized at the same temperature by introducing gaseous ammonia. From the beginning of the introduction of the phosphorus trichloride until the end of the neutralization, temperatures above -20 ° must be avoided at all times. The neutrality at the end of the process can e.g. B. can be recognized by the envelope of methyl orange, which was added to the reaction mixture in solid form. The ester is separated off by extraction with 11% water. Here, "may not fall below the value S of the pH value of the aqueous phase. The triethyl phosphite obtained, if necessary, can be purified by distillation under water pump vacuum (bp. 10 Torr 45: 0). Yield of pure distillate 133 g = 80%.
Claims (1)
Deutsche Patentschrift Nr. 628 273;
USA.-Patentschrift Nr. 2582817.Referred publications:
German Patent No. 628 273;
U.S. Patent No. 2582817.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF10530A DE937946C (en) | 1952-12-04 | 1952-12-05 | Process for the preparation of tertiary esters of phosphorous acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE749550X | 1952-12-04 | ||
| DEF10530A DE937946C (en) | 1952-12-04 | 1952-12-05 | Process for the preparation of tertiary esters of phosphorous acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE937946C true DE937946C (en) | 1956-01-19 |
Family
ID=25947535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF10530A Expired DE937946C (en) | 1952-12-04 | 1952-12-05 | Process for the preparation of tertiary esters of phosphorous acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE937946C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1132552B (en) * | 1956-05-28 | 1962-07-05 | Monsanto Chemicals | Process for the preparation of trialkyl phosphites |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE628273C (en) * | 1932-12-29 | 1936-03-31 | Chem Fab Von Heyden Akt Ges | Process for the continuous production of organic phosphites |
| US2582817A (en) * | 1949-09-07 | 1952-01-15 | Monsanto Chemicals | Method of producing c1-c3 dialkyl hydrogen phosphites |
-
1952
- 1952-12-05 DE DEF10530A patent/DE937946C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE628273C (en) * | 1932-12-29 | 1936-03-31 | Chem Fab Von Heyden Akt Ges | Process for the continuous production of organic phosphites |
| US2582817A (en) * | 1949-09-07 | 1952-01-15 | Monsanto Chemicals | Method of producing c1-c3 dialkyl hydrogen phosphites |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1132552B (en) * | 1956-05-28 | 1962-07-05 | Monsanto Chemicals | Process for the preparation of trialkyl phosphites |
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