ES367098A1 - A procedure for the preparation of phosphonic acid. (Machine-translation by Google Translate, not legally binding) - Google Patents
A procedure for the preparation of phosphonic acid. (Machine-translation by Google Translate, not legally binding)Info
- Publication number
- ES367098A1 ES367098A1 ES367098A ES367098A ES367098A1 ES 367098 A1 ES367098 A1 ES 367098A1 ES 367098 A ES367098 A ES 367098A ES 367098 A ES367098 A ES 367098A ES 367098 A1 ES367098 A1 ES 367098A1
- Authority
- ES
- Spain
- Prior art keywords
- cis
- optically active
- propenyl
- benzyl
- phosphonate
- 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract 6
- 238000000034 method Methods 0.000 title abstract 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract 15
- -1 diphenyl propenyl phosphonate Chemical compound 0.000 abstract 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 9
- 239000002253 acid Substances 0.000 abstract 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 5
- 239000000047 product Substances 0.000 abstract 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 4
- XWCIXXXLOAAWPU-IHWYPQMZSA-N [(z)-prop-1-enyl]phosphonic acid Chemical compound C\C=C/P(O)(O)=O XWCIXXXLOAAWPU-IHWYPQMZSA-N 0.000 abstract 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract 3
- 239000001257 hydrogen Substances 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract 3
- 229910052698 phosphorus 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
- 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 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-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
- 239000004305 biphenyl Substances 0.000 abstract 2
- 235000010290 biphenyl Nutrition 0.000 abstract 2
- 125000006267 biphenyl group Chemical group 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000006735 epoxidation reaction Methods 0.000 abstract 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 2
- FUWGSUOSJRCEIV-UHFFFAOYSA-N phosphonothioic O,O-acid Chemical compound OP(O)=S FUWGSUOSJRCEIV-UHFFFAOYSA-N 0.000 abstract 2
- 125000004437 phosphorous atom Chemical group 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-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 1
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 abstract 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 1
- 125000000028 D-cysteine group Chemical class [H]N([H])[C@@]([H])(C(=O)[*])C(S[H])([H])[H] 0.000 abstract 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 abstract 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-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
- GTSOBGIMTNKIPJ-UHFFFAOYSA-N OP(Cl)=O Chemical class OP(Cl)=O GTSOBGIMTNKIPJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical class NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000003862 amino acid derivatives Chemical class 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 abstract 1
- 150000003939 benzylamines Chemical class 0.000 abstract 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 abstract 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical class C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003729 cation exchange resin Substances 0.000 abstract 1
- 239000007795 chemical reaction product 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
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000004966 cyanoalkyl group Chemical group 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 229940073579 ethanolamine hydrochloride Drugs 0.000 abstract 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 abstract 1
- 238000001640 fractional crystallisation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229960004873 levomenthol Drugs 0.000 abstract 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- MXRQJLCXKVCRFJ-UHFFFAOYSA-N oxan-2-yl 2-hydroxyacetate Chemical compound OCC(=O)OC1CCCCO1 MXRQJLCXKVCRFJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 150000003009 phosphonic acids Chemical class 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 abstract 1
- 229940116357 potassium thiocyanate Drugs 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 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
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 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
- C07F9/28—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
- C07F9/3826—Acyclic unsaturated acids
-
- 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)
Abstract
An optically active derivative of cis-propenyl phosphonic or thiophosphonic is reacted with an epoxidizing agent and a derivative of an optical form of (cis-1,2-epoxypropyl)phosphonic or thiophosphonic acid is recovered from the reaction product. The invention also includes reacting an optically active derivative of cispropenyl-phosphonic or thiophosphonic acid with an epoxidizing agent to form a mixture of diastereoisomers of a derivative of (cis-1,2- epoxypropyl)phosphonic or thiophosphonic acid, said mixture containing a preponderance of one of the diastereoisomers. The optically active derivative used as starting material may have an optically active phosphorus centre and have the general formula CH 3 CH = CH-P( :X)(Y)(Z) wherein X is O or S, Y and Z are different, Y is OR, SR, NRR 1 or halogen, Z is OR1, SR1, NR1R 1 or halogen, R is a univalent substituted or unsubstituted hydrocarbyl or heterocyclic group and R 1 and R1 are hydrogen or a univalent substituted or unsubstituted hydrocarbyl or heterocyclic group. The optically active starting materials may alternatively have attached to the phosphorus atom a substituent containing an optically active centre or may contain an optically active centre substituted on the terminal methyl group of the acid. Compounds of the latter type may have the formula CH 2 (B)CH 2 = CH-P(:X)(Y)(Z) wherein X, Y and Z are as defined above and B is a group containing an optically active centre which is convertible to hydrogen. Thus diphenyl propenyl phosphonate may be brominated to produce diphenyl 3-bromopropenyl phosphonate which is then reacted with an optically active amino acid derivative, e.g. with sodium L-N-acetyl ethyl cysteinate in ethanol to form S-[3-(diphenoxyphosphinyl)allyl]-N- acetyl-L-cysteine ethyl ester which is then epoxidized and the resulting epoxide treated with Raney nickel to yield a mixture from which an optically active form of diphenyl (cis-1,2- epoxypropyl)phosphonate is recovered. Similarly when the D-cysteine derivative is used the other optically active form of diphenyl (cis-1,2- epoxypropyl)phosphonate is recovered. When the derivative contains an optically active phosphorus atom the (+) and ( - ) enantiomers of such derivative can be separated by forming a diastereoisomer of such derivative, e.g. by reaction of a derivative containing a basic or acidic ester-forming group with an optically active acid or base respectively, or by forming the OR group from an optically active alcohol and separating the diastereoisomers in each case. Thus, the diastereoisomers of (1) the (+) 10- camphorsulphonic acid salt of benzyl 2-aminoethyl cis-propenyl phosphonate, (2) benzyl L- (2 - carbobenzyloxyamine - 2 - ethoxycarbonyl)- ethyl cis-propenyl phosphate, (3) methyl ( - ) menthyl cis-propenyl phosphonate and (4) the (+) phenethylamine salt of benzyl carboxymethyl cis-propenyl phosphonate, may be separated. In the case of (1) the separated diastereoisomers are converted to the (+) and ( - ) antipodes of benzyl 2-aminoethyl cispropenyl phosphonate which are then separately epoxidized and the ester groups in the products cleaved to form the ( + ) and ( - ) enantiomers of (cis - 1,2 - epoxypropyl)phosphonic acid. The diastereoisomers of (2), (3) and (4) are separately epoxidized and the epoxides converted to ( + ) and ( -) (cis-1,2-epoxypropyl)phosphonic acid or salt derivative. Other optically active derivatives which can be used for the epoxidation include, (a) the ( + ) [alpha]-phenethylamine salt of cis-propenyl phosphonic acid and (b) optically active cyanoalkyl esters of cis-propenyl phosphonic acid, e.g. ( + ) and ( - ) benzyl cyanomethyl cis-propenyl phosphonic acid which are epoxidized with H 2 O 2 in the presence of methanol containing sodium bicarbonate to form the (+) and ( - ) benzyl carbamoylmethyl (cis-1,2- epoxypropyl)-phosphonates which are then converted to ( + ) and ( -) (cis-1,2-epoxypropyl) phosphonic acids by hydrogenolysis followed by passage through a cation exchange resin on the hydrogen cycle. In another example benzyl cis-propenylphosphonochloridate is treated with H 2 S and triethylamine added to yield the corresponding phosphonothioic acid which is then treated with ( - ) quinine to form diastereoisomeric quinine salts which are separated and converted to the two optically active antipodes of the free phosphonothioic acid, these antipodes are then separately epoxidized and converted to (+) and ( - ) benzyl (cis-1,2- epoxypropyl) phosphonochloridates by treatment of the sodium salt of each epoxidized product with phosgene in hexane solution at -40 to - 60 C. and then warming to room temperature, the resulting phosphonochloridate ester being finally converted to the benzylamine salts of (+) and ( - ) (cis-1,2-epoxypropyl)- phosphonic acid by hydrogenolysis followed by the addition of benzylamine hydrochloride. Cis-propenyl phosphoric dichloride is obtained by adding the free phosphonic acid dissolved in tetrahydrofuran to a suspension of PCl 5 in CCl 4 . Benzyl cis - propenylphosphonochloridate is obtained by reacting the dichloride dissolved in benzene with benzyl alcohol in the presence of triethylamine and the product is converted to benzyl 2-amino ethyl cis-propenyl phosphonate by reaction with ethanolamine hydrochloride in tetrahydrofuran in the presence of pyridine. Benzyl [(2 - tetrahydropyranyloxy)- carbonyl]- methyl cis-propenyl phosphonate is obtained by reacting benzyl cis-propenylphosphonochloridate with hydroxy acetic acid tetrahydropyranyl ester in the presence of triethylamine and is converted to benzyl carboxymethyl cispropenyl phosphonate by acidification with 1NHCl. Diphenyl propenyl phosphonate is obtained by reacting propenyl phosphonic acid with phenol in CH 2 Cl 2 in the presence of dicyclohexylcarbodiimide and is converted to diphenyl 3-bromo propenyl phosphonate by reacting with N-bromosuccinimide in CCl 4 under irradiation with U.V. light. Methyl cis - propenylphosphonochloridate is obtained by reacting the dichloride with methanol in benzene in the presence of triethylamine and is converted to methyl ( - ) menthyl cispropenyl phosphonate by reacting with ( - ) menthol in benzene in the presence of triethylamine, the product being separated into the ( + ) and ( - ) diastereoisomeric forms by fractional crystallization from ethyl acetate-hexane. (+)(cis - 1,2 - Epoxypropyl)phosphonic acid is converted to cis-propenyl phosphonic acid by heating with potassium thiocyanate in aqueous methanol and the product may be converted to ( - )(cis-1,2-epoxypropyl)phosphonic acid by the epoxidation procedure of the invention.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72939668A | 1968-05-15 | 1968-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES367098A1 true ES367098A1 (en) | 1971-05-01 |
Family
ID=24930845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES367098A Expired ES367098A1 (en) | 1968-05-15 | 1969-05-12 | A procedure for the preparation of phosphonic acid. (Machine-translation by Google Translate, not legally binding) |
Country Status (7)
| Country | Link |
|---|---|
| AT (1) | AT300830B (en) |
| BE (1) | BE733039A (en) |
| DE (1) | DE1924155A1 (en) |
| ES (1) | ES367098A1 (en) |
| GB (1) | GB1226472A (en) |
| IL (1) | IL32117A0 (en) |
| NL (1) | NL6904139A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE9100303U1 (en) * | 1991-01-11 | 1992-05-07 | Schomburg, Heinrich, Dipl.-Phys. Dr., 4300 Essen | Pump chamber for laser devices |
-
1969
- 1969-03-18 NL NL6904139A patent/NL6904139A/xx unknown
- 1969-05-01 IL IL32117A patent/IL32117A0/en unknown
- 1969-05-08 AT AT441869A patent/AT300830B/en not_active IP Right Cessation
- 1969-05-12 GB GB1226472D patent/GB1226472A/en not_active Expired
- 1969-05-12 ES ES367098A patent/ES367098A1/en not_active Expired
- 1969-05-12 DE DE19691924155 patent/DE1924155A1/en active Pending
- 1969-05-14 BE BE733039D patent/BE733039A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1226472A (en) | 1971-03-31 |
| AT300830B (en) | 1972-08-10 |
| DE1924155A1 (en) | 1970-04-23 |
| BE733039A (en) | 1969-11-14 |
| IL32117A0 (en) | 1969-07-30 |
| NL6904139A (en) | 1969-11-18 |
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