ES367118A1 - Process for preparing a diastereomer of an optically active ester or amide of (cis-1,2-epoxypropyl)-phosphonic acid - Google Patents
Process for preparing a diastereomer of an optically active ester or amide of (cis-1,2-epoxypropyl)-phosphonic acidInfo
- Publication number
- ES367118A1 ES367118A1 ES367118A ES367118A ES367118A1 ES 367118 A1 ES367118 A1 ES 367118A1 ES 367118 A ES367118 A ES 367118A ES 367118 A ES367118 A ES 367118A ES 367118 A1 ES367118 A1 ES 367118A1
- Authority
- ES
- Spain
- Prior art keywords
- epoxypropyl
- cis
- acid
- optically active
- group
- 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
- 150000002148 esters Chemical class 0.000 title abstract 14
- 150000001408 amides Chemical class 0.000 title abstract 9
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002253 acid Substances 0.000 abstract 18
- 150000003839 salts Chemical class 0.000 abstract 11
- 230000002378 acidificating effect Effects 0.000 abstract 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 7
- 239000000203 mixture Substances 0.000 abstract 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 6
- 150000001412 amines Chemical class 0.000 abstract 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 4
- 150000007513 acids Chemical class 0.000 abstract 4
- 229940117803 phenethylamine Drugs 0.000 abstract 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 4
- -1 amide compounds Chemical class 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract 3
- 125000001183 hydrocarbyl group Chemical group 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
- 239000011734 sodium Substances 0.000 abstract 3
- 229910052708 sodium Inorganic materials 0.000 abstract 3
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 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 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 abstract 2
- WUEAMTVQNGYLRI-UHFFFAOYSA-N 2-dichlorophosphoryl-1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=C(P(Cl)(Cl)=O)C(C(C)C)=C1 WUEAMTVQNGYLRI-UHFFFAOYSA-N 0.000 abstract 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 abstract 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 2
- 125000004185 ester group Chemical group 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 125000001475 halogen functional group Chemical group 0.000 abstract 2
- 239000003456 ion exchange resin Substances 0.000 abstract 2
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 abstract 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 abstract 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-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
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 150000001345 alkine derivatives Chemical class 0.000 abstract 1
- 125000003368 amide group Chemical group 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000002421 anti-septic effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 abstract 1
- 230000003115 biocidal effect Effects 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract 1
- 229940106681 chloroacetic acid Drugs 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 150000005690 diesters Chemical class 0.000 abstract 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000001640 fractional crystallisation Methods 0.000 abstract 1
- SKHIBNDAFWIOPB-UHFFFAOYSA-N hydron;2-phenylethanamine;chloride Chemical compound Cl.NCCC1=CC=CC=C1 SKHIBNDAFWIOPB-UHFFFAOYSA-N 0.000 abstract 1
- 229960004873 levomenthol Drugs 0.000 abstract 1
- 239000000546 pharmaceutical excipient Substances 0.000 abstract 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical group OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 abstract 1
- 125000005499 phosphonyl group Chemical group 0.000 abstract 1
- ZPFBCFAPICAMJZ-UHFFFAOYSA-M potassium;ethanethiolate Chemical compound [K+].CC[S-] ZPFBCFAPICAMJZ-UHFFFAOYSA-M 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 150000003335 secondary amines Chemical class 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 235000010344 sodium nitrate Nutrition 0.000 abstract 1
- 239000004317 sodium nitrate Substances 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 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)
- Detergent Compositions (AREA)
Abstract
Diastereoisomers of (cis - 1,2 - epoxypropyl) phosphonic (or thiophosphonic) acid derivatives are separated by (a) forming a diastereoisomeric mixture of (1) an ester or amide of (cis- 1,2 - epoxypropyl) - phosphonic (or thiophosphonic) acid containing an optically active ester or amide group or (2) of a salt of an optically active acid or base with an ester or amide of (cis - 1,2 - epoxypropyl)phosphonic or thiophosphonic acid containing a basic or acidic group respectively, the (cis-1,2-epoxypropyl)- phosphonic or thiophosphonic acid residue being present in the diastereoisomeric mixture in both its optically active forms by starting from a mixture of enantiomers of (cis-1,2-epoxypropyl)phosphonic or thiophosphonic acid or a salt or an ester or amide thereof, and (b) separating a diastereoisomer from the diastereoisomeric mixture. The diastereoisomers may be compounds of the formula wherein X is O or S, Y is halo, OR, SR or NRR, and Z is OR1, SR1 or NR1R 1 wherein R is a substituted or unsubstituted hydrocarbyl or heterocyclic group containing an optically active centre and each of R1 and R 1 is H or a substituted or unsubstituted hydrocarbyl or heterocyclic group with the proviso that whenY is halo, R1 is a substituted or unsubstituted hydrocarbyl or heterocyclic group containing an optically active centre. The optically active consituent of the ester group or groups may be derived from an optically active alcohol and the optically active amides may be derived from an optically active primary or secondary amine. The diastereoisomers after separation can be converted to the (+) or (-) enantiomer of cis-1,2-epoxypropyl phosphonic acid or its salts. The individual diastereoisomeric esters can be separated from the mixture thereof by fractional crystallization, chromatography, ion exchange resin procedures or by inclusion or cloth rate compounds. When the diastereoisomers are salts of optically active acids or bases with an ester or amide of (cis-1,2,-epoxypropyl)phosphonic or thiophosphonic acid containing a basic or acidic group respectively the acidic group may be a carboxy, sulphonic, sulphinic, phosphonic or phosphonous acid group and such ester or amide compounds can be prepared (1) by reacting anhydrides (including mono- and dihalides) of (cis-1,2-epoxypropyl) phosphonic acid with strong acids with appropriate alcohols, thio-alcohols, amines, metal alcoholates or thioalcoholates, which also carry an acidic group or a group convertible to an acidic group, (2) by reacting (cis-1,2-epoxypropyl) phosphonic acid or basic salt thereof with an alcohol, thioalcohol or amine carrying such acidic group, or (3) by reacting a metal salt of the phosphonic acid with an appropriate ester of a strong acid (e.g. chloroacetic acid) or with another derivative, the ester or said other derivative also carrying an acidic group or group convertible to an acid group, or (4) by reacting (cis-1,2- epoxypropyl)phosphonic acid or metal salt thereof with alkenes or alkynes in which one of the carbons bearing the unsaturation is also substituted with an electron withdrawing or electronegative atom or group and which also carries an acid group or a group convertible to an acid group. When the diastereoisomers are salts of optically active acids with an ester or amide of (cis-1,2-epoxypropyl) phosphonie acid the said ester or amide may be obtained by a method as in (1) to (4) above but using the corresponding organic reactant containing a basic (e.g. amino) group instead of an acid group. A list of optically active amines (a) and acids (b) suitable for forming the optically acid salts is given and several optically active alcohols (c) and amines (d) suitable for preparing the esters or amides are also specified. In the examples given the optically active amines (a) used include (+) and (-) [alpha]-phenethylamine for (a) and (+) [alpha]-phenethylamine for (d), (+) tartaric acid for (b) and (-) menthol for (c), the ester used in conjunction with the (+) tartaric acid being racemic bis(2-aminoethyl)(cis-1,2-epoxypropyl) phosphonic acid which is obtained by passing racemic monobenzylammonium (cis- 1,2-epoxypropyl) phosphonate in methanol through a strongly acidic ion exchange resin on the H+ cycle, collecting the effluent in pyridine, removing the methanol and then adding ethyleneimine and stirring the mixture at 50 C., the pyridine being finally removed to leave the racemic diester. By using ethylene episulphide instead of ethyleneimine in the above process racemic - bis(2 - mercaptoethyl)(cis - 1,2 - epoxypropyl) phosphonate is obtained which may be reacted with H 2 O 2 and NaHCO 3 in water to form a solution containing racemic disodium (cis - 1,2 - epoxypropyl) - phosphonyl - O,O1- bis(2 - ethylsulphonate) which on treatment with (+) phenethylamine hydrochloride in aqueous solution gives a mixture of diastereoisomeric salts which is recovered by filtering the hot aqueous slurry and the salts then separated by cooling the filtrate to 0 C. and filtering. The following compounds (inter alia) are also prepared in various steps in the examples given: (1) bis-(2-nitroethyl)(-)(cis-1,2-epoxypropyl) phosphonate by adding a solution of sodium nitrate and sodium cobaltinitrate to (cis - 1,2 - epoxypropyl) phosphonyl - O,O1- bis - 2 - ethyl ammonium (+) tartrate (2) N- benzoyl - N - (+) - [alpha] - phenethyl (-) (cis - 1,2- epoxypropyl)-phosphors chloridate from racemic (cis-1,2-epoxypropyl) phosphonic dichloride, (+)-[alpha]-phenethylamine and benzoyl chloride, (3) N - methyl - N(+) - [alpha] - phenethyl - S- ethyl(-)(cis - 1,2 - epoxypropyl) - thiophosphoramidate from the phosphonic dichloride and N-methyl-(+)-[alpha]-phenethylamine with subsequent reaction with potassium ethane thiolate, (4) sodium 2-nitroethyl - (-) (cis - 1,2 - epoxypropyl) phosphonate from sodium nitrite, sodium cobaltinitrite and 2-aminoethyl(-)(cis- 1,2 - epoxypropyl) - phosphonate. The (-)- (cis - 1,2 - epoxypropyl) phosphonic acid and salts thereof obtainable by the invention have antibiotic and antiseptic properties and may be administered orally or parenterally in admixture with suitable diluents and other usual pharmaceutical additives.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72946868A | 1968-05-15 | 1968-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES367118A1 true ES367118A1 (en) | 1971-05-01 |
Family
ID=24931178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES367118A Expired ES367118A1 (en) | 1968-05-15 | 1969-05-12 | Process for preparing a diastereomer of an optically active ester or amide of (cis-1,2-epoxypropyl)-phosphonic acid |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US3595869A (en) |
| AT (1) | AT300832B (en) |
| BE (1) | BE733060A (en) |
| BR (1) | BR6908795D0 (en) |
| DE (1) | DE1924085A1 (en) |
| ES (1) | ES367118A1 (en) |
| GB (1) | GB1259798A (en) |
| IE (1) | IE32801B1 (en) |
| LU (1) | LU58639A1 (en) |
| NL (1) | NL6905475A (en) |
| OA (1) | OA03052A (en) |
| ZM (1) | ZM5869A1 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451401A (en) * | 1993-09-29 | 1995-09-19 | The Procter & Gamble Company | Diphosphonic acid esters as tartar control agents |
| US9828324B2 (en) | 2010-10-20 | 2017-11-28 | Sirrus, Inc. | Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom |
| US9279022B1 (en) | 2014-09-08 | 2016-03-08 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
| US10414839B2 (en) | 2010-10-20 | 2019-09-17 | Sirrus, Inc. | Polymers including a methylene beta-ketoester and products formed therefrom |
| US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| WO2013059473A2 (en) | 2011-10-19 | 2013-04-25 | Bioformix Inc. | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom |
| US9234107B2 (en) | 2012-03-30 | 2016-01-12 | Sirrus, Inc. | Ink coating formulations and polymerizable systems for producing the same |
| CA2869108A1 (en) | 2012-03-30 | 2013-10-03 | Bioformix Inc. | Methods for activating polymerizable compositions, polymerizable systems, and products formed thereby |
| US10913875B2 (en) | 2012-03-30 | 2021-02-09 | Sirrus, Inc. | Composite and laminate articles and polymerizable systems for producing the same |
| WO2013181600A2 (en) | 2012-06-01 | 2013-12-05 | Bioformix Inc. | Optical material and articles formed therefrom |
| EP2920231B1 (en) | 2012-11-16 | 2020-05-06 | Sirrus, Inc. | Plastics bonding systems and methods |
| WO2014085570A1 (en) | 2012-11-30 | 2014-06-05 | Bioformix, Inc. | Composite compositions for electronics applications |
| CN105008321A (en) | 2013-01-11 | 2015-10-28 | 瑟拉斯公司 | Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway |
| WO2016029330A1 (en) * | 2014-08-26 | 2016-03-03 | 北京美倍他药物研究有限公司 | Novel phosphonate derivative and medical use thereof |
| US9315597B2 (en) | 2014-09-08 | 2016-04-19 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US9416091B1 (en) | 2015-02-04 | 2016-08-16 | Sirrus, Inc. | Catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US10501400B2 (en) | 2015-02-04 | 2019-12-10 | Sirrus, Inc. | Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
| US9334430B1 (en) | 2015-05-29 | 2016-05-10 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US9217098B1 (en) | 2015-06-01 | 2015-12-22 | Sirrus, Inc. | Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound |
| US9518001B1 (en) | 2016-05-13 | 2016-12-13 | Sirrus, Inc. | High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation |
| US10428177B2 (en) | 2016-06-03 | 2019-10-01 | Sirrus, Inc. | Water absorbing or water soluble polymers, intermediate compounds, and methods thereof |
| US10196481B2 (en) | 2016-06-03 | 2019-02-05 | Sirrus, Inc. | Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof |
| US9567475B1 (en) | 2016-06-03 | 2017-02-14 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US9617377B1 (en) | 2016-06-03 | 2017-04-11 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
-
1968
- 1968-05-15 US US729468A patent/US3595869A/en not_active Expired - Lifetime
-
1969
- 1969-04-09 NL NL6905475A patent/NL6905475A/xx unknown
- 1969-04-30 ZM ZM58/69A patent/ZM5869A1/en unknown
- 1969-05-02 IE IE618/69A patent/IE32801B1/en unknown
- 1969-05-06 OA OA53601A patent/OA03052A/en unknown
- 1969-05-12 ES ES367118A patent/ES367118A1/en not_active Expired
- 1969-05-12 DE DE19691924085 patent/DE1924085A1/en active Pending
- 1969-05-12 GB GB23987/69A patent/GB1259798A/en not_active Expired
- 1969-05-14 AT AT463769A patent/AT300832B/en not_active IP Right Cessation
- 1969-05-14 LU LU58639D patent/LU58639A1/xx unknown
- 1969-05-14 BR BR208795/69A patent/BR6908795D0/en unknown
- 1969-05-14 BE BE733060D patent/BE733060A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL6905475A (en) | 1969-11-18 |
| IE32801B1 (en) | 1973-12-12 |
| IE32801L (en) | 1969-11-15 |
| ZM5869A1 (en) | 1970-12-21 |
| DE1924085A1 (en) | 1970-01-15 |
| LU58639A1 (en) | 1970-01-13 |
| BR6908795D0 (en) | 1973-05-17 |
| AT300832B (en) | 1972-08-10 |
| OA03052A (en) | 1970-12-15 |
| US3595869A (en) | 1971-07-27 |
| GB1259798A (en) | 1972-01-12 |
| BE733060A (en) | 1969-11-14 |
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