GB1204448A - Production of cis-propenylphosphonic acid and salts and esters thereof - Google Patents
Production of cis-propenylphosphonic acid and salts and esters thereofInfo
- Publication number
- GB1204448A GB1204448A GB50637/68A GB5063768A GB1204448A GB 1204448 A GB1204448 A GB 1204448A GB 50637/68 A GB50637/68 A GB 50637/68A GB 5063768 A GB5063768 A GB 5063768A GB 1204448 A GB1204448 A GB 1204448A
- Authority
- GB
- United Kingdom
- Prior art keywords
- salt
- isomer
- cis
- phosphonic acid
- salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000003839 salts Chemical class 0.000 title abstract 7
- XWCIXXXLOAAWPU-IHWYPQMZSA-N [(z)-prop-1-enyl]phosphonic acid Chemical compound C\C=C/P(O)(O)=O XWCIXXXLOAAWPU-IHWYPQMZSA-N 0.000 title abstract 5
- 150000002148 esters Chemical class 0.000 title abstract 5
- -1 phosphonium halide Chemical class 0.000 abstract 10
- 125000000217 alkyl group Chemical group 0.000 abstract 5
- 150000003863 ammonium salts Chemical class 0.000 abstract 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 abstract 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 3
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 abstract 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 abstract 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract 2
- 239000012991 xanthate Substances 0.000 abstract 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract 1
- JYDBWTLMEMXTBB-UHFFFAOYSA-N 1-[butoxy-[(Z)-prop-1-enyl]phosphoryl]oxybutane Chemical compound C(CCC)OP(OCCCC)(=O)C=C/C JYDBWTLMEMXTBB-UHFFFAOYSA-N 0.000 abstract 1
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical class CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 abstract 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 abstract 1
- 235000001258 Cinchona calisaya Nutrition 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- XWCIXXXLOAAWPU-NSCUHMNNSA-N [(e)-prop-1-enyl]phosphonic acid Chemical compound C\C=C\P(O)(O)=O XWCIXXXLOAAWPU-NSCUHMNNSA-N 0.000 abstract 1
- WTKUDAMSULHEKV-UHFFFAOYSA-N [Se](C#N)C#N.[K] Chemical compound [Se](C#N)C#N.[K] WTKUDAMSULHEKV-UHFFFAOYSA-N 0.000 abstract 1
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical class [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 abstract 1
- 229940073608 benzyl chloride Drugs 0.000 abstract 1
- 230000003115 biocidal effect Effects 0.000 abstract 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 abstract 1
- 229940109126 chromous chloride Drugs 0.000 abstract 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000005690 diesters Chemical class 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 229940087654 iron carbonyl Drugs 0.000 abstract 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 abstract 1
- 150000003003 phosphines Chemical class 0.000 abstract 1
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- 229960000948 quinine Drugs 0.000 abstract 1
- 239000011833 salt mixture Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract 1
- 150000003567 thiocyanates Chemical class 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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
1,204,448. Preparing cis-propenyl phosphonic acid and derivatives thereof. MERCK & CO. Inc. 24 Oct., 1968 [30 Oct., 1967; 15 May, 1968], No. 50637/68. Heading C2C. The ( + ) isomer, or a mixture containing ( + ) and ( - ) isomers, of (cis-1,2-epoxypropyl)- phosphonic acid or a salt or ester thereof is reacted with a de-epoxidizing agent to produce cis-propenyl phosphonic acid or a salt or ester thereof. The de-epoxidizing agent may be a reducing metal salt, preferably chromous chloride or acetate, hydrogen iodide or compounds which form hydrogen iodide in solution, e.g. NaI or KI, phosphorus compounds, e.g. triaryl phosphines, tri-(C 1 -C 7 alkyl)-phosphines or -phosphites, or a phosphonium halide, e.g. a phosphonium iodide, a sulphur compound, e.g. (C 1 -C 7 alkyl) xanthates such as Na or K-nbutyl xanthates and thiocyanate salts, e.g. Na-, K- or ammonium thiocyanates, a potassium iron carbonyl compound, e.g. KHFe(CO) 4 , K 2 Fe(CO) 4 or K 2 Fe(CO) 8 , or potassium selenocyanide. De-epoxidation is generally carried out in a solvent and the reaction conditions and solvent used depend on the particular type of de-epoxidizing agent used. The cis-propenyl phosphonic acid may be epoxidized to form a racemic mixture of (cis1,2-epoxypropyl)-phosphonic acid and the latter then resolved to form the pure ( - ) isomer which is useful as an antibiotic. The ester derivatives may be mono- or di-esters, e.g. aryl or aralkyl esters or C 1 -C 7 alkyl, C 2 -C 7 alkenyl or C 2 -C 7 alkynyl esters and the alkyl or aryl groups present may be substituted. The salts may be mono- or di-salts and may be metal salts or ammonium or organosubstituted ammonium salts, including the mono - benzylammonium, mono - cyclohexylamine, phenylamine, bis-hexylamine and isopropyl phenethylammonium ester salt. Di - n - butyl - cis - propenylphosphonate is obtained by selectively reducing the corresponding propynyl ester and is hydrolysed to the free acid (cis-propenyl phosphonic acid) by means of conc. HCl, the free acid is neutralized with NH 4 OH and epoxidized with H 2 O 2 in the presence of sodium tungstate to form the ammonium salt of ()(cis-1,2-epoxypropyl)-phosphonic acid which is then resolved by use of quinine in methanol to yield the ammonium salt of the ( - ) isomer and the ammonium salt of a mixture of the ( + ) isomer and a small amount of the ( - ) isomer, the latter salt mixture being converted to the ( - ) α-phenylethylamine salt of the ( + ) isomer and the latter converted to the diammonium salt of the (+) isomer which may be converted to the monobenzylammonium salt or to various esters of the ( + ) isomer by passage through a strongly acid ion exchange resin and either treating the eluate with benzylamine or with NaOH followed by reaction with an alkyl, alkenyl, or alkynyl halide or benzyl chloride. Aryl trans-propenyl phosphonates may be obtained by dissolving trans-propenyl phosphonic acid (obtained from its monobenzylammonium salt), thionyl chloride and pyridine in benzene and then reacting with phenol or a substituted phenol and may be epoxidized.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67920367A | 1967-10-30 | 1967-10-30 | |
| US72941868A | 1968-05-15 | 1968-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1204448A true GB1204448A (en) | 1970-09-09 |
Family
ID=27102171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB50637/68A Expired GB1204448A (en) | 1967-10-30 | 1968-10-24 | Production of cis-propenylphosphonic acid and salts and esters thereof |
Country Status (11)
| Country | Link |
|---|---|
| AT (1) | AT292732B (en) |
| BE (1) | BE723070A (en) |
| CH (1) | CH506565A (en) |
| DE (1) | DE1805676B2 (en) |
| ES (1) | ES359537A1 (en) |
| GB (1) | GB1204448A (en) |
| IL (1) | IL30917A0 (en) |
| LU (1) | LU57181A1 (en) |
| MT (1) | MTP583B (en) |
| NL (1) | NL6814973A (en) |
| OA (1) | OA02907A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2257959A1 (en) * | 2005-01-21 | 2006-08-01 | Universidad De Huelva | Preparation of an epoxy propyl phosphonic derivative comprises catalytic reaction employing tungsten dioxy complexes |
| ES2270703A1 (en) * | 2005-05-20 | 2007-04-01 | Universidad De Huelva | Continuous hydrogenation of di-tert-butyl propanedienylphosphonate, useful for preparing di-tert-butyl propenylphosphonate, intermediate for phosphomycin |
-
1968
- 1968-10-18 NL NL6814973A patent/NL6814973A/xx unknown
- 1968-10-21 IL IL30917A patent/IL30917A0/en unknown
- 1968-10-22 CH CH1578568A patent/CH506565A/en not_active IP Right Cessation
- 1968-10-23 OA OA53387A patent/OA02907A/en unknown
- 1968-10-24 GB GB50637/68A patent/GB1204448A/en not_active Expired
- 1968-10-25 ES ES359537A patent/ES359537A1/en not_active Expired
- 1968-10-28 DE DE19681805676 patent/DE1805676B2/en active Pending
- 1968-10-29 BE BE723070D patent/BE723070A/xx unknown
- 1968-10-29 LU LU57181D patent/LU57181A1/xx unknown
- 1968-10-30 MT MT583A patent/MTP583B/en unknown
- 1968-10-30 AT AT1056268A patent/AT292732B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2257959A1 (en) * | 2005-01-21 | 2006-08-01 | Universidad De Huelva | Preparation of an epoxy propyl phosphonic derivative comprises catalytic reaction employing tungsten dioxy complexes |
| ES2270703A1 (en) * | 2005-05-20 | 2007-04-01 | Universidad De Huelva | Continuous hydrogenation of di-tert-butyl propanedienylphosphonate, useful for preparing di-tert-butyl propenylphosphonate, intermediate for phosphomycin |
Also Published As
| Publication number | Publication date |
|---|---|
| IL30917A0 (en) | 1968-12-26 |
| DE1805676A1 (en) | 1969-12-11 |
| MTP583B (en) | 1969-09-22 |
| LU57181A1 (en) | 1969-05-16 |
| AT292732B (en) | 1971-09-10 |
| ES359537A1 (en) | 1970-08-16 |
| BE723070A (en) | 1969-04-29 |
| NL6814973A (en) | 1969-05-02 |
| CH506565A (en) | 1971-04-30 |
| DE1805676B2 (en) | 1971-12-09 |
| OA02907A (en) | 1970-12-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PLNP | Patent lapsed through nonpayment of renewal fees |