GB1242185A - Preparation of (cis-1,2-epoxypropyl)phosphonic acid and salts and esters thereof - Google Patents
Preparation of (cis-1,2-epoxypropyl)phosphonic acid and salts and esters thereofInfo
- Publication number
- GB1242185A GB1242185A GB23981/69A GB2398169A GB1242185A GB 1242185 A GB1242185 A GB 1242185A GB 23981/69 A GB23981/69 A GB 23981/69A GB 2398169 A GB2398169 A GB 2398169A GB 1242185 A GB1242185 A GB 1242185A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cis
- salt
- ester
- converted
- compounds
- 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 11
- 150000002148 esters Chemical class 0.000 title abstract 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 abstract 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 4
- 239000002253 acid Substances 0.000 abstract 4
- -1 azo compound Chemical class 0.000 abstract 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 3
- 239000000047 product Substances 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 239000012442 inert solvent Substances 0.000 abstract 2
- 229940101209 mercuric oxide Drugs 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract 1
- 239000004593 Epoxy Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract 1
- 239000012965 benzophenone Substances 0.000 abstract 1
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000002480 mineral oil Substances 0.000 abstract 1
- 235000010446 mineral oil Nutrition 0.000 abstract 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000003504 photosensitizing agent Substances 0.000 abstract 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000375 suspending agent Substances 0.000 abstract 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 abstract 1
- 239000008096 xylene Substances 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
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
- C07F9/2491—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-N (X = O, S, Se; n = 0, 1)
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
1,242,185. Preparing (cis-1,2-epoxypropyl)- phosphonic acid and intermediates thereof. MERCK & CO. Inc. 12 May, 1969 [15 May, 1968], No. 23981/69. Heading C2C. (cis - 1,2 - Epoxypropyl)phosphonic acid or an ester or salt thereof is obtained by eliminating nitrogen from a cis azo phosphonic compound of the formula wherein each R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl or heterocyclic radical, or from an organic or inorganic salt of such compound in which at least one R is a hydrogen atom. The elimination of nitrogen may be effected by irradiating a solution of the azo compound with U.V. light preferably in the presence of a photo-sensitizing agent, e.g. benzophenone or acetophenone, or by heating the azo compound, generally at above 80 C., e.g. from 100 to 300 C., the heating being carried out directly or with the azo compound suspended or dissolved in an appropriate suspending agent, e.g. a mineral oil, or inert solvent, e.g. toluene, pyridine, chloroform, cumene or xylene. Suitable solvents for use in the U.V. light treatment include water, C 1 -C 6 alkanols, dioxane, acetonitrile or tributyl amine, or aqueous mixtures thereof. If the starting material contains any of the trans isomer the latter can be separated or the cis/trans mixture can be converted by the defined process to a mixture of cis- and trans-1,2-epoxy propyl phosphonic and the trans isomer then separated and if desired converted to the cis isomer by irradiation with U.V. light. If the free phosphonic acid is used in the process it is preferred to isolate the product as a salt, e.g. the sodium or benzyl ammonium slat and if the starting material is an ester the ester product may be converted to the free acid or salt thereof by hydrolysis or reductive removal of the ester group. The end products are generally racemic mixtures which can be resolved into their optically active (+) and (-) forms. The ()(cis - 1,2 - epoxypropyl)phosphonic acid and salts thereof have antimicrobial properties. The starting materials I may be prepared by the following reaction scheme: In these reactions the compounds V are converted to I by epoxidation and the compounds VI are converted to I by oxidation with mercuric oxide. The phosphonic reactants and products may be in the form of the free acids, esters or salts. Compounds IV or their salts are obtained by reacting chlorophosphonic acid or ester or salt thereof with hydrazine hydrate at low temperature, generally below 0 C. and in an inert solvent. Compounds II can be obtained by the following reaction scheme: The salt, ester or free acid of the phosphorus acid may be used (a salt being shown) and compounds VIII are converted to 1,2-epoxy-2- chloro-ethyl phosphonic acid or salt or ester thereof by treatment with water, this being followed by treatment with methylhydrazine to form compounds IX which are finally treated with mercuric oxide to form II.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72937168A | 1968-05-15 | 1968-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1242185A true GB1242185A (en) | 1971-08-11 |
Family
ID=24930737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB23981/69A Expired GB1242185A (en) | 1968-05-15 | 1969-05-12 | Preparation of (cis-1,2-epoxypropyl)phosphonic acid and salts and esters thereof |
Country Status (9)
| Country | Link |
|---|---|
| BE (1) | BE733035A (en) |
| BR (1) | BR6908803D0 (en) |
| CH (1) | CH519522A (en) |
| DE (1) | DE1924072A1 (en) |
| ES (1) | ES367094A1 (en) |
| GB (1) | GB1242185A (en) |
| IL (1) | IL32119A0 (en) |
| NL (1) | NL6904140A (en) |
| SE (1) | SE351656B (en) |
-
1969
- 1969-03-18 NL NL6904140A patent/NL6904140A/xx unknown
- 1969-03-31 SE SE04505/69A patent/SE351656B/xx unknown
- 1969-05-01 IL IL32119A patent/IL32119A0/en unknown
- 1969-05-08 CH CH709169A patent/CH519522A/en not_active IP Right Cessation
- 1969-05-12 DE DE19691924072 patent/DE1924072A1/en active Pending
- 1969-05-12 GB GB23981/69A patent/GB1242185A/en not_active Expired
- 1969-05-12 ES ES367094A patent/ES367094A1/en not_active Expired
- 1969-05-14 BE BE733035D patent/BE733035A/xx unknown
- 1969-05-14 BR BR208803/69A patent/BR6908803D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE1924072A1 (en) | 1970-01-29 |
| ES367094A1 (en) | 1971-07-01 |
| IL32119A0 (en) | 1969-07-30 |
| BE733035A (en) | 1969-11-14 |
| SE351656B (en) | 1972-12-04 |
| NL6904140A (en) | 1969-11-18 |
| BR6908803D0 (en) | 1973-06-07 |
| CH519522A (en) | 1972-02-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| IL57752A (en) | Preparation of 1-desoxy-nojirimicin and n-substituted derivatives thereof | |
| DE1146486B (en) | Process for the preparation of O, O-dialkyl-dithiophosphoryl fatty acid amides | |
| US2901481A (en) | Process for preparing dialkyldithiophosphoric acid ester derivatives having two amide groups in the molecule and the insecticidal compounds obtained thereby | |
| ATE82569T1 (en) | PRODUCTION OF QUINOLINECARBONIC ACIDS. | |
| DE3854109T2 (en) | METHOD FOR PRODUCING CHINOLINE CARBONIC ACIDS. | |
| GB1242185A (en) | Preparation of (cis-1,2-epoxypropyl)phosphonic acid and salts and esters thereof | |
| US3803202A (en) | Process for the production of 2-cyano-3,4,5,6-tetrahalogenbenzoic acid alkyl esters | |
| CH589653A5 (en) | Acyloxyalkyl esters of penicillin and cephalosporin cpds - - readily absorbed after oral admin and less toxic | |
| GB1213707A (en) | Phosphorus-containing 1,2,4-oxadiazole derivatives | |
| US3068268A (en) | Preparation of vinyl esters of phosphorus acids useful as insecticides | |
| DE1257152B (en) | Process for the preparation of substituted malonic acid hydrazides | |
| US2653157A (en) | p-amino-salicylic acid derivatives and their production | |
| EP0002721B1 (en) | Process for preparing hydrazines | |
| SU455529A3 (en) | The method of obtaining - (aminophenyl) -aliphatic carboxylic acids or their derivatives or their salts | |
| US3052687A (en) | Process for the production of | |
| US3019230A (en) | Method for the preparation of z | |
| DE1081471B (en) | Process for the preparation of N- [4, 5, 6, 7, 10, 10-hexachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydro-phthalanyl- (1)] - ª ‡ -aminocarboxylic acid esters | |
| US3153041A (en) | Process for preparation of glutarimide derivatives | |
| US3268516A (en) | Amino-acylamino-acylamino-penicillanic acids | |
| AT250362B (en) | Process for the preparation of new pyridine derivatives | |
| US2516240A (en) | Preparation of penicillamine | |
| DE2002065A1 (en) | Sulphimides prepn | |
| DE2026952C3 (en) | Process for the preparation of L-3,4-dihydroxyphenylalanine | |
| DE1184344B (en) | Process for the preparation of isoquinoline derivatives | |
| GB1200538A (en) | PROCESS FOR THE PREPARATION OF alpha-PHENOXYALKYL-PENICILLINS |