ES359538A1 - Cis-propenyl phosphonic acid and derivatives thereof - Google Patents
Cis-propenyl phosphonic acid and derivatives thereofInfo
- Publication number
- ES359538A1 ES359538A1 ES359538A ES359538A ES359538A1 ES 359538 A1 ES359538 A1 ES 359538A1 ES 359538 A ES359538 A ES 359538A ES 359538 A ES359538 A ES 359538A ES 359538 A1 ES359538 A1 ES 359538A1
- Authority
- ES
- Spain
- Prior art keywords
- cis
- propenyl
- compounds
- acid
- phosphonic acid
- 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
- 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 4
- 150000001875 compounds Chemical class 0.000 abstract 7
- -1 propynyl compound Chemical class 0.000 abstract 7
- 150000003839 salts Chemical class 0.000 abstract 6
- 150000004820 halides Chemical class 0.000 abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 150000001408 amides Chemical class 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 abstract 3
- 125000005843 halogen group Chemical group 0.000 abstract 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 2
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 2
- 239000005864 Sulphur Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 150000002440 hydroxy compounds Chemical class 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 239000003960 organic solvent Substances 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 150000003009 phosphonic acids Chemical class 0.000 abstract 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 abstract 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- 125000004434 sulfur atom Chemical group 0.000 abstract 2
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 abstract 1
- 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 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000007818 Grignard reagent Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 125000000732 arylene group Chemical group 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- MCKANBCWFDYIJO-UHFFFAOYSA-N chloro-dihydroxy-imino-$l^{5}-phosphane Chemical compound NP(O)(Cl)=O MCKANBCWFDYIJO-UHFFFAOYSA-N 0.000 abstract 1
- HPFKOFNYNQMWEF-UHFFFAOYSA-N chloro-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(Cl)=S HPFKOFNYNQMWEF-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 150000001470 diamides Chemical class 0.000 abstract 1
- 150000005690 diesters Chemical class 0.000 abstract 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 abstract 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 abstract 1
- 229940046892 lead acetate Drugs 0.000 abstract 1
- OYICOGPBEIHJEO-UHFFFAOYSA-L magnesium;acetylene;dibromide Chemical compound [Mg+2].[Br-].[Br-].C#C OYICOGPBEIHJEO-UHFFFAOYSA-L 0.000 abstract 1
- 125000002757 morpholinyl group Chemical group 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 150000007530 organic bases Chemical class 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 125000005541 phosphonamide group Chemical group 0.000 abstract 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 1
- FUWGSUOSJRCEIV-UHFFFAOYSA-N phosphonothioic O,O-acid Chemical compound OP(O)=S FUWGSUOSJRCEIV-UHFFFAOYSA-N 0.000 abstract 1
- 125000003386 piperidinyl group Chemical group 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 229910001961 silver nitrate Inorganic materials 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 150000003573 thiols Chemical class 0.000 abstract 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004246 zinc acetate 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
- C07F9/547—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
- C07F9/06—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
- C07F9/6564—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
The invention comprises cis - propenyl phosphonic acid and derivatives thereof of the formula wherein X is an O or S atom, Y is -OR, -SR, halo, or -NR 1 R 2 or other substituted amino group, Z is -OR, SR, halo, or -NR 1 R 2 or other substituted amino group, and each of R, R 1 and R 2 is a hydrogen atom or a substituted or unsubstituted hydrocarbyl or heterocyclic radical, or an acyl radical, and organic or inorganic salts of such compounds in which one or both of Y and Z is an OH group. The invention also includes such compounds but in which NR 1 R 2 is a heterocyclic ring and also such compounds in which Y and Z together from a bridged arylene or substituted or unsubstituted alkylene radical which may contain an interrupting, hetero atom e.g. -S- or -NH- and also compounds in which Y and Z together for an alkylene or arylene bridge and one of Y and Z is nitrogencontaining. When the radical NR 1 R 2 is a heterocyclic radical it may be e.g. morpholinyl, thiomorpholinyl or piperidinyl. The acid, salt and ester products may be obtained by the selective hydrogenation of cis - propynyl phosphonic acid or ester or salt thereof in the presence of a solvent e.g. an inert organic solvent such as a C 1 -C 6 alkanol, ether, benzene, toluene, ethyl acetate or methylene chloride. The hydrogenation is suitably effected in the presence of a hydrogenation catalyst such as Pd, e.g. palladium on calcium carbonate, or a Raney nickel catalyst, and is preferably stopped when one mole of hydrogen has been taken up per mole of the propynyl compound. A small amount of a poisoning agent, e.g. lead acetate for the Pd catalyst, and zinc acetate and/or an organic base for the Raney nickel catalyst, may be added. The dihalides wherein Y and Z are halo are prepared by treating the free phosphonic acid with 2 molecular proportions of a halogenating agent e.g. a thionyl halide, PCl 5 or phosphonyl fluoro bromide in an organic solvent and the compounds where Y and/or Z are -OR or -OR are obtained by treating the dihalide with an appropriate molar amount of a hydroxy compound or mercaptan to yield the diester or monoester halide. The amides (Y and/or Z are NR 1 R 2 ) are prepared by reacting the dihalide with 1 or 2 moles of ammonia or a primary or secondary amine or other amino compound preferably in the presence of a tertiary base to give the phosphonohalidic amides or the diamides. The amide esters or amide thioesters may be obtained by reacting the phosphonohalidic amides with an appropriate hydroxy compound or thiol. Compounds in which X is sulphur may be obtained analogously by using cis-propenyl phosphonothioic dihalide as starting material, the latter being obtainable by reacting cis-propenyl phosphonic dihalide with P 2 S 5 . The products (I) which are halides, phosphonamides or thioates may also be obtained by catalytic hydrogenation of the corresponding propynyl phosphonic halide, phosphonoamide or phosphonothioate, the starting propynyl compounds being obtainable by reacting a metal acetylene Grignard reagent such as a metal acetylene magnesium bromide with the appropriate chlorophosphonic halide, chlorophosphonothioate or chlorophosphonicamide. Di-t-butyl cis-propenyl phosphonate may also be obtained by hydrogenating di-tbutyl-propodienyl phosphonate in the presence of a Pd or carbon catalyst and in the presence of a solvent. The products in which at least one of Y and Z is other than OH may be hydrolysed, e.g. with acid, to produce cis-propenylphosphonic acid or salt thereof. The products (I) may be epoxidized to form the corresponding ( )(cis - 1,2 - epoxypropyl)phosphonic acid compounds which may then be resolved, or if Y and/or Z is other than OH they may be hydrolysed prior to epoxidation. Bis - (cis - propenyl)pyrophosphonic acid is obtained by heating cis-propenyl phosphonic acid to 200 C. under a nitrogen atmosphere at 200 mm. Hg. pressure. Cic - propenyl phosphonic acid cyclic dianhydride is obtained by adding water to cispropenyl phosphonic dichloride at below 10 C. and then heating to 120 C. under 50 mm. pressure. Cis - propenylisohypophosphoric acid is obtained in the form of its sodium salt by reacting diethylchlorophosphate with ethyl cis-propenyl phosphonate in ethanol and then adding NaOH. When X in Formula I is a sulphur atom the S atom may be replaced by O by treating the sulphur-containing compound with peroxytrifluoroacetic acid or with bromine water and when Y and/or Z are -SR the products may be converted to phosphonates by treatment with silver nitrate. The ( )(cis - 1,2 - epoxypropyl)phosphonic acid salts obtainable from the products (I) have antibacterial properties and may be resolved into the optical enantiomers by forming a salt with an optically active amine, separating the diastereomers and regeneration of the enantiomeric salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67920367A | 1967-10-30 | 1967-10-30 | |
| US72942068A | 1968-05-15 | 1968-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES359538A1 true ES359538A1 (en) | 1970-08-16 |
Family
ID=27102173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES359538A Expired ES359538A1 (en) | 1967-10-30 | 1968-10-25 | Cis-propenyl phosphonic acid and derivatives thereof |
Country Status (15)
| Country | Link |
|---|---|
| AT (1) | AT292731B (en) |
| BE (1) | BE723071A (en) |
| CH (1) | CH531012A (en) |
| DK (1) | DK132585C (en) |
| ES (1) | ES359538A1 (en) |
| FI (1) | FI51357C (en) |
| FR (1) | FR1592151A (en) |
| GB (1) | GB1239988A (en) |
| IE (1) | IE32525B1 (en) |
| IL (1) | IL30902A0 (en) |
| LU (1) | LU57182A1 (en) |
| MT (1) | MTP579B (en) |
| NL (1) | NL6814978A (en) |
| NO (1) | NO133200C (en) |
| SE (1) | SE369910B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA774977B (en) * | 1976-09-06 | 1978-06-28 | Sab Soc Etudes Applic Biolog | Process for the preparation of 1,2-expoxypropyl-phosphonic acid derivatives |
| EP2270021A1 (en) | 2009-06-18 | 2011-01-05 | Centre National de la Recherche Scientifique | Phosphonates synthons for the synthesis of phosphonates derivatives showing better bioavailability |
-
1968
- 1968-10-18 NL NL6814978A patent/NL6814978A/xx unknown
- 1968-10-20 IL IL30902A patent/IL30902A0/en unknown
- 1968-10-21 CH CH1569868A patent/CH531012A/en not_active IP Right Cessation
- 1968-10-21 IE IE1257/68A patent/IE32525B1/en unknown
- 1968-10-24 GB GB50636/68A patent/GB1239988A/en not_active Expired
- 1968-10-25 ES ES359538A patent/ES359538A1/en not_active Expired
- 1968-10-29 FI FI683065A patent/FI51357C/en active
- 1968-10-29 DK DK521968A patent/DK132585C/en active
- 1968-10-29 SE SE14617/68A patent/SE369910B/xx unknown
- 1968-10-29 LU LU57182D patent/LU57182A1/xx unknown
- 1968-10-29 BE BE723071D patent/BE723071A/xx unknown
- 1968-10-29 NO NO4276/68A patent/NO133200C/no unknown
- 1968-10-30 AT AT1055368A patent/AT292731B/en not_active IP Right Cessation
- 1968-10-30 FR FR1592151D patent/FR1592151A/fr not_active Expired
- 1968-10-30 MT MT579A patent/MTP579B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IE32525L (en) | 1969-04-30 |
| AT292731B (en) | 1971-09-10 |
| FI51357C (en) | 1976-12-10 |
| SE369910B (en) | 1974-09-23 |
| FI51357B (en) | 1976-08-31 |
| DE1805677A1 (en) | 1969-12-11 |
| NO133200B (en) | 1975-12-15 |
| DK132585B (en) | 1976-01-05 |
| DK132585C (en) | 1976-05-31 |
| BE723071A (en) | 1969-04-29 |
| IE32525B1 (en) | 1973-09-05 |
| CH531012A (en) | 1972-11-30 |
| NO133200C (en) | 1976-03-24 |
| GB1239988A (en) | 1971-07-21 |
| NL6814978A (en) | 1969-05-02 |
| MTP579B (en) | 1969-10-13 |
| IL30902A0 (en) | 1969-02-27 |
| LU57182A1 (en) | 1969-05-16 |
| FR1592151A (en) | 1970-05-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FD1A | Patent lapsed |
Effective date: 19890311 |