DE1203772B - Process for the production of phosphonium compounds - Google Patents
Process for the production of phosphonium compoundsInfo
- Publication number
- DE1203772B DE1203772B DEF44424A DEF0044424A DE1203772B DE 1203772 B DE1203772 B DE 1203772B DE F44424 A DEF44424 A DE F44424A DE F0044424 A DEF0044424 A DE F0044424A DE 1203772 B DE1203772 B DE 1203772B
- Authority
- DE
- Germany
- Prior art keywords
- phosphonium compounds
- tris
- production
- ester
- methyl
- 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
- 150000004714 phosphonium salts Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- -1 aromatic aliphatic radical Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- LRIWHHSVZCKNJL-UHFFFAOYSA-N 1-diethoxyphosphoryldodecane Chemical compound CCCCCCCCCCCCP(=O)(OCC)OCC LRIWHHSVZCKNJL-UHFFFAOYSA-N 0.000 description 1
- GAXCMCDOFDHUKP-UHFFFAOYSA-N COP(OC)=O.C1(=CC=CC=C1)C=C Chemical compound COP(OC)=O.C1(=CC=CC=C1)C=C GAXCMCDOFDHUKP-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- ATLPLEZDTSBZQG-UHFFFAOYSA-L dioxido-oxo-propan-2-yl-$l^{5}-phosphane Chemical compound CC(C)P([O-])([O-])=O ATLPLEZDTSBZQG-UHFFFAOYSA-L 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WKSYTZHMRBAPAO-UHFFFAOYSA-M tetraethylphosphanium;iodide Chemical compound [I-].CC[P+](CC)(CC)CC WKSYTZHMRBAPAO-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (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 Phosphoniumverbindungen Gegenstand der Erfindung ist ein Verfahren zur Herstellung neuartiger Phosphoniumverbindungen.Process for the preparation of phosphonium compounds Invention is a process for the preparation of novel phosphonium compounds.
Tris-hydroxymethyl-phosphin reagiert ebenso wie Phosphine, wie z. B. Triäthylphosphin oder Tributylphosphin, und Amidophosphine, wie z. B. das Bis-(dimethylamido)-äthylphosphin, leicht mit Alkylhalogeniden, Dimethylsulfat und Trimethylphosphat zu den entsprechenden Phosphoniumverbindungen. Tris-hydroxymethyl-phosphine reacts just like phosphines, such as. B. triethylphosphine or tributylphosphine, and amidophosphines, such as. B. bis (dimethylamido) ethylphosphine, easily with alkyl halides, dimethyl sulfate and trimethyl phosphate to the corresponding Phosphonium compounds.
Wie sich zeigen läßt, liegt dabei beispielsweise die Reaktionsfähigkeit des Tris-hydroxymethyl-phosphins, sich mit Äthyljodid zu quartärisieren, zwischen der von Triäthylphosphin und Bis-(diäthylamido)-äthylphosphin; denn setzt man ein Gemisch von je 1/,,Mol Triäthylphosphin und Tris-hydroxymethyl-phosphin in Methanol bei 50"C mit 1/,,Mol Äthyljodid um, so erhält man fast ausschließlich Tetraäthylphosphoniumjodid, während Tris-hydroxymethyl-phosphin beinahe vollständig zurückgewonnen werden kann. As can be shown, this is, for example, the ability to react of tris-hydroxymethyl-phosphine to quaternize with ethyl iodide between that of triethylphosphine and bis (diethylamido) ethylphosphine; because one uses Mixture of 1 / ,, mol each of triethylphosphine and tris-hydroxymethylphosphine in methanol at 50 "C with 1 / ,, mol of ethyl iodide, one obtains almost exclusively tetraethylphosphonium iodide, while tris-hydroxymethyl-phosphine can be almost completely recovered.
Bis-(diäthylamido)-äthylphosphin setzt sich erst bei noch höheren Temperaturen mit Äthyljodid um.Bis (diethylamido) ethylphosphine only sets in at even higher levels Temperatures with ethyl iodide around.
Selbst nach mehrstündigem Kochen unter Rückfluß von 1 Mol Triäthylphosphin und 1 Mol Methanphosphonsäuredimethylester läßt sich mit einfachen Mitteln (etwa durch Zusatz von Methyljodid) das gesamte Triäthylphosphin abtrennen.Even after several hours of refluxing 1 mol of triethylphosphine and 1 mole of dimethyl methanephosphonate can be obtained with simple means (e.g. Separate all of the triethylphosphine by adding methyl iodide).
Es wurde nun überraschenderweise gefunden, daß man Phosphoniumverbindungen erhält, wenn man Phosphonsäureester der allgemeinen Formel in der R einen aromatischen, einen gesättigten oder ungesättigten aliphatischen oder aromatisch-aliphatischen Rest, R' den Methyl- oder Äthylrest und R" eine Alkylgruppe bedeutet, vorzugsweise ohne organisches Lösungsmittel, unter Erwärmen mit Trishydroxymethyl-phosphin umsetzt. Dabei erhält man in meist quantitativer Ausbeute Phosphoniumver bindungen des Typs in der die Reste R, R' und R" die vorstehend angegebene Bedeutung haben. Man setzt die Ausgangsstoffe bevorzugt im Molverhältnis 1 : 1 um. Die Umsetzung erfolgt vorzugsweise ohne organisches Lösungsmittel bei Temperaturen von etwa 80 bis etwa 180°C, vorzugsweise 100 bis 1500C.It has now surprisingly been found that phosphonium compounds are obtained when phosphonic acid esters of the general formula are obtained in which R is an aromatic, a saturated or unsaturated aliphatic or aromatic-aliphatic radical, R 'is the methyl or ethyl radical and R "is an alkyl group, preferably without an organic solvent, is reacted with trishydroxymethylphosphine with heating Yield Phosphoniumver compounds of the type in which the radicals R, R 'and R "have the meaning given above. The starting materials are preferably reacted in a molar ratio of 1: 1. The reaction is preferably carried out without an organic solvent at temperatures of about 80 to about 180.degree. C., preferably 100 to 1500C.
Im allgemeinen wird die Umsetzung bei Normaldruck ausgeführt, doch kann auch bei erhöhtem Druck bis etwa 6 atü gearbeitet werden. Als Phosphonsäureester werden für das Verfahren Phosphonsäuren der vorstehend angegebenen allgemeinen Formel, z. B. Methan-, Äthan-, Butan-, Dodecan-, Benzol-, 4-Methylbenzol-, Hydroxymethan-, 1-Hydroxy-1-phenyl-äthan-(1)-, Athylen- und 1-Phenyl-äthylen-phosphonsäure verwendet, die wenigstens eine Methyl-oder Äthylestergruppe und eine beliebige Alkylestergruppe enthalten. In general, the reaction is carried out at normal pressure, however can also be used at increased pressure up to about 6 atmospheres. As a phosphonic acid ester phosphonic acids of the general formula given above are used for the process, z. B. methane, ethane, butane, dodecane, benzene, 4-methylbenzene, hydroxymethane, 1-hydroxy-1-phenyl-ethane- (1) -, ethylene- and 1-phenyl-ethylene-phosphonic acid used, the at least one methyl or ethyl ester group and any alkyl ester group contain.
Die Aufarbeitung erfolgt nach beendeter Reaktion auf übliche Weise, z. B. durch anschließendes Erhitzen unter vermindertem Druck. After the reaction has ended, it is worked up in the usual way, z. B. by subsequent heating under reduced pressure.
Die auf diese Weise herstellbaren Phosphoniumverbindungen fallen häufig als Öle in so großer Reinheit an, daß sich eine weitere Reinigung erübrigt. The phosphonium compounds that can be prepared in this way fall often as oils in such great purity that further purification is not necessary.
Diese neuen Verbindungen können unter anderem zum Flammfestmachen von Textilien und Papier verwendet werden. These new compounds can be used, among other things, to make them flame resistant used by textiles and paper.
Beispiel 1 In einem Dreihalskolben mit Rührer, Thermometer, Tropftrichter und Gaseinleitungsrohr werden unter Rühren und Luftausschuß 24,8 g (1/5 Mol) Tris-(hydroxymethyl)-phosphin auf 1000 C erhitzt und langsam 24,8 g (l/ Mol) Methanphosphonsäure-dimethylester zugetropft. Die Reaktion läuft unter Erwärmung des Kolbeninhalts ab. Beim anschließenden Erwärmen im Vakuum bis 120"C kann kein Methanphosphonsäure-dimethylesterabdestilliertwerden. Nach dem Abkühlen werden 49,6 g nahezu farbloses Ö1 erhalten, das nach einiger Zeit zu einer farblosen Kristallmasse von wachsartiger Beschaffenheit erstarrt. Example 1 In a three-necked flask with stirrer, thermometer, dropping funnel and the gas inlet pipe, 24.8 g (1/5 mol) of tris (hydroxymethyl) phosphine are added with stirring and rejecting air heated to 1000 C and slowly 24.8 g (l / mol) methanephosphonic acid dimethyl ester added dropwise. The reaction takes place while the contents of the flask are heated. During the subsequent If heated in a vacuum to 120 "C, no methanephosphonic acid dimethyl ester can be distilled off. After cooling, 49.6 g of almost colorless oil are obtained, which after some time solidified to a colorless crystal mass of waxy consistency.
Das Produkt ist löslich in Wasser, Methanol, Isopropanol, Dimethylformamid und Pyridin, aber unlöslich in Äther, Tetrahydrofuran, Benzol, Tetrachlorkohlenstoff und Aceton.The product is soluble in water, methanol, isopropanol, dimethylformamide and pyridine, however insoluble in ether, tetrahydrofuran, benzene, carbon tetrachloride and acetone.
Das KMR-Spektrum stimmt mit der Struktur überein. Es treten je ein Dublett bei 1,37 ppm und 2,10ppm, beide mit der relativen Fläche 3 auf, die entsprechend den Shiftwerten und Kopplungsparametern direkt an Phosphor gebundenen Methyl- gruppen zugeordnet werden. Ein weiteres Dublett der relativen Flächen 3 erscheint bei 3,68 ppm und entspricht einer P -0 - CH3-Gruppierung. Eine breite, nicht aufgespaltene Linie bei 4,85 ppm mit der relativen Fläche 6 wird der Methylengruppe neben Phosphor zugeordnet. Für das Hydroxidsignal bei 9,4 ppm wird erwartungsgemäß die Fläche 3 gefunden. Die elektrische Leitfähigkeit einer wäßrigen Lösung dieser Verbindung liegt in der gleichen Größenordnung wie die einer äquivalenten Lösung von Tetrakis-hydroxymethyl-phosphoniumchlorid in Wasser.The KMR spectrum agrees with the structure match. A doublet each occurs at 1.37 ppm and 2.10 ppm, both with the relative area 3, which are assigned to methyl groups directly bound to phosphorus in accordance with the shift values and coupling parameters. Another doublet of the relative areas 3 appears at 3.68 ppm and corresponds to a P -0-CH3 group. A broad, unsplit line at 4.85 ppm with a relative area of 6 is assigned to the methylene group next to phosphorus. As expected, area 3 is found for the hydroxide signal at 9.4 ppm. The electrical conductivity of an aqueous solution of this compound is of the same order of magnitude as that of an equivalent solution of tetrakis-hydroxymethyl-phosphonium chloride in water.
Nach der gleichen Methode wurde Tris-hydroxymethyl-phosphin ferner
umgesetzt mit
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF44424A DE1203772B (en) | 1964-11-12 | 1964-11-12 | Process for the production of phosphonium compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF44424A DE1203772B (en) | 1964-11-12 | 1964-11-12 | Process for the production of phosphonium compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1203772B true DE1203772B (en) | 1965-10-28 |
Family
ID=7100030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF44424A Pending DE1203772B (en) | 1964-11-12 | 1964-11-12 | Process for the production of phosphonium compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1203772B (en) |
-
1964
- 1964-11-12 DE DEF44424A patent/DE1203772B/en active Pending
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