IL29622A - Process for producing aliphatic phosphonic acids - Google Patents
Process for producing aliphatic phosphonic acidsInfo
- Publication number
- IL29622A IL29622A IL2962268A IL2962268A IL29622A IL 29622 A IL29622 A IL 29622A IL 2962268 A IL2962268 A IL 2962268A IL 2962268 A IL2962268 A IL 2962268A IL 29622 A IL29622 A IL 29622A
- Authority
- IL
- Israel
- Prior art keywords
- beta
- ester
- acid
- temperature
- phosphonic acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 25
- -1 aliphatic phosphonic acids Chemical class 0.000 title description 4
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- ZFFPZOJIBMKDGH-UHFFFAOYSA-N 2-chloropropylphosphonic acid Chemical compound CC(Cl)CP(O)(O)=O ZFFPZOJIBMKDGH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003009 phosphonic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012467 final product Substances 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
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical group [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- AQKIXTCXLQZFMW-UHFFFAOYSA-N 1-[hexoxy(hexyl)phosphoryl]oxyhexane Chemical compound CCCCCCOP(=O)(CCCCCC)OCCCCCC AQKIXTCXLQZFMW-UHFFFAOYSA-N 0.000 description 1
- UPFSQTGEVLHCIQ-UHFFFAOYSA-N 2-[propan-2-yl(propan-2-yloxy)phosphoryl]oxypropane Chemical compound CC(C)OP(=O)(C(C)C)OC(C)C UPFSQTGEVLHCIQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000003756 stirring 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)]
- C07F9/40—Esters 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
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 PRODUCING ALIPHATIC PHOSPHONIC ACIDS This invention relates to the production of phosphonic acids and more particularly to a new and improved process for producing aliphatic phosphonic acids and still more particularly to the production of beta-chloroethylphosphonic acid.
Phosphonic acids are generally produced by the hydrolysis of a corresponding ester in the presence of a mineral acid. These processes, however, are not generally suitable for the commercial production of such acids, and in particular to the production of beta-chloroethylphosphonic acid. Thus, for example, Kosolopoff Organophosphorous Reactions (Page 139) John Wiley & Sons (1950), discloses producing beta-chloroethylphosphonic acid by the hydrolysis of bis (2-chloroethyl) beta-chloroethylphosphonate. This process, however, requires a large excess of acid which must be neutralized and in addition produces toxic ethylene chlorohydrin as a by-product which is not completely removed even after evaporation of water, an evaporation which raises the cost of the process. Moreover, the hydrolysis reaction proceeds very slowly, requiring as much as three days to effect completion thereof.
In accordance with the invention, an ester of an aliphatic phosphonic acid which is stable at a temperature of above about 140°C. is contacted with anhydrous hydrogen chloride, or hydrogen bromide, preferably hydrogen chloride, the contacting being effected at a temperature above 140eC. and below the decomposition temperature of the ester, preferably a temperature between about 145°C. and about 220eC. The treatment with hydrogen chloride cleaves the ester, producing the corresponding aliphatic phosphonic acid.
The esters which may e cleaved by the process of the invention are represented by the formula: wherein Rj_, R2 and R3 are either an alkyl group or a haloalkyl group, preferably a 2-haloalkyl group, not containing more than six carbon atoms, wherein the halo group is either fluoro, chloro, bromo or iodo; and R^ , R2 and R3 may be the same or different groups, and preferably are the same group.
The hereinabove mentioned esters having identical Ri , 2 and R3 groups may be produced, for example, by the isomerization of the corresponding phosphite. Thus, a tris (2-chloroalkyl) phosphit such as tris (2-chloroethyl) phosphite may be heated in the absence of a diluent to effect isomerization thereof to bie (2-chloroethyl) beta-chloroethylphosphonate, as taught by Kabachnik, "Bull. acid. sci. U.R.S.S classe sci. chim." 1946, 403 [C.A. 42^7243 (1948)] also repor ed in Organic Reations Vol. VI, Pages 287-8. This reaction, however, is violently exothermic (almost explosive) and very dangerous on a large scale. Consequently, it is preferred to effect the isomerization in the presence of an inert organic diluent, such as o-dichloro-benzene, cumene, xylene, and the like, at an elevated temperature, for example about 160°C. The organic diluent moderates the isomeriza-tion sufficiently to enable large scale production of the phosphonate ester. The isomerization reaction in the presence of a diluent is the tris (alkyl) phosphites may be -isomerized to the bis (alkyl) alkylphosphonates .
As representative examples of esters which may be cleaved in accordance with the process of the invention there may be mentioned: bis (2-chloroethyl) beta-chloroethylphosphonate; bis (2-chloropropyl) beta-chloropropylphosphonate dimethyl methyl-phosphonate ; diethyl ethylphosphonate ; di-isopropyl isopropyl-phosphonate ; di-n-hexyl n-hexylphosphonate ; and the like .
The process of the invention is particularly suitable for producing water soluble phosphonic acids, and in particular, beta-chloroethylphosphonic acid by cleaving bis (2-chloroethyl) beta-chloroethylphosphonate with anhydrous hydrogen chloride. The reaction for producing 2-chloroethylphosphonic acid also produces an almost quantitative yield of 1,2-dichloroethane as a by-product which under the conditions of the reaction ia recovered as a gaseous effluent.
The invention will be further described with reference to the following examples: EXAMPLE I 1938 grams of crude bis (2-chloroethyl) beta-chloroethylphosphonate, prepared by the rearrangement of tris (2-chloroethyl) phosphite in o-dichlorobenzene, were introduced into a 3 liter 3 neck flask, equipped with stirrer, glass inlet tube and a "Y" tube, containing a thermometer which extended below the liquid surface. The other arm of the HY" tube was attached to a down dropping bulb condenser attached to a one liter one neck distillation flask, containing a side arm which was connected to a cascade water scrubbing tower for removal of excess hydrogen chloride.
The crude ester was heated, with stirring, to a temperature of 171°C, at which temperature hydrogen chloride from a pressure cylinder was introduced beneath the surface of the liquid, resulting in vigorous evolution of 1, 2-dichloroethane. The addition of hydrogen chloride was continued for 6.5 hours while maintaining a temperature of 175eC. The evolution of 1,2-dichloro-ethane was very rapid during the first four hours. After the addition of hydrogen chloride was terminated, nitrogen was bubbled through the reaction mixture at a temperature of 170°C. to remove hydrogen chloride therefrom. The resulting product, 2-chloro-ethylphosphonic acid, weighed 1039 grams (an essentially quantitative yield) and had a melting point of 35-55°C.
EXAMPLE II In accordance with the procedure of Example I, 1000 grams of bis (2-chloropropyl) beta-chloropropylphosphonate are cleaved with anhydrous hydrogen chloride to produce 525 grams of beta-chloropropylphosphonic acid. 1, 2-dichloropropane is recovered as a by product.
The 2-chloroethylphosphosphonic acid produced by the process of the invention, with or without purification, may be reacted with phosphorous pentachloride to produce 2-chloroethyl-phosphonyl dichloride. The beta-haloethylphosphonic acids have also growth regulating properties and aqueous solutions thereof may be applied to growing plants, e. g. , to control apical dominance. The beta-haloethylphosphonic acids are generally sprayed onto the The process ί the invention is an improvement over the hydrolysis reactions heretofore known in the art in that the overall reaction time is reduced, no costly evaporation of the final product is required and a greater weight of product is produced per a unit volume of reaction mixture. Moreover, the final product has a higher purity than those produced by the prior art hydrolysis processes, in producing beta-chloroethyl-phosphonic acid, the by-product, 1,2-dichloroethane is readily separated from the final product, in contradistinction to the hydrolysis process wherein the toxic by-product, ethylene chlorohydrin, is only separated after a costly procedure (.
Consequently, the beta-chloroethylphosphonic acid produced by the process of the invention is of high purity and particularly suitable for application to growing plants.
Claims (6)
1. Having now particularly described and ascertained the nature of our said invention and in what manner the same is to be performed, declare that WHAT WE CLAIM IS: 1. A process for producing an aliphatic phosphonic acid selected from the group consisting of alkylphosphonic acids and beta-haloalkylphosphonic acids containing no more than six carbon atoms, comprising contacting an ester of the aliphatic phosphonic acid which is stable at a temperature of above about 140°C. with anhydrous hydrogen bromide or hydrogen chloride, at a temperature above about 140°C. and below the decomposition temperature of the ester to produce the aliphatic phosphonic acid.
2. The process as claimed in Claim 1 wherein the ester is represented by the formula: 0 wherein R^, and are alkyl or haloalkyl containing no more than six carbon atoms.
3. The process as claimed in Claim 2, wherein R^, R2 and R^ are 2-haloalkyl.
4. The process as claimed in Claim 2, wherein R^, and R„ are alkyl. 2 3
5. The process as claimed in Claim 3, wherein R^, R^ and R^ are 2-chloroalkyl.
6. The process as claimed in Claim 2, wherein the c ntactin is effected at a tem erature between 145°C. and 220°C. phosphonic acid is beta-chloropropylphosphonic acid. 8. The process as claimed in claim 6, wherein the ester is bis (2-chloroethyl) beta-chloroethylphosphonate and the phosphonic acid is beta-chloroethylphosphonic acid. 9. The process as claimed in Claim 9 wherein the contacting is effected at a temperature of 175°C. ' E-1748 10. The process claimed in any one of the preceding claims substantially as herein described and exemplified.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62883967A | 1967-04-06 | 1967-04-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IL29622A true IL29622A (en) | 1971-06-23 |
Family
ID=24520519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL2962268A IL29622A (en) | 1967-04-06 | 1968-03-12 | Process for producing aliphatic phosphonic acids |
Country Status (6)
| Country | Link |
|---|---|
| CH (1) | CH499551A (en) |
| DE (1) | DE1768061B2 (en) |
| FR (1) | FR1559483A (en) |
| GB (1) | GB1187002A (en) |
| IL (1) | IL29622A (en) |
| MY (1) | MY7100076A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD258237A5 (en) * | 1985-10-18 | 1988-07-13 | ��K@�����`�������@����������k�� | PROCESS FOR PREPARING AN ALIPHATIC PHOSPHONIC ACID |
-
1968
- 1968-03-12 IL IL2962268A patent/IL29622A/en unknown
- 1968-03-27 CH CH452868A patent/CH499551A/en not_active IP Right Cessation
- 1968-03-27 DE DE19681768061 patent/DE1768061B2/en active Pending
- 1968-04-02 GB GB1588268A patent/GB1187002A/en not_active Expired
- 1968-04-03 FR FR1559483D patent/FR1559483A/fr not_active Expired
-
1971
- 1971-12-31 MY MY7100076A patent/MY7100076A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MY7100076A (en) | 1971-12-31 |
| GB1187002A (en) | 1970-04-08 |
| DE1768061B2 (en) | 1974-11-14 |
| DE1768061A1 (en) | 1972-01-13 |
| CH499551A (en) | 1970-11-30 |
| FR1559483A (en) | 1969-03-07 |
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