IL38340A - Process for the manufacture of 2-chloroethane-phosphonic acid - Google Patents
Process for the manufacture of 2-chloroethane-phosphonic acidInfo
- Publication number
- IL38340A IL38340A IL38340A IL3834071A IL38340A IL 38340 A IL38340 A IL 38340A IL 38340 A IL38340 A IL 38340A IL 3834071 A IL3834071 A IL 3834071A IL 38340 A IL38340 A IL 38340A
- Authority
- IL
- Israel
- Prior art keywords
- chloroethane
- hydrogen chloride
- phosphonic acid
- acid
- pressure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 title description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 81
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 37
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 6
- 238000003776 cleavage reaction Methods 0.000 claims description 6
- 230000007017 scission Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
- XXIDKSWYSYEFAG-UHFFFAOYSA-N 1-chloro-2-[2-chloroethoxy(2-chloroethyl)phosphoryl]oxyethane Chemical compound ClCCOP(=O)(CCCl)OCCCl XXIDKSWYSYEFAG-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QBSWHWLQSRONOM-UHFFFAOYSA-N 1-[bis(2-chloroethoxy)phosphoryl]-1-chloroethane Chemical compound ClCCOP(=O)(C(Cl)C)OCCCl QBSWHWLQSRONOM-UHFFFAOYSA-N 0.000 description 1
- SEHJHHHUIGULEI-UHFFFAOYSA-N 2-hydroxyethylphosphonic acid Chemical compound OCCP(O)(O)=O SEHJHHHUIGULEI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KKQCMAJELBNKNV-UHFFFAOYSA-N ClCCOP(O)=O.ClCC Chemical compound ClCCOP(O)=O.ClCC KKQCMAJELBNKNV-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000008096 xylene 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
- C07F9/28—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)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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
PROCESS FOR THE MANUFACTURE OF 2-CHL0E0ETHAHE- PHOSPHOHIC ACID.
(HOE 70/E 280K) HOE 70/P 280K The present invention relates to a process for the manufacture of 2-chloroethane-phosphonic acid. 2-Chloroethane-phosphonic acid is of industrial importance as ripening promotor and grov/th regulator as well as in-termediate for the manufacture of polyvinyl-phosphonic acid used in corrosion protection.
Processes for the manufacture of 2-chloroethane-phosphonic acid and its precursors have "been described in German Patent 1,123,667 and French Patent 1,558,691; furthermore by Kabachnik et al. (Chem. Abstr. 42, 7241-43), French Patent 1,565,742 and German Application 1,815,999 laid open to public inspection.
The most economic process from among the three former publications appears to be the three step process disclosed by Kabachnik et al. and carried out according to the following scheme: I II oCl) ά Cone. 0 III C1CH9CH P(0CH9CH9C1)9 > 010Η90Η9Ρ( OH) „- + ^ ,, ^ ά HC1 " 0 0 2 C1CH2CH2C1 owing to the fact that the starting products phosphorus trichloride and ethylene oxide are cheap industrial products. However, according to Kabachnik, of a non-distillable residue 10 to 207$ are formed in the first step and more than 50$ in the second step. Although this amount of residue could be reduced b carrying out the reactions in suitable solvents this would require in both steps costly distillations under HOE 70/F 280K strongly reduced pressure and at elevated temperature. In the third step Kabachnik et al. describe the hydrolysis of the pure 2-chloroethane-phosphonic acid bis-( 2-chloroethyl) ester by means of concentrated hydrochloric acid but with partial success only. The reaction product must therefore be subjected, after distillation of the excess hydrochloric acid, to further purification operations to obtain a product of satisfactory purity.
In further developing the aforesaid process French Patent 1,565,742 describes the rearrangement of tris-( 2-chloroeth 1) -phosphite in high boiling solvents, for example o-dichloro-benzene, cumene or xylene, at 150 to 160°C. The phosphonate obtained is hydrolized, without further purification, with gaseous hydrogen chloride or 20 aqueous hydrochloric acid.
The product obtained with gaseous hydrogen chloride according to Example 1 of that patent contains about; 30 of 2-chloroethane-phosphonic acid anhydride as a by-product besides 2-chloroethane-phosphonic acid as is evidenced by Example 1 of German Patent 1,815,999 cited above and describing exactly the same procedure. The reproduction of Example 2 yielded 112$ of the weight to be expected of a non-crystallizing colorless oil containing, according to the analysis, 0.5$ of 2-chloroethane-phosphonic acid bis-( 2-chloroethyl) ester, 8$ of 2-chloroethane phosphonic acid mono-( 2-chloroethyl) ester, 40$ of 2-chloroethane-phosphonic acid, and 8 - 9$ of 2-hydroxy-ethane-phosphonic acid. According to Tetrahedron Letters 1 , pages 1281 - 1284 the latter is formed in a secondary reaction when 2-chloroethane-phosphonic acid is heated with 20$ hydrochloric acid. The remainder which could not be determined by the analysis must be considered as partially dissociated poly- condensate.
The present invention provides a process for the manufacture of 2-chloroethane-phosphonic acid by cleavage of 2-chloro-ethane-phosphonic acid bis( 2-chloroethyl) ester which comprises carrying out the cleavage with aqueous hydrochloric acid, optionally in the presence of excess gaseous hydrogen chloride, at a temperature above 100°C under elevated pressure, distilling off the 1 , 2-dichloroethane formed during the reaction either continuously or discontinuously , and compensating the fall in pressure during the reaction by adding gaseous hydrogen chloride. When operating in this manner 2-chloroethane-phosphonic acid is obtained in good yield and with good purity.
The crude ester obtained is hydrolized with hydrochloric acid at elevated temperature and under pressure according to the following scheme : 0 C1CH2CH2P(0H)2 + C1CH2CH2C1 + C1CH2CH20H 0 To perform the hydrolysis the crude organic product is heated at a temperature above 100°C, preferably above 120°C, while stirring in an autoclave made of a material that is resistant to hydrochloric acid, with 0.1 to 500 by weight, calculated on the basis of crude chloroethane-phosphonic acid bis (2-chloroethyl) ester, of hydrochloric acid having a strength preferably of 30 to 38 . With increasing temperature the purity of the final product gradually decreases BO that it is not advisable to operate at temperatures above 200°C. In order to maintain always an excess amount of HOI in the autoclave, the HC1 deficiency resulting from the use of small amounts of aqueous hydrochloric acid is compensated by adding gaseous hydrogen chloride. In the reaction vessel a pressure in the range of from 1 to 10 atmospheres gauge, preferably 3 to 6 atmospheres gauge, is maintained, if necessary by forcing in hydrogen chloride. The dichloroethane formed is repeatedl distilled off by releasing the overpressure. The escaping hydrogen chloride and the hydrogen chloride used up by the reaction are replenished by forcing in again hydrogen chloride. When the reaction vessel is connected with a collecting vessel by means of a closed reflux condenser the dichloroethane can be remolded continuously, whereby losses of hydrogen chloride are avoided.
At a temperature of 130°C, for example, the hydrolysis is terminated after approximately 4 hours. The aqueous hydrochloric acid which still contains small amounts of 2-chloro-ethanol is distilled off at 20 - 100°C under reduced pressure.
In the process according to the present invention the desired 2-chloroethane-phosphonic acid is obtained practically pure and with excellent yields. The reaction can be performed with pure starting compound as well as with a non-purified product as obtained by the reaction of ethylene oxide with phosphorus trichloride with subsequent rearrangement of the tris( 2-chloroethyl) -phosphite formed to the corresponding phosphonate.
The following Examples illustrate the invention.
E A M P L E 1; a) Preparation of 2-chloroethane-phosphonic acid bis( 2-chloroethyl) ester.
The reaction was carried out in a 2 liter flask provided with stirrer, thermometer and reflux condenser the outlet of which was closed by a pressure compensating vessel containing as sealing liquid o-dichlorobenzene saturated with ethylene oxide and which contained a mixture of 500 grams of phosphorus trichloride and 500 grams of o-dichloro"benzene . The apparatus was scavenged with nitrogen and, while stirring and cooling at 20 - 30°C, 500 grams of ethylene oxide were introduced into the mixture at a rate such that the ethylene oxide was fully absorbed. The introduction of ethylene oxide was continued for 5 to 4 hours while cooling with ice. The reaction mixture was allowed to stand for 6 hours at room temperature and then heated for 8 hours at 160°C. The o-dichlorobenzene was distilled off at 2 to 20 Torr leaving a residue of 855 grams of crude 2-chloroethane-phosphonic acid bis(2-chloroethyl) ester. b) Hydrolysis of the crude 2-chloroethane-phosphonic acid bis(2-chloroethyl) ester.
In an enamelled autoclave provided with stirrer and havin a capacity of at least 2.5 liters the product of a) was heated for 2 hours at 120°C together with 850 grams of concentrated hydrochloric acid. During heating the pressure rose to about 4 atmospheres gauge. The pressure of the autoclave was released over a condenser and the 1 , 2-dichloroethane formed was thus distilled off. The temperature of the reaction mixture dropped to 95°C. Through an inlet in the cover of the autoclave (no ascending tube) hydrogen chloride from a bomb was forced in to increase the pressure again to 3 atmospheres gauge. The temperature rose to 130°C and was maintained at 130 - 140°C for 2 hours by heating. The pressure of the autoclave was then released again over the condenser whereb another 430 grams of 1 , 2-dichloroethane were obtained. The aqueous hydrochloric acid was distilled off at an internal HOE 70/F 280K temperature of 100°C, first at 30 to 70 Torr finally at 2 Torr. 450 - 470 Grams of 2-chloroethane-phosphonic acid having a solidification point of 62 - 66°C and a purity of 94 -98o were obtained (about 90 of the theory over all three steps, calculated on the amount of phosphorus trichloride used).
E X A M P L E 2: An enamelled steel vessel having a capacity of 150 liters and provided with heating jacket, stirrer, thermometer and a descending condenser connected via a valve was filled with a mixture of 30 kilograms of phosphorus trichloride and 30 kilograms of o-dichlorobenzene. It was then scavenged with nitrogen and, while stirring and cooling at 20 - 35°C, 30 kilograms of ethylene oxide were introduced during the course of 3 to 5 hours at a rate such that the ethylene oxide was completely absorbed. Stirring of the reaction mixture was continued for 6 hous at room temperature, then the mixture was heated for 8 hours at 150 - 170°C and the o-dichlorobenzene was distilled off at 2 to 20 Torr.
After adding 60 kilograms of concentrated hydrochloric acid the connection of the reaction vessel to the descending condenser and all other openings of the vessel were closed. The reaction mixture was heated to 130°C during the course of 1 hour whereby the internal pressure rose to 5 atmospheres gauge. The overpressure was released by opening the valve to the condenser. The 1, 2-dichloroethane formed distilled off while the content of the vessel cooled to 100°C.
The internal pressure of the reaction vessel was increased to 3 atmospheres gauge by forcing in gaseous hydrogen chloride from a steel cylinder whereby the internal temperature > HOE 70/F 280K rose to 130°C. This operation was repeated twice at intervals of one hour. A total amount of 15 to 16 kilograms of 1, 2-dichloroethane was distilled off. After the last repetition the reaction mixture was heated at 130 - 140°C for another hour, the pressure of the vessel was released and aqueous hydrochloric acid and a small amount of 2-chloroethan-ol were distilled off at an internal temperature of 100°C, first at 40 and finally at 2 to 5 Torr. 28 to 29 Kilograms of 2-chloroethane phosphonic acid having a solidifcation point of 63 - 64°C and a purity of 95$ were obtained, the overall yield being 92$ of the theory. E X A M P LE 3: 3590 Grams of crude 2-chloroethane-phosphonic acid bis(2-chloroethyl) ester obtained in the manner described above and containing about 50$ of non-distillable components, and 150 grams of concentrated hydrochloric acid were introduced into an enamelled autoclave having a capacity of at least 3 liters provided with an inlet through the cover connected with a hydrogen chloride bomb and an outlet connected with a condenser via a valve. Hydrogen chloride was forced into the autoclave until the pressure amounted to 1 atmosphere gauge. Next the reaction mixture was heated at 130 - 140°C while the pressure, which initially rose but then dropped owing to the consumption ofhydrogen chloride, was maintained at 3 - 6 atmospheres gauge by forcing in hydrogen chloride. After 1 hour the dichloroethane formed was distilled off over the condenser by opening the valve. The valve was closed again and the pressure was increased to 3 - 5 atmospheres gauge by forcing in again hydrogen chloride while heating. At intervals of about 1 hour this operation was repeated until no more di- HOE 70/P 280K chloroethane distilled off. The reaction mixture was maintained at 130 - 140°C for a further 3 hours under a hydrogen chloride pressure of 3 to 5 atmospheres gauge. When the reaction was terminated the reaction mixture was cooled, the excess of hydrogen chloride was removed and hydrochloric acid and the remainder of dichloroethane were distilled off under reduced pressure. 2050 Grams of 2-chloroethane-phosphonic acid having a solidification point of 62 - 66°C were obtained. By gas chromatographic analysis of the product methylated by means of diazomethane 93 to 95 of 2-chloroethane-phosphonic acid besides 5 to 7 of phosphoric acid was found, corresponding to a yield of about 90$ of the theory, calculated on the amount of phosphorus trichloride used.
E XA M P LE 4: The procedure of Example 3 was repeated with the exception that in the ester cleavage 90 grams of water were used instead of 150 grams of concentrated hydrochloric acid. The same result as in Example 3 was obtained.
B; X A M P L E 5: Tris(2-chloroethyl) -phosphite prepared from 50 kilograms of phosphorus trichloride and 50 kilograms of ethylene oxide was rearranged to the phosphonic acid ester by heating it for several hours at 160 - 170°C in a 100 liter enamelled vessel provided with stirrer and an enamelled reflux condenser con-nected with a separator. After distillation of the dichloroethane the outlets of the reflux condenser and separator were closed. At a temperature of from 130 to 140°C an internal pressure of 3 to 6 atmospheres was produced by forcing in gaseous hydrogen chloride. After the addition of hydrogen chloride 4 liters of water were introduced into the vessel.
The cleavage set in and the dichloroethane formed was distilled off by opening the connection between the reflux condenser and the separator. The pressure in the reaction vessel which decreased owing to the consumption of hydrogen chloride was maintained at 3 to 6 atmospheres gauge by forcing in hydrogen chloride at 130 - 140°C until the formation of dichloroethane was terminated after 15 to 20 hours. The reaction mixture was then maintained at 130 - 150°C for a further 3 hours under a hydrogen chloride pressure of 3 to 6 atmospheres gauge.
After distilling off the aqueous hydrochloric acid under a slightly reduced pressure 52 kilograms of crude 2-chloroethane-phosphonic acid having a solidification point of 62 - 64°C were obtained. The product consisted of 93 to 97 of pure 2-chloroethane-phosphonic acid besides 3 to 7°/o of phosphoric acid.
E A M P L E 6; Tris(2-chloroethyl) -phosphite obtained from 56 kilograms of phosphorus trichloride and 56 kilograms of ethylene oxide was rearranged to the 2-chloroethane-phosphonic acid bis (2-chloroethyl) ester by heating t for 6 hours at 15 - 165°C in the presence of 22 kilograms of chlorobenzene in an enamel-lined autoclave having a capacity of 150 liters and provided with stirrer, heating jacket and reflux condenser connected with a collecting vessel via a cock. The chlorobenzene was removed by distillation and 5 kilograms of concentrated hydrochloric acid were added. Next, the openings of the autoclave were closed and hydrogen chloride was introduced to increase the internal pressure to 1 atmosphere gauge. The reaction mixture was heated at 130 - 140°C . The pressure which increased initially and then dropped owing to the consumption of hydrogen chloride was maintained at 3 to 5 atmospheres gauge by forcing in hydrogen chloride. At intervals of about 1 hour dichloroethane was distilled off as described in Example 3 and hydrogen chloride was forced in. The formation of dichloroethane was terminated after 8 - 10 hours.
The reaction mixture was heated for another 3 hours at 130 -140°C under a hydrogen chloride pressure of 3 to 5 atmospheres gauge.
After removal of excess hydrogen chloride and distillation of hydrochloric acid under a slightly reduced pressure 53 kilograms of 2-chloroethane-phosphonic acid having a solidification point of 62 to 66°C remained behind. The product had a degree of purity of 94 to 97$ and contained 3 to 5$ of phosphoric acid. In the reaction 45. o 50 kilograms of hydrogen chloride were consumed.
E M P L E 7: The reaction of Example 5 was repeated using an enamel-lined reflux condenser made of steel with a collecting vessel of the same material which resisted a pressure of 6 atmospheres gauge and permitted continuous distillation from the closed system of the dichloroethane formed. With otherwise the same reaction conditions and yield, only 30 kilograms of hydrogen chloride were consumed.
E A M P L E 8: 100 Kilograms of crude 2-chloroethane-phosphonic acid bis( 2-chloroethyl) ester and 5 kilograms of concentrated hydrochloric acid were heated at the reaction temperature while stirring in an 150 liter enamel-lined autoclave connected with an enamel-lined reflux condenser which in turn was connected with a collecting vessel vi a cock. While distil- y HOE 70/F 280K ling off the dichloroethane formed a HCl overpressure was produced by supplying hydrogen chloride and maintained until the formation of dichloroethane was terminated. The reaction mixture was heated at the reaction temperature for a further 3 hours, then the heating of the autoclave was switched off, the excess amount of hydrogen chloride was removed and the water contained in the reaction mixture was distilled off under reduced pressure. Finally, the residual amount of hydrogen chloride still present in the reaction mixture was removed by passing through nitrogen for one hour.
The following table summarizes reaction periods, consumption of hydrogen chloride, yields and purity of the reaction products obtained in a series of experiments carried out with a starting material containing 62$ of 2-chloroethane-phosphonic acid bis( 2-chloroethyl) ester at different temperatures.
T A B L E Temp. period H 0°C hrs . s 160 20 34 55.5 96 170 15 35 53.5 94 180 14 36 53 91 190 13 34 53 90
Claims (1)
1. WHAT CLAIMED IS A process for the manufacture of phoaphonic acid by cleavage with to 500 calculated on the basis of crude acid bis of hydrochloric acid having a concentration from 30 to by weight of acid which comprises carrying out the cleavage optionally the presence of excess gaseous hydrogen chloride at a perature above and under elevated continuously or discontinuously distilling off the formed during the and compensating the fall in pressure during the reaction by adding gaseous hydrogen The process o claim wherein a of from 1 to 10 atmospheres gauge maintained during The process of claim 2 wherein the pressure is 3 to 6 atmospheres The process of claim wherein the is carried out at a temperature of from 110 to A process for manufacture of phoaphonic acid by cleavage of acid substantially as hereinbefore described and with reference insufficientOCRQuality
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702061610 DE2061610C (en) | 1970-12-15 | Process for the preparation of 2 chlorathosphonic acid | |
| DE19712134346 DE2134346C (en) | 1971-07-09 | Process for the production of 2 chlorine athanphosphonic acid | |
| DE19712148549 DE2148549C3 (en) | 1971-09-29 | 1971-09-29 | Process for the preparation of 2-chlorathosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL38340A0 IL38340A0 (en) | 1972-02-29 |
| IL38340A true IL38340A (en) | 1974-10-22 |
Family
ID=27183043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL38340A IL38340A (en) | 1970-12-15 | 1971-12-13 | Process for the manufacture of 2-chloroethane-phosphonic acid |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS594440B1 (en) |
| BE (1) | BE776735A (en) |
| CA (1) | CA942316A (en) |
| CH (1) | CH569031A5 (en) |
| CS (1) | CS167336B2 (en) |
| FR (1) | FR2118579A5 (en) |
| GB (1) | GB1373513A (en) |
| IL (1) | IL38340A (en) |
| IT (1) | IT943888B (en) |
| NL (1) | NL7116981A (en) |
| RO (1) | RO60363A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1085870A (en) * | 1976-12-20 | 1980-09-16 | Robert J. Kiesel | Preparation of haloalylphosphonic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL41275A (en) * | 1967-04-27 | 1973-10-25 | Gen Aniline & Film Corp | Process for producing beta-haloethyl-phosphonic acids |
-
1971
- 1971-12-08 CS CS8549A patent/CS167336B2/cs unknown
- 1971-12-10 NL NL7116981A patent/NL7116981A/xx unknown
- 1971-12-10 GB GB5746971A patent/GB1373513A/en not_active Expired
- 1971-12-10 CH CH1812071A patent/CH569031A5/xx not_active IP Right Cessation
- 1971-12-13 IT IT32311/71A patent/IT943888B/en active
- 1971-12-13 IL IL38340A patent/IL38340A/en unknown
- 1971-12-14 CA CA130,083A patent/CA942316A/en not_active Expired
- 1971-12-14 FR FR7144825A patent/FR2118579A5/fr not_active Expired
- 1971-12-14 RO RO69049A patent/RO60363A/ro unknown
- 1971-12-14 JP JP46100789A patent/JPS594440B1/ja active Pending
- 1971-12-15 BE BE776735A patent/BE776735A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IT943888B (en) | 1973-04-10 |
| GB1373513A (en) | 1974-11-13 |
| FR2118579A5 (en) | 1972-07-28 |
| CA942316A (en) | 1974-02-19 |
| NL7116981A (en) | 1972-06-19 |
| JPS594440B1 (en) | 1984-01-30 |
| CS167336B2 (en) | 1976-04-29 |
| IL38340A0 (en) | 1972-02-29 |
| CH569031A5 (en) | 1975-11-14 |
| RO60363A (en) | 1976-06-15 |
| BE776735A (en) | 1972-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3184496A (en) | Process for the preparation and recovery of triethyl phosphite and derivatives thereof | |
| Allen | Phosphorus (V) Acid Esters of Oximes | |
| US4110539A (en) | Process for the preparation of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate | |
| US4322371A (en) | Process for the manufacture of 2-chloroethane-phosphonic acid | |
| US2816128A (en) | Phosphate esters of oximes | |
| US4018819A (en) | Process for the manufacture of 2-chloroethane-phosphonic acid | |
| IL38340A (en) | Process for the manufacture of 2-chloroethane-phosphonic acid | |
| JPH04234894A (en) | Process for producing 1-halogen-1-oxophospholene | |
| US5177238A (en) | Preparation of dialkyl allylphosphonic acid diesters | |
| US2879302A (en) | Polyfluoroperhaloethylenediphosphines | |
| US5177272A (en) | Process for preparing perhalogenated olefins | |
| US4296047A (en) | Continuous preparation of phosphoric acid alkyl ester dichlorides | |
| US4034022A (en) | Phosphoric esters of polyfluorinated alcohols, and their preparation | |
| Rezaei et al. | Preparation of 1-Bromo-1-chloro-, 1, 1-Dibromo-or 1, 1-Dichloroalk-1-enes from Ketones | |
| US3153670A (en) | Vinyl amines | |
| US3988368A (en) | Process for producing phenylphosphonothioic dichloride | |
| US3188281A (en) | Production of methyl dichlorophosphine oxide | |
| US2974159A (en) | Production of primary-2-hydroxy-ethylphosphite | |
| RU2528053C2 (en) | Method of obtaining dialkylphosphites | |
| US3998886A (en) | Production of halogen-containing tertiary phosphine oxides | |
| US3238237A (en) | Method of producing trialkoxy aluminum compounds | |
| US4447623A (en) | Process for the preparation of 4,5-dichloro-1,2-dithiacyclopenten-3-one | |
| US3420921A (en) | Process for preparation of dialkyl phosphonates | |
| US2666778A (en) | Method for the synthesis of organic phosphates | |
| US3644602A (en) | Process for producing trialkyl phosphates |