GB1283791A - Preparation of (cis-1,2,-epoxypropyl)phosphonic acid compounds; also intermediates therefor and their preparation - Google Patents
Preparation of (cis-1,2,-epoxypropyl)phosphonic acid compounds; also intermediates therefor and their preparationInfo
- Publication number
- GB1283791A GB1283791A GB2504/70A GB250470A GB1283791A GB 1283791 A GB1283791 A GB 1283791A GB 2504/70 A GB2504/70 A GB 2504/70A GB 250470 A GB250470 A GB 250470A GB 1283791 A GB1283791 A GB 1283791A
- Authority
- GB
- United Kingdom
- Prior art keywords
- epoxypropyl
- cis
- phosphonic acid
- acid
- optically active
- 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
- 238000002360 preparation method Methods 0.000 title abstract 3
- 239000000543 intermediate Substances 0.000 title 1
- 150000003009 phosphonic acids Chemical class 0.000 title 1
- 150000002148 esters Chemical class 0.000 abstract 5
- 150000003839 salts Chemical class 0.000 abstract 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 4
- 239000002253 acid Substances 0.000 abstract 4
- 150000001412 amines Chemical class 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 3
- -1 propadienyl phosphonic acid compound Chemical class 0.000 abstract 3
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N D-aspartic acid Chemical compound OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 abstract 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000001640 fractional crystallisation Methods 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 230000003287 optical effect Effects 0.000 abstract 2
- 238000011946 reduction process Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract 1
- VRXGHOPIMKAYJL-UHFFFAOYSA-N 1-dichlorophosphorylpropa-1,2-diene Chemical compound ClP(Cl)(=O)C=C=C VRXGHOPIMKAYJL-UHFFFAOYSA-N 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 abstract 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 abstract 1
- 235000001258 Cinchona calisaya Nutrition 0.000 abstract 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 abstract 1
- 125000000030 D-alanine group Chemical group [H]N([H])[C@](C([H])([H])[H])(C(=O)[*])[H] 0.000 abstract 1
- WHUUTDBJXJRKMK-GSVOUGTGSA-N D-glutamic acid Chemical compound OC(=O)[C@H](N)CCC(O)=O WHUUTDBJXJRKMK-GSVOUGTGSA-N 0.000 abstract 1
- 229930182847 D-glutamic acid Natural products 0.000 abstract 1
- KDXKERNSBIXSRK-RXMQYKEDSA-N D-lysine group Chemical group N[C@H](CCCCN)C(=O)O KDXKERNSBIXSRK-RXMQYKEDSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 abstract 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 abstract 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 abstract 1
- 241001465754 Metazoa Species 0.000 abstract 1
- 239000007868 Raney catalyst Substances 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 229940024606 amino acid Drugs 0.000 abstract 1
- 150000001413 amino acids Chemical class 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 229960005261 aspartic acid Drugs 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- RRKTZKIUPZVBMF-IBTVXLQLSA-N brucine Chemical compound O([C@@H]1[C@H]([C@H]2C3)[C@@H]4N(C(C1)=O)C=1C=C(C(=CC=11)OC)OC)CC=C2CN2[C@@H]3[C@]41CC2 RRKTZKIUPZVBMF-IBTVXLQLSA-N 0.000 abstract 1
- RRKTZKIUPZVBMF-UHFFFAOYSA-N brucine Natural products C1=2C=C(OC)C(OC)=CC=2N(C(C2)=O)C3C(C4C5)C2OCC=C4CN2C5C31CC2 RRKTZKIUPZVBMF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002775 capsule Substances 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
- 239000011248 coating agent Substances 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 239000000796 flavoring agent Substances 0.000 abstract 1
- 235000013355 food flavoring agent Nutrition 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 229960002989 glutamic acid Drugs 0.000 abstract 1
- 239000003979 granulating agent Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000006193 liquid solution Substances 0.000 abstract 1
- 239000006194 liquid suspension Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000000813 microbial effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 abstract 1
- OPSHPJNGHQXCNF-UHFFFAOYSA-N propa-1,2-dienylphosphonic acid Chemical compound OP(O)(=O)C=C=C OPSHPJNGHQXCNF-UHFFFAOYSA-N 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 229960000948 quinine Drugs 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- 150000003512 tertiary amines Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/547—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
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)
- Catalysts (AREA)
Abstract
1283791 1,2-Epoxyallylphosphonic acid compounds and their conversion to the corresponding epoxypropyl phosphonic compounds MERCK & CO Inc 19 Jan 1970 [23 Jan 1969] 2504/70 Heading C2P A propadienyl phosphonic acid compound (I) is treated with a substantially equimolar quantity of an epoxidizing agent to produce a novel (1,2-epoxyallyl)-phosphonic acid compound (II) which is then reduced to form a (cis-1,2-epoxypropyl) phosphonic acid compound (III), e.g. as illustrated by the following reaction scheme: In the formulµ each of R and R 1 is halogen, OH, OY wherein Y is a metal or other saltforming radical, 0Y 1 where Y 1 is a substituted or unsubstituted hydrocarbon or heterocyclic radical or -NY 3 Y 4 where each of Y 3 and Y 4 is H or a hydrocarbon radical or NY 3 Y 4 is the residue of a cyclic amine and R and R 1 may be the same or different in each compound. A wide variety of epoxidizing agents can be used and when epoxidation of I is complete the product II may, without isolation, be submitted directly to the reduction process. Alternatively the compound II which is formed as a racemate may be resolved into its optically active isomers and either or both of the latter subjected to the reduction process to produce the corresponding optical isomer of III. Resolution may be effected by use of an optically active amine to produce a pair of diastereoisomers, separating the diastereoisomers, e.g. by fractional crystallization, and regenerating the appropriate enantiomer from the diastereoisomer. Suitable optically active amines for use in the resolution are quinine, brucine, and α- phenethylamine. The reduction step is conveniently effected with hydrogen in the presence of a catalyst, e.g. Pt, Pd or Raney nickel, or may be effected by means of an alkali or alkaline earth metal borohydride. The reduction can be carried out so as to form either the (+) or ( - ) isomers of III from the resolved isomers of II. The reduction may be carried out asymmetrically so as to obtain the (+) or (-) isomer of III. This may be done by using in the hydrogenation process a catalyst having adsorbed thereon an optically active amino acid such as d- or l-alanine, d- or l-glutamic acid, d- or l-aspartic acid or d- or l-lysine. Alternatively when () (cis-1,2-epoxypropyl) phosphosphonic acid salts are obtained they may be resolved into their optical isomers by forming diastereoisomers with an optically active amine such as α-phenethylamine followed by separation of the diastereoisomers by fractional crystallization. When the final products are esters of (cis-1,2- epoxypropyl) phosphonic acid they may be converted by various defined methods to the free acid or salt thereof, e.g. by alkaline hydrolysis, hydrogenolysis, U.V. irradiation in the presence of a base, treatment with sodium in a tertiary amine, or enzymolysis, according to the nature of the ester to be converted. Examples are given for the preparation of the d-α-phenethylamine salt of (- )(cis-1,2-epoxypropyl)- phosphonic acid and of various salts and esters of () (cis-1,2-epoxypropyl) phosphonic acid and also for the conversion of various esters of (cis-1,2-epoxypropyl) phosphonic acid to salts thereof. ( -) and ()(cis-1,2-epoxypropyl) phosphonic acid and salts and labile esters thereof have microbial properties and may be used to combat bacteria in man or lower animals. They may be administered orally as capsules or tablets or in liquid solution or suspension and suitable formulations can include diluents, granulating agents, preservatives, binders, flavouring agents and coating agents. They may also be administered parenterally by injection in a sterile vehicle. Propadienyl phosphonic acid is obtained by adding water dropwise to a solution of propadienyl phosphonic dichloride in dioxane containing pyridine and is converted to its sodium salt by the addition of aqueous sodium bicarbonate solution to an aqueous solution of the acid to give a pH of 5À5 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79359269A | 1969-01-23 | 1969-01-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1283791A true GB1283791A (en) | 1972-08-02 |
Family
ID=25160292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2504/70A Expired GB1283791A (en) | 1969-01-23 | 1970-01-19 | Preparation of (cis-1,2,-epoxypropyl)phosphonic acid compounds; also intermediates therefor and their preparation |
Country Status (10)
| Country | Link |
|---|---|
| AT (1) | AT303062B (en) |
| AU (1) | AU1038470A (en) |
| BE (1) | BE744802A (en) |
| DE (1) | DE2002863A1 (en) |
| ES (1) | ES375607A1 (en) |
| FR (1) | FR2028975A1 (en) |
| GB (1) | GB1283791A (en) |
| IL (1) | IL33713A0 (en) |
| NL (1) | NL7000165A (en) |
| ZA (1) | ZA698401B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109055469A (en) * | 2018-08-29 | 2018-12-21 | 武汉轻工大学 | A kind of preparation method of pumpkin albumen |
-
1969
- 1969-12-02 ZA ZA698401A patent/ZA698401B/en unknown
-
1970
- 1970-01-07 NL NL7000165A patent/NL7000165A/xx unknown
- 1970-01-15 IL IL33713A patent/IL33713A0/en unknown
- 1970-01-16 AU AU10384/70A patent/AU1038470A/en not_active Expired
- 1970-01-19 GB GB2504/70A patent/GB1283791A/en not_active Expired
- 1970-01-19 ES ES375607A patent/ES375607A1/en not_active Expired
- 1970-01-21 AT AT54770A patent/AT303062B/en not_active IP Right Cessation
- 1970-01-22 DE DE19702002863 patent/DE2002863A1/en active Pending
- 1970-01-22 FR FR7002295A patent/FR2028975A1/fr active Pending
- 1970-01-22 BE BE744802D patent/BE744802A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES375607A1 (en) | 1972-08-16 |
| AT303062B (en) | 1972-11-10 |
| IL33713A0 (en) | 1970-03-22 |
| DE2002863A1 (en) | 1970-12-03 |
| AU1038470A (en) | 1971-07-22 |
| FR2028975A1 (en) | 1970-10-16 |
| NL7000165A (en) | 1970-07-27 |
| ZA698401B (en) | 1971-07-28 |
| BE744802A (en) | 1970-07-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| CSNS | Application of which complete specification have been accepted and published, but patent is not sealed |