GB2175904A - Preparation of phosphonic acid derivatives - Google Patents
Preparation of phosphonic acid derivatives Download PDFInfo
- Publication number
- GB2175904A GB2175904A GB08611939A GB8611939A GB2175904A GB 2175904 A GB2175904 A GB 2175904A GB 08611939 A GB08611939 A GB 08611939A GB 8611939 A GB8611939 A GB 8611939A GB 2175904 A GB2175904 A GB 2175904A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphonic acid
- formula
- acid derivative
- dichloride
- phosphorus pentachloride
- 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.)
- Withdrawn
Links
- 150000003007 phosphonic acid derivatives Chemical class 0.000 title claims abstract description 20
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 12
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- NJLHHACGWKAWKL-UHFFFAOYSA-N ClP(Cl)=O Chemical compound ClP(Cl)=O NJLHHACGWKAWKL-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- LOUZURPQCYZSJH-UHFFFAOYSA-N 1-chloro-2-dichlorophosphorylethane Chemical compound ClCCP(Cl)(Cl)=O LOUZURPQCYZSJH-UHFFFAOYSA-N 0.000 abstract description 6
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 abstract description 5
- KCKMCFYLQPTGGE-UHFFFAOYSA-N ClCCOP(OCCCl)=O.ClCC Chemical compound ClCCOP(OCCCl)=O.ClCC KCKMCFYLQPTGGE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006317 isomerization reaction Methods 0.000 abstract description 5
- MLSZIADXWDYFKM-UHFFFAOYSA-N 1-dichlorophosphorylethene Chemical compound ClP(Cl)(=O)C=C MLSZIADXWDYFKM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013058 crude material Substances 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000005648 plant growth regulator Substances 0.000 abstract description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001459 lithography Methods 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QJSFUOBKBXVTMN-UHFFFAOYSA-N C=C.P(O)(O)=O Chemical compound C=C.P(O)(O)=O QJSFUOBKBXVTMN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- KYTYFLLFJMDIFW-UHFFFAOYSA-N P(=O)(Cl)Cl.C=C Chemical compound P(=O)(Cl)Cl.C=C KYTYFLLFJMDIFW-UHFFFAOYSA-N 0.000 description 1
- 101100462600 Solanum lycopersicum PAL5 gene Proteins 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/42—Halides 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
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)
Abstract
Phosphonic acid derivatives are prepared by reacting 2-chloro-ethane phosphonic acid-bis-(2- chloroethyl) ester with phosphorus pentachloride. The resultant 2-chloroethane phosphonic acid dichloride may then be hydrolysed to produce 2-chloroethane phosphonic acid or subjected to dehydrohalogenation to produce vinyl phosphonic acid dichloride. The vinyl phosphonic acid dichloride may then be hydrolysed to form vinyl phosphonic acid. It is particularly preferred for the 2-chloroethane phosphonic acid-bis-(2- chloroethyl) ester to be a crude material produced by subjecting tris(2-chloroethyl) phosphite to thermal isomerisation. The phosphonic acid derivatives are particularly useful as plant growth regulators or flame retardants and the vinyl substituted derivatives can be polymerised for use in lithography and the manufacture of dental compositions.
Description
SPECIFICATION
Improvements in or relating to phosphonic acid derivatives
This invention relates to the preparation of phosphonic acid derivatives.
The reaction between phosphorus trichloride and ethylene oxide produces tris(2-chloroethyl)phosphite which on subsequent rearrangement under heat (i.e. thermal isomerisation) is converted into 2-chloroethane phosphonic acid-bis-(2-chloro-ethyl)ester together with non-volatile oligomers. Kabachnick et al (Chemical Abstracts CA 42 7241-3,1948) treated this crude material with phosphorus pentachloride to obtain a 52% yield of 2-chloroethane phosphonic acid dichloride.
It is one object of the present invention to provide a route whereby, from such crude starting material, it is possible to prepare, in high yield and quality, 2-chloroethane phosphonic acid dichloride which can be further processed to give phosphonic acid derivatives which could otherwise only be obtained through more difficult preparative routes.
According to one aspect of the present invention, there is provided a method of preparing a phosphonic acid derivative which method comprises the steps of reacting a phosphonic acid ester of the formula
with phosphorus pentachloride to produce a phosphonic acid dichloride of the formula
and thereafter converting the phosphonic acid dichloride into a phosphonic acid derivative by (i) hydrolysing it to produce a phosphonic acid derivative of the formula
or by (ii) dehydrohalogenating it to produce a phosphonic acid derivative of the formula
The term phosphonic acid ester is intended to include the mixture of 2-chloroethane phosphonic acid-bis-(2-chloroethyl) ester and additional products produced by thermal isomerisation of tris(2-chloroethyl)phosphite.
The reaction between the ester and the phosphorus pentachloride is carried out above 120 degC, preferably at a temperature of 130-140 degC and the phosphorus pentachloride can be added as a solid or can be formed in situ by using phosphorus trichloride and chlorine gas. A catalyst is ordinarily required and this may be, for example, a metal salt, particularly a chloride, for example, ferric chloride, cuprous or cupric chloride, nickel chloride, cobalt chloride or lithium chloride. In this way, the crude material obtained from the thermal isomerisation of tris(2-chloroethyl)phosphite can be converted to 2-chloroethane phosphonic acid dichloride in yields approaching the theoretical, i.e. 90% or greater and this material can then be used as an intermediate in the preparation of valuable phosphonic acid derivatives such as substituted phosphonic acid and esters.
The phosphonic acid derivative of formula
may be hydrolysed to form a further phosphonic acid derivative of formula
The above hydrolysis treatments may be carried out by adding the appropriate acid dichloride to water. However, it is a further object of the present invention to provide an improved method of hydrolysing phosphonic acid dichlorides.
Accordingly, a further aspect of the present invention provides a method of hydrolysing a phosphonic acid dichloride of formula
which method comprises dissolving the dichloride in an inert water immiscible solvent and adding water to the resultant solution.
Any inert, water immiscible, solvent for example, toluene, di-, tri-, or tetra-chloromethane, di-, tri-, or tetra-chloroethane, or xylene may be used.
The 2-chloroethane phosphonic acid which may be produced in accordance with the present invention is well known for its agricultural properties particularly as a plant growth regulator, but heretofore it has only been generally available via the high temperature and/or high pressure hydrolysis reaction between hydrogen chloride and 2-chloroethane phosphonic acid-bis-(2-chloroethyl)ester.
The dehydrohalogenation is preferably carried out by dissolving the acid dichloride in an inert solvent and adding an organic base such as a tertiary amine, for example triethylamine, pyridine or tri-n-butylamine.
The vinyl phosphonic acid dichloride produced by such dehydrohalogenation (i.e. ethene phosphonyl dichloride), is a useful intermediate in polymer chemistry and in the manufacture of flame retardants, as in fact is 2chloroethane phosphonyl dichloride.
The vinyl phosphonic acid (i.e. ethene phosphonic acid) produced by the hydrolysis of the vinyl phosphonic acid dichloride, is useful in a polymerised form in lithographic and dental compositions.
The following Examples illustrate the invention
Example I
Bis-(0,0-2-chloroethyl)-2'-chloroethane phosphonate is available under the name Biscep from Mobil Oil Corporation and, in this form, consists of a mixture of the ester and a polymeric phosphonate produced by the thermal isomerisation of tris(2-chloroethyl)phosphite.
1.58 kg (5.87 mol) of Biscep was charged into a vessel set up for heating, stirring and continuous addition of a solid above a distillation head, and 13.5 g of ferric chloride were added. The mixture was heated, with stirring, to a temperature of 135 degC. Phosphorus pentachloride (2.45 Kg, 11.75 mol) was added portionwise over a period of 1 hour, the temperature being maintained at about 130 degC so as to allow POCI3 and dichloroethane to distill off as they were formed. When all the PCl5 had been added, the mixture was held at the reaction temperature until the
POCI3 and dichloroethane had distilled off and was then cooled. Vacuum distillation at 15-20 mm Hg produced 1kg (5.5 mol i.e. 94% theoretical) of the product (2-chloroethane phosphonic acid dichloride) at a temperature of 95-96 degC.
Using the same quantities of starting materials and reaction conditions, replacement of the ferric chloride with 15.8 g of cuprous chloride or 17.29 of cupric chloride produced yields respectively of .98 kg (5.39 mol i.e.
92% theoretical) and .987 kg (5.43 mol i.e.
92.5% theoretical).
The phosphonic acid dichloride (1 kg) was added dropwise to 290 g of ice cold water with vigorous stirring and external cooling.
The reaction was substantially exothermic and hydrogen chloride gas was evolved. The rate of addition and degree of cooling were adjusted to keep the reaction temperature below 80 degC. A 90% solution of 2-chloroethane phosphonic acid was produced.
The same amount of the phosphonic acid dichloride was dissolved in toluene and water (5% excess) added. The reaction was again exothermic and hydrogen chloride gas was evolved. However, the presence of the solvent meant that the heat produced was more easily dissipated. A gummy solution of 2-chloroethane phosphonic acid was produced.
1 kg of 2-chloroethane phosphonic acid dichloride was dissolved in toluene and external cooling provided to maintain the temperature at 15-20 degC. Triethylamine (0.55 kg, 5.5 mol) was added dropwise with stirring. A heavy precipitate of triethylamine hydrochloride was formed and after standing for 3-4 hours at room temperature, this was filtered off. Under vacuum distillation at 15-20 mm Hg. the toluene distilled off at 25 degC and the product (ethene phosphonic acid dichloride) distil!ed off at 68-70 degC in a yield of 540 g.
Hydrolysis of this product to the acid was carried out in the same way as described above.
Example II
Biscep (1.58 kg) was charged to a vessel equipped for heating and stirring, for the continuous addition of gas and liquid, and for fractional distillation via a variable take-off head. Ferric chloride (13.5 g) was added and the mixture heated to 135 degC. Chlorine gas was added and with the system set to total reflux, 10% of the PCl3 was added dropwise over a period of 15 minutes. The PCl3 refluxed initially but, after a short while, this ceased as it was converted to PAL5. POCI3 and dichloroethane were allowed to distil off at a still-head temperature of 90 degC. When the distillation slowed down, the distillation outlet was closed and total reflux allowed. The process was repeated with further quantities of PCl3 until 1.61 kg (11.7 mol) had been added.
When distillation had ceased, the mixture was cooled and submitted to vacuum distillation at 15 mm Hg. The product boiled at 95-96 degC.
Hydrolysis of the product was carried out by dissolving it in trichloroethane and adding water (30% excess) to the solution in a cooled vessel. The reaction was exothermic and hydrogen chloride gas was evolved. A concentrated solution of 2-chloroethane phosphonic acid was separated.
Claims (19)
1. A method of preparing a phosphonic acid derivative which method comprises the steps of reacting a phosphonic acid ester of the formula
with phosphorus pentachloride to produce a phosphonic acid dichloride of the formula
and thereafter converting the phosphonic acid dichloride into a phosphonic acid derivative by (i) hydrolysing it to produce a phosphonic acid derivative of the formula
or by (ii) dehydrohalogenating it to produce a phosphonic acid derivative of the formula
2. A method in accordance with claim 1 comprising the further step of hydrolysing the phosphonic acid derivative of the formula
to produce a further phosphonic acid derivative of formula
3.A method according to claim 1 or 2 wherein the dehydrohalogenation step is effected by dissolving the substance to be dehydrohalogenated in an inert solvent and adding an organic base to the resultant solution.
4. A method according to claim 3 wherein the organic base is a tertiary amine.
5. A method according to claim 4 wherein the tertiary amine is triethylamine, pyridine, or tri-n-butylamine.
6. A method according to any one of the preceding claims wherein the reaction between the phosphonic acid ester and the phosphorus pentachloride is carried out in the presence of a metal salt catalyst.
7. A method according to claim 6 wherein the metal salt catalyst is ferric chloride, copper chloride, nickel chloride, cobalt chloride, or lithium chloride.
8. A method according to any one of the preceding claims wherein the reaction between the phosphorus pentachloride and said phosphonic acid ester is carried out at a temperature of greater than 120 C.
9. A method according to claim 8 wherein said reaction is carried out at a temperature of from 130 to 140"C.
10. A method according to any one of the preceding claims wherein the phosphorus pentachloride is added in solid form.
11. A method according to any one of claims 1 to 9 wherein the phosphorus pentachloride is generated in situ from phosphorus trichloride and gaseous chlorine.
12. A method according to any one of the preceding claims wherein said phosphonic acid ester is obtained by thermally isomerising tris(2-chloroethyl) phosphite.
13. A method according to claim 12, wherein the tris(2-chloroethyl) phosphite is produced by reacting phosphorus trichloride and ethylene oxide.
14. A method according to any one of the preceding claims wherein the or each hydrolysis step is carried out by adding the substance to be hydrolysed to water.
15. A method according to any one of claims 1 to 13 wherein the or each hydrolysis step is carried out by dissolving the substance to be hydrolysed in an inert water immiscible solvent and adding water to the resultant solution.
16. A method of hydrolysing a phosphonic acid dichloride of formula
which method comprises dissolving the dichloride in an inert water immiscible solvent and adding water to the resultant solution.
17. A method according to claim 15 or 16 wherein the inert solvent is toluene, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, or xylene.
18. A method according to claim 1 or 16 substantially as hereinbefore described in
Example 1 or 2.
19. A phosphonic acid derivative whenever produced by the method claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858512507A GB8512507D0 (en) | 1985-05-17 | 1985-05-17 | Phosphonic acid derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8611939D0 GB8611939D0 (en) | 1986-06-25 |
| GB2175904A true GB2175904A (en) | 1986-12-10 |
Family
ID=10579283
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB858512507A Pending GB8512507D0 (en) | 1985-05-17 | 1985-05-17 | Phosphonic acid derivatives |
| GB08611939A Withdrawn GB2175904A (en) | 1985-05-17 | 1986-05-16 | Preparation of phosphonic acid derivatives |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB858512507A Pending GB8512507D0 (en) | 1985-05-17 | 1985-05-17 | Phosphonic acid derivatives |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB8512507D0 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761252A (en) * | 1986-08-30 | 1988-08-02 | Hoechst Aktiengesellschaft | Process for the preparation of vinylphosphonic dichloride |
| CN105949236A (en) * | 2016-05-30 | 2016-09-21 | 淮阴工学院 | Joint production method of ethephon and vinylphosphonic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858057A (en) * | 1956-03-14 | 1961-01-04 | Hoechst Ag | Vinyl phosphonic acid and derivatives thereof and a process for their manufacture |
| US3775470A (en) * | 1971-07-07 | 1973-11-27 | Gaf Corp | Process for the preparation of organophosphonyl dichlorides |
-
1985
- 1985-05-17 GB GB858512507A patent/GB8512507D0/en active Pending
-
1986
- 1986-05-16 GB GB08611939A patent/GB2175904A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858057A (en) * | 1956-03-14 | 1961-01-04 | Hoechst Ag | Vinyl phosphonic acid and derivatives thereof and a process for their manufacture |
| US3775470A (en) * | 1971-07-07 | 1973-11-27 | Gaf Corp | Process for the preparation of organophosphonyl dichlorides |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS CA 42 7241-3, 1948 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761252A (en) * | 1986-08-30 | 1988-08-02 | Hoechst Aktiengesellschaft | Process for the preparation of vinylphosphonic dichloride |
| CN105949236A (en) * | 2016-05-30 | 2016-09-21 | 淮阴工学院 | Joint production method of ethephon and vinylphosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8512507D0 (en) | 1985-06-19 |
| GB8611939D0 (en) | 1986-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2632018A (en) | Halogen-containing phosphorus acids and esters | |
| GB2175904A (en) | Preparation of phosphonic acid derivatives | |
| JPH04234894A (en) | Process for producing 1-halogen-1-oxophospholene | |
| US4507249A (en) | Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid | |
| US4521347A (en) | Process for preparing chlorophenylphosphanes | |
| US5391798A (en) | Process for preparing 6-chloro-(6H)-dibenz [C,-E][1,2]- oxaphosphorin | |
| US4311652A (en) | Arbuzov reactions employing an aliphatic solvent | |
| US5177238A (en) | Preparation of dialkyl allylphosphonic acid diesters | |
| US3642960A (en) | Method of producing thiono- or dithio-phosphonic acid esters | |
| US3078304A (en) | Preparation of diorganohalophosphines | |
| US4521346A (en) | Process for preparing chlorodiphenylphosphane | |
| US4708824A (en) | Process for the preparation of chloro(phenyl)phospines | |
| US4670601A (en) | Process for the preparation of bifunctional tertiary aromatic phosphine sulfides | |
| US2654784A (en) | Method for the manufacture of phosphoric acid anhydrides | |
| US4000190A (en) | Process for preparing alkyl- and aryl phosphonothioic dihalides | |
| US4173578A (en) | Production of alkenyl phosphinic acids | |
| US4632995A (en) | Process for the preparation of phenyl- and thienyl-chlorophosphane derivatives | |
| US2870204A (en) | Preparation of phosphonothioic dichlorides, tetrachlorophosphoranes, and phosphonic dichlorides | |
| US3790629A (en) | Process for preparing alkyl or aryl thiophosphorus halides and mixed isomers thereof | |
| US4052463A (en) | Process for preparing tertiary phosphine sulfides and oxides | |
| US3962323A (en) | Process for preparing alkyl- or aryl-phosphonothioic dihalides | |
| US3976690A (en) | Process for preparing alkane bis-dihalophosphines | |
| CA1230885A (en) | Process for preparing organic chlorophosphanes | |
| US6156930A (en) | Method for producing trifluoromethanesulfonyl chloride | |
| US4781867A (en) | Process for making phosphinic or phosphonic acid chlorides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |