IE32804L - Preparation of (cis-1,2-epoxypropyl) phosphonic acid¹and derivatives - Google Patents
Preparation of (cis-1,2-epoxypropyl) phosphonic acid¹and derivativesInfo
- Publication number
- IE32804L IE32804L IE690635A IE63569A IE32804L IE 32804 L IE32804 L IE 32804L IE 690635 A IE690635 A IE 690635A IE 63569 A IE63569 A IE 63569A IE 32804 L IE32804 L IE 32804L
- Authority
- IE
- Ireland
- Prior art keywords
- alkyl
- acid
- salt
- compounds
- reaction
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title abstract 2
- -1 1,2-disubstituted n-propyl phosphonic acid Chemical class 0.000 abstract 13
- 238000006243 chemical reaction Methods 0.000 abstract 12
- 150000001875 compounds Chemical class 0.000 abstract 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 9
- 239000002253 acid Substances 0.000 abstract 7
- 239000007858 starting material Substances 0.000 abstract 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 6
- 150000003839 salts Chemical class 0.000 abstract 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 4
- 229910052799 carbon Inorganic materials 0.000 abstract 4
- 229910052736 halogen Inorganic materials 0.000 abstract 4
- 229910052760 oxygen Inorganic materials 0.000 abstract 4
- 239000001301 oxygen Substances 0.000 abstract 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 3
- 150000001340 alkali metals Chemical class 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 125000003118 aryl group Chemical group 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 150000002148 esters Chemical class 0.000 abstract 3
- 125000005843 halogen group Chemical group 0.000 abstract 3
- 230000002140 halogenating effect Effects 0.000 abstract 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 3
- 229910052751 metal Inorganic materials 0.000 abstract 3
- 239000002184 metal Substances 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 3
- 125000001453 quaternary ammonium group Chemical class 0.000 abstract 3
- 125000001424 substituent group Chemical group 0.000 abstract 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 abstract 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 2
- 239000002585 base Substances 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract 2
- 239000011707 mineral Substances 0.000 abstract 2
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract 2
- 125000004953 trihalomethyl group Chemical group 0.000 abstract 2
- XFKAMBULGKHYIY-UHFFFAOYSA-N (1-chloro-1-oxopropan-2-yl) 4-methylbenzenesulfonate Chemical compound ClC(=O)C(C)OS(=O)(=O)C1=CC=C(C)C=C1 XFKAMBULGKHYIY-UHFFFAOYSA-N 0.000 abstract 1
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 abstract 1
- QXYOROBKCZWFKK-UHFFFAOYSA-N 2-(4-methylphenyl)sulfonyloxypropanoic acid Chemical compound OC(=O)C(C)OS(=O)(=O)C1=CC=C(C)C=C1 QXYOROBKCZWFKK-UHFFFAOYSA-N 0.000 abstract 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000002841 Lewis acid Substances 0.000 abstract 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003929 acidic solution Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 125000003282 alkyl amino group Chemical group 0.000 abstract 1
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical class [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 125000004104 aryloxy group Chemical group 0.000 abstract 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 abstract 1
- VTIDIAIZOPXIFZ-UHFFFAOYSA-N benzyl 2-(4-methylphenyl)sulfonyloxypropanoate Chemical compound C=1C=CC=CC=1COC(=O)C(C)OS(=O)(=O)C1=CC=C(C)C=C1 VTIDIAIZOPXIFZ-UHFFFAOYSA-N 0.000 abstract 1
- ZYTLPUIDJRKAAM-UHFFFAOYSA-N benzyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OCC1=CC=CC=C1 ZYTLPUIDJRKAAM-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002775 capsule Substances 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 125000006310 cycloalkyl amino group Chemical group 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- KYTBWOMLGWBGOL-UHFFFAOYSA-N dimethyl(phenyl)azanium;iodide Chemical class [I-].C[NH+](C)C1=CC=CC=C1 KYTBWOMLGWBGOL-UHFFFAOYSA-N 0.000 abstract 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 239000006193 liquid solution Substances 0.000 abstract 1
- 239000006194 liquid suspension Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- CTRLRINCMYICJO-UHFFFAOYSA-N phenyl azide Chemical compound [N-]=[N+]=NC1=CC=CC=C1 CTRLRINCMYICJO-UHFFFAOYSA-N 0.000 abstract 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 abstract 1
- 125000001501 propionyl group Chemical class O=C([*])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
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 abstract 1
- 229940071536 silver acetate Drugs 0.000 abstract 1
- 239000008221 sterile excipient Substances 0.000 abstract 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 abstract 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/564—Three-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
1,266,611. Preparing (cis-1,2-epoxypropyl)- phosphonic acid and derivatives thereof. MERCK & CO. Inc. 12 May, 1969 [15 May, 1968; 27 Aug., 1968; 25 April, 1969], No. 23990/69. Headings C2C and C2P. (Cis-1,2-epoxypropyl)-phosphonic acid or a salt or ester thereof (I) is obtained by treating a 1,2-disubstituted n-propyl phosphonic acid or salt or ester thereof with a reagent capable of effecting epoxide ring closure, at least one of the substituents being OH or functionally equivalent oxygen-containing radical and the other of the said substituents being any leaving group that can be displaced under the reaction conditions. The starting phosphonic compound may have the formula CH 3 CHX<SP>1</SP>CHXP(O)(OR) 2 (II) wherein each R is H or a C 1 -C 5 alkyl, C 2 -C 5 alkenyl, mononuclear aryl or -aralkyl, a metal of Group Ia, IIa, Ib or IIb of the Periodic Table, an amine salt-forming cation, and X and X<SP>1</SP> are halo, hydroxy, azido, C 1 -C 5 alkanoyloxy, trihalomethyl substituted C 1 -C 5 alkanoyloxy, C 1 -C 5 alkylsulphonyloxy, aryl (alkaryl- or aralkyl-) sulphonyloxy, tri-(C 1 -C 5 alkyl) quaternary ammonium salt-forming group, N- cycloalkyl (or N-phenyl) di-(C 1 -C 5 alkyl) quaternary ammonium salt-forming group, di- (C 1 -C 5 ) alkyl sulphonium salt-forming group, aryloxy, aralkoxy, dialkoxyphosphino, N- (alkanesulphonyl) alkylamino or N-alkarylsulphonyl cycloalkylamino with the proviso that at least one of X and X<SP>1</SP> is hydroxy or functionally equivalent oxygen-containing radical. The ring closure may be effected by treating the starting material (which may be formed in situ) with (1) an acid, e.g. H 2 SO 4 , peracetic acid or nitrous acid; with a Lewis acid such as BF 3 or P 2 O 5 ; or with hexafluoroacetone in a protonic acid such as a mineral acid or p-toluene sulphonic acid, (2) with a solution of a metal or metal compound capable of forming metal ions in a neutral or acidic solution, e.g. with silver acetate in a mineral acid, e.g. HCl, (3) with a base having a pH equal to or greater than 7, or (4) by passing a solution of the starting material through an ion exchange column on the basic cycle. Different optically active isomers are obtained according to the particular optically active isomer used as starting material and epoxy formation occurs with a net inversion of the configuration at the carbon atom bearing the leaving substituent X or X<SP>1</SP>. The invention is more particularly directed to the production of ( ) and (-) (cis-1,2-epoxypropyl) phosphonic acid derivatives and when the product is an ester it may be converted to the free acid which may then be converted to a salt especially an alkali metal or alkaline earth metal salt by treatment with a base. The free ( ) and (-) cis-1,2-epoxypropyl phosphonic acid and salts thereof are useful antibacterial agents and may be formulated with diluents and conventional additives. They may be administered orally in capsule or tablet form or in a liquid solution or suspension or parenterally by injection in a sterile excipient. Several methods are described for preparing various types of starting materials of Formula II. Thus, the (1-hydroxy-2-organosulphonyl. oxypropyl) phosphonic compounds may be prepared by treating a compound: wherein R<SP>1</SP> is alkyl, aryl or aralkyl and X<SP>3</SP> is halogen, e.g. Cl or Br, with a phosphite P(OR) 3 and then reducing the resulting intermediate CH 3 CH(OSO 2 R<SP>1</SP>)C(O)P(O)(OR) 2 with a reducing agent, e.g. NaBH 4 . Compounds of Formula II in which X<SP>1</SP> is a dialkylsulphonium salt-forming radical may be obtained by the following reaction scheme: wherein R<SP>2</SP> is C 1 -C 5 alkyl, R<SP>1</SP>Z is an alkyl halide and Z<SP>(-)</SP> is a halogen anion. Starting compounds in which the sulphonium radical is bonded to the 1-carbon atom may be obtained by the following reaction: wherein R<SP>2</SP>SZ is a C 1 -C 5 alkylsulphenyl halide, R<SP>2</SP>X is a C 1 -C 5 alkyl halide, R<SP>3</SP> is C 1 -C 5 alkyl, R<SP>3</SP>COOM is a metal salt of a C 1 -C 5 alkanoic acid, X# is a halogen anion and R, R<SP>2</SP> and Z are as defined above. Compounds of the type in which an oxygen-containing radical is bonded to the 2-C atom, e.g. as in (IIb) below may be obtained by a reaction of the type: wherein R<SP>4</SP> is C 1 -C 5 alkyl, trihalomethyl, or trihalomethyl-substituted C 1 -C 5 alkyl. Compounds in which X is halogen in Formula II may be obtained by either (a) the following reaction: wherein R<SP>5</SP> is a hydrocarbyl radical or an alkali metal or alkaline earth metal and wherein the N-bromo-succinimide may be replaced by other functionally equivalent halogenating agents; or (b) by the following reaction sequences wherein X<SP>4</SP> is a halogen atom, this method being particularly suitable for the preparation of the ( ) threo (1-halo-2-hydroxypropyl) phosphonic acid (IIj) which may then be converted to the (+) threo derivative (IIm) by resolution as shown. Starting compounds in which the leaving group X is a substituted amino radical may be obtained by the following reaction: wherein R<SP>6</SP> is alkyl or mononuclear cycloalkyl, X<SP>2</SP> is a halogenating agent, H+ is the cation derived from an acid, and the chloroform is used as reaction medium for the halogenating agent. In another method the above intermediate compound VI is converted to the compound IIp below by the following reaction: wherein M, R and R<SP>6</SP> are as defined above and wherein other appropriate sulphonyl halides may also be used instead of the reagent shown. Compounds (II) in which the oxygen-containing radical is bonded to the 1-carbon atom may be obtained by the following reaction: with further reaction of the OH group on the 1-carbon atom with an appropriate organic acid halide if required. The starting compounds in which R is C 1 -C 5 alkyl, X is OH and X<SP>1</SP> is tri- (C 1 - 5 alkyl) quaternary ammonium or a di- (C 1 -C 5 alkyl) sulphonium salt forming group may be prepared by the latter reaction using compounds in which X<SP>1</SP> is NH 2 or (C 1 -C 5 alkyl) mercapto and then treating the product with a C 1 -C 5 alkyl halide. Compounds II may also be obtained by reacting a suitably substituted propionyl halide with a phosphite triester to form a (2-X<SP>1</SP>-substituted propionyl) phosphonate and then reducing the latter, e.g. with an alkali metal borohydride: Threo dimethyl - [1 - (phenylamino) - 2 - hydroxyprepyl] phosphonate is obtained by reacting cis-1-propenyl phosphonate with phenyl azide to form (1,2 - N - phenyliminopropyl) phosphonate and then treating the latter with 2N H 2 SO 4 at 40 C. Treatment of the product with methyl iodide in methanol, removal of the methanol, addition of benzene and its evaporation to azeotrope the reaction mixture to dryness, followed by further reaction with methyl iodide in benzene yields the corresponding N-phenyl dimethylammonium iodide derivative. Benzyl-2-tosyloxypropionate is obtained by reacting benzyl lactate (dissolved in benzene) with p-toluene sulphonyl chloride in the presence of pyridine and on hydrogenation over a Pd on charcoal catalyst yields 2-tosyloxypropionic acid which is then treated with thionyl chloride to form 2-tosyloxypropionyl chloride.
[GB1266611A]
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72942468A | 1968-05-15 | 1968-05-15 | |
US75572968A | 1968-08-27 | 1968-08-27 | |
US81944769A | 1969-04-25 | 1969-04-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
IE32804L true IE32804L (en) | 1969-11-15 |
IE32804B1 IE32804B1 (en) | 1973-12-12 |
Family
ID=27419130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE635/69A IE32804B1 (en) | 1968-05-15 | 1969-05-06 | Preparation of (cis-1,2-epoxypropyl)phosphonic acid and derivatives thereof |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS4919264B1 (en) |
AR (1) | AR195479A1 (en) |
AT (1) | AT306052B (en) |
BE (1) | BE733050A (en) |
CA (1) | CA939366A (en) |
CH (1) | CH513924A (en) |
DE (1) | DE1924169C3 (en) |
ES (2) | ES367269A1 (en) |
FI (1) | FI53216C (en) |
FR (1) | FR2008620B1 (en) |
GB (1) | GB1266611A (en) |
IE (1) | IE32804B1 (en) |
IL (1) | IL32180A0 (en) |
NL (1) | NL6907465A (en) |
YU (1) | YU120469A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4937367A (en) * | 1987-07-15 | 1990-06-26 | Zambon Group S.P.A. | Process for the preparation of intermediates for the synthesis of fosfomycin |
CN114540619B (en) * | 2020-11-25 | 2024-02-13 | 厦门稀土材料研究所 | Functional ionic liquid and preparation method and application thereof |
-
1969
- 1969-05-06 IL IL32180A patent/IL32180A0/en unknown
- 1969-05-06 IE IE635/69A patent/IE32804B1/en unknown
- 1969-05-12 GB GB1266611D patent/GB1266611A/en not_active Expired
- 1969-05-12 DE DE1924169A patent/DE1924169C3/en not_active Expired
- 1969-05-12 CA CA051,319A patent/CA939366A/en not_active Expired
- 1969-05-14 BE BE733050D patent/BE733050A/xx unknown
- 1969-05-14 YU YU01204/69A patent/YU120469A/en unknown
- 1969-05-14 FI FI1443/69A patent/FI53216C/fi active
- 1969-05-14 CH CH743369A patent/CH513924A/en not_active IP Right Cessation
- 1969-05-14 NL NL6907465A patent/NL6907465A/xx not_active Application Discontinuation
- 1969-05-14 ES ES367269A patent/ES367269A1/en not_active Expired
- 1969-05-14 AT AT462869A patent/AT306052B/en not_active IP Right Cessation
- 1969-05-15 JP JP44037097A patent/JPS4919264B1/ja active Pending
- 1969-05-16 FR FR6915925A patent/FR2008620B1/fr not_active Expired
-
1971
- 1971-09-16 ES ES395161A patent/ES395161A1/en not_active Expired
-
1972
- 1972-02-11 AR AR240490A patent/AR195479A1/en active
Also Published As
Publication number | Publication date |
---|---|
FR2008620A1 (en) | 1970-01-23 |
CH513924A (en) | 1971-10-15 |
FI53216B (en) | 1977-11-30 |
GB1266611A (en) | 1972-03-15 |
FI53216C (en) | 1978-03-10 |
ES395161A1 (en) | 1974-11-16 |
FR2008620B1 (en) | 1975-10-31 |
ES367269A1 (en) | 1972-02-16 |
AT306052B (en) | 1973-03-26 |
AR195479A1 (en) | 1973-10-15 |
IL32180A0 (en) | 1969-07-30 |
DE1924169C3 (en) | 1974-02-21 |
DE1924169B2 (en) | 1973-07-05 |
BE733050A (en) | 1969-11-14 |
IE32804B1 (en) | 1973-12-12 |
NL6907465A (en) | 1969-11-18 |
CA939366A (en) | 1974-01-01 |
JPS4919264B1 (en) | 1974-05-16 |
DE1924169A1 (en) | 1970-02-05 |
YU120469A (en) | 1979-10-31 |
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