HU177441B - Process for preparing syn isomers of 3,7-disubstituted 3-cephem-4-carboxylic acid derivatives - Google Patents
Process for preparing syn isomers of 3,7-disubstituted 3-cephem-4-carboxylic acid derivatives Download PDFInfo
- Publication number
- HU177441B HU177441B HU77FU348A HUFU000348A HU177441B HU 177441 B HU177441 B HU 177441B HU 77FU348 A HU77FU348 A HU 77FU348A HU FU000348 A HUFU000348 A HU FU000348A HU 177441 B HU177441 B HU 177441B
- Authority
- HU
- Hungary
- Prior art keywords
- group
- formula
- alkyl
- cephem
- carboxylic acid
- Prior art date
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- -1 3,7-disubstituted 3-cephem-4-carboxylic acid Chemical class 0.000 title claims abstract description 500
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 233
- 150000003839 salts Chemical class 0.000 claims abstract description 90
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 79
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 39
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000002367 halogens Chemical group 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 18
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 14
- 125000005042 acyloxymethyl group Chemical group 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 8
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims abstract description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 135
- 238000000034 method Methods 0.000 claims description 118
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 117
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 66
- 239000002253 acid Substances 0.000 claims description 56
- 125000002252 acyl group Chemical group 0.000 claims description 50
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 239000007858 starting material Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 16
- 125000006239 protecting group Chemical group 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical group [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 claims description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 12
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 125000005859 (C1-C6)alkanoyloxymethyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 5
- 239000008194 pharmaceutical composition Substances 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims 3
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 claims 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 239000003937 drug carrier Substances 0.000 claims 1
- 125000000842 isoxazolyl group Chemical group 0.000 claims 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 5
- 244000052616 bacterial pathogen Species 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 490
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 261
- 239000000243 solution Substances 0.000 description 244
- 239000000203 mixture Substances 0.000 description 214
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 210
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 167
- 238000002329 infrared spectrum Methods 0.000 description 163
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 157
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 153
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 125
- 238000005481 NMR spectroscopy Methods 0.000 description 123
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 120
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 116
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 108
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 101
- 239000011541 reaction mixture Substances 0.000 description 101
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 88
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 80
- 238000003756 stirring Methods 0.000 description 76
- 239000002904 solvent Substances 0.000 description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- 238000001816 cooling Methods 0.000 description 65
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 60
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 58
- 235000019341 magnesium sulphate Nutrition 0.000 description 58
- 239000010410 layer Substances 0.000 description 56
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 53
- 235000017557 sodium bicarbonate Nutrition 0.000 description 53
- 239000000284 extract Substances 0.000 description 50
- 229920006395 saturated elastomer Polymers 0.000 description 50
- 241000786363 Rhampholeon spectrum Species 0.000 description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 46
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 42
- 239000002244 precipitate Substances 0.000 description 41
- 239000000706 filtrate Substances 0.000 description 40
- 239000011780 sodium chloride Substances 0.000 description 40
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 35
- 239000000843 powder Substances 0.000 description 33
- 235000011054 acetic acid Nutrition 0.000 description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 27
- 239000013078 crystal Substances 0.000 description 27
- 239000003921 oil Substances 0.000 description 24
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 24
- 239000000725 suspension Substances 0.000 description 23
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 22
- 239000002198 insoluble material Substances 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 22
- 229910052783 alkali metal Inorganic materials 0.000 description 21
- 238000001228 spectrum Methods 0.000 description 21
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 20
- 230000007062 hydrolysis Effects 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 239000002585 base Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000012267 brine Substances 0.000 description 17
- 125000004521 1,3,4-thiadiazol-2-yl group Chemical group S1C(=NN=C1)* 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 16
- LWFWUJCJKPUZLV-UHFFFAOYSA-N n-trimethylsilylacetamide Chemical compound CC(=O)N[Si](C)(C)C LWFWUJCJKPUZLV-UHFFFAOYSA-N 0.000 description 16
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 14
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 14
- 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 description 14
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 14
- NYBWUHOMYZZKOR-UHFFFAOYSA-N tes-adt Chemical class C1=C2C(C#C[Si](CC)(CC)CC)=C(C=C3C(SC=C3)=C3)C3=C(C#C[Si](CC)(CC)CC)C2=CC2=C1SC=C2 NYBWUHOMYZZKOR-UHFFFAOYSA-N 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000008346 aqueous phase Substances 0.000 description 12
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 12
- 238000011282 treatment Methods 0.000 description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 11
- 235000019253 formic acid Nutrition 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000007522 mineralic acids Chemical class 0.000 description 11
- 150000007524 organic acids Chemical class 0.000 description 11
- 150000007530 organic bases Chemical class 0.000 description 11
- 241000699666 Mus <mouse, genus> Species 0.000 description 10
- 150000007529 inorganic bases Chemical class 0.000 description 10
- 239000002609 medium Substances 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 235000011181 potassium carbonates Nutrition 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 241000699670 Mus sp. Species 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 9
- POOAXOGRBVEUFA-UHFFFAOYSA-N n-(1,3-thiazol-2-yl)formamide Chemical compound O=CNC1=NC=CS1 POOAXOGRBVEUFA-UHFFFAOYSA-N 0.000 description 9
- 235000005985 organic acids Nutrition 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 8
- VGIJLQLDEHZKNU-UHFFFAOYSA-N 2-(3-hydroxyphenyl)-2-methoxyiminoacetic acid Chemical compound CON=C(C(O)=O)C1=CC=CC(O)=C1 VGIJLQLDEHZKNU-UHFFFAOYSA-N 0.000 description 7
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 7
- SIOVKLKJSOKLIF-UHFFFAOYSA-N bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)OC(C)=N[Si](C)(C)C SIOVKLKJSOKLIF-UHFFFAOYSA-N 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000012442 inert solvent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 7
- 235000017281 sodium acetate Nutrition 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- DDLWWOLZXHAVNY-PVQCJRHBSA-N (6R)-3-(carbamoyloxymethyl)-7-[[2-(3-hydroxyphenyl)-2-methoxyiminoacetyl]amino]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid Chemical compound CON=C(C(=O)NC1[C@@H]2N(C(=C(CS2)COC(N)=O)C(=O)O)C1=O)C1=CC(=CC=C1)O DDLWWOLZXHAVNY-PVQCJRHBSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical group CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 125000005270 trialkylamine group Chemical group 0.000 description 6
- RVBOFXPFJHCIBC-UHFFFAOYSA-N 2-(3-chloro-4-hydroxyphenyl)-2-methoxyiminoacetic acid Chemical compound CON=C(C(O)=O)C1=CC=C(O)C(Cl)=C1 RVBOFXPFJHCIBC-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 208000015181 infectious disease Diseases 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
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- 244000000010 microbial pathogen Species 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XHRRYUDVWPPWIP-UHFFFAOYSA-N pentyl carbonochloridate Chemical compound CCCCCOC(Cl)=O XHRRYUDVWPPWIP-UHFFFAOYSA-N 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 125000004495 thiazol-4-yl group Chemical group S1C=NC(=C1)* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 238000011200 topical administration Methods 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CRKADHVTAQCXRA-UHFFFAOYSA-K trisodium;phosphate;dihydrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O CRKADHVTAQCXRA-UHFFFAOYSA-K 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/38—Nitrogen atoms
- C07D277/44—Acylated amino or imino radicals
- C07D277/48—Acylated amino or imino radicals by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof, e.g. carbonylguanidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/587—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with aliphatic hydrocarbon radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms, said aliphatic radicals being substituted in the alpha-position to the ring by a hetero atom, e.g. with m >= 0, Z being a singly or a doubly bound hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cephalosporin Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB14916/76A GB1576625A (en) | 1976-04-12 | 1976-04-12 | Syn isomer 3,7 disubstituted 3 cephem 4 carboxylic acid compounds and processes for the preparation thereof |
GB2349076 | 1976-06-07 | ||
JP51125826A JPS5941995B2 (ja) | 1976-04-12 | 1976-10-19 | 3,7−ジ置換−3−セフエム−4−カルボン酸化合物およびその塩類およびそれらの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
HU177441B true HU177441B (en) | 1981-10-28 |
Family
ID=27257189
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
HU77FU348A HU177441B (en) | 1976-04-12 | 1977-02-28 | Process for preparing syn isomers of 3,7-disubstituted 3-cephem-4-carboxylic acid derivatives |
Country Status (13)
Country | Link |
---|---|
AR (2) | AR227864A1 (en, 2012) |
AT (1) | AT358728B (en, 2012) |
CA (1) | CA1337522C (en, 2012) |
CH (2) | CH638532A5 (en, 2012) |
DE (1) | DE2707565A1 (en, 2012) |
DK (1) | DK162391C (en, 2012) |
ES (7) | ES457191A1 (en, 2012) |
FR (1) | FR2348219A1 (en, 2012) |
HU (1) | HU177441B (en, 2012) |
IE (1) | IE45597B1 (en, 2012) |
MX (1) | MX4985E (en, 2012) |
NL (1) | NL191259C (en, 2012) |
SE (2) | SE443981B (en, 2012) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3192167A (en) * | 1962-09-20 | 1965-06-29 | Ogawa Abiko | Low pressure liquid vaporizer which is electrically heated |
BE878514A (fr) * | 1978-09-04 | 1980-02-29 | Fujisawa Pharmaceutical Co | Procede de preparation de composes d'acide 3-cephem-4-carboxylique a disubstitution en positions 3 et 7, nouveaux produits ainsi obtenus et leur utilisation pour leur activite antibacterienne |
DE2760484C2 (en, 2012) * | 1976-04-14 | 1992-12-03 | Takeda Chemical Industries, Ltd., Osaka, Jp | |
FR2381053A1 (fr) * | 1977-02-18 | 1978-09-15 | Roussel Uclaf | Nouvelles oximes derivees de l'acide 3-thiadiazolyl thiomethyl 7-aminothiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
FR2399418A1 (fr) * | 1977-03-14 | 1979-03-02 | Fujisawa Pharmaceutical Co | Procede de preparation d'acides iminoacetiques et nouveaux produits ainsi obtenus, utilises pour la synthese d'acides cepham- ou cephem-carboxyliques |
PH17188A (en) | 1977-03-14 | 1984-06-14 | Fujisawa Pharmaceutical Co | New cephem and cepham compounds and their pharmaceutical compositions and method of use |
SE439312B (sv) * | 1977-03-25 | 1985-06-10 | Roussel Uclaf | Sett att framstella nya oximderivat av 3-acetoximetyl-7-aminotiazolylacetamido cefalosporansyra |
DE2714880A1 (de) * | 1977-04-02 | 1978-10-26 | Hoechst Ag | Cephemderivate und verfahren zu ihrer herstellung |
JPS5498795A (en) * | 1978-01-13 | 1979-08-03 | Takeda Chem Ind Ltd | Cephalosporin derivative and its preparation |
FR2432521A1 (fr) * | 1978-03-31 | 1980-02-29 | Roussel Uclaf | Nouvelles oximes o-substituees derivees de l'acide 7-amino thiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
FR2553770B2 (fr) * | 1978-03-31 | 1986-03-14 | Roussel Uclaf | Nouveaux produits derives de l'acide 2(2-amino thiazol-4-yl) 2-alcoxy-imino acetique substitues sur l'oxime et leur procede de preparation |
FR2421907A1 (fr) * | 1978-04-07 | 1979-11-02 | Roussel Uclaf | Nouvelles cephalosporines derivees de l'acide 7-/2-(2-amino 4-thiazolyl)2-(carboxymethoxyimino/acetamido 3-substitue cephalosporanique, leur procede de preparation et leur application comme medicaments |
FR2438051A2 (fr) * | 1978-10-05 | 1980-04-30 | Roussel Uclaf | Nouvelles oximes derivees de l'acide 3-azidomethyl 7-amino thiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
MC1259A1 (fr) | 1978-05-30 | 1980-01-14 | Hoffmann La Roche | Derives acyles |
US4284631A (en) * | 1978-07-31 | 1981-08-18 | Fujisawa Pharmaceutical Co., Ltd. | 7-Substituted cephem compounds and pharmaceutical antibacterial compositions containing them |
FR2453161A1 (fr) * | 1978-08-31 | 1980-10-31 | Fujisawa Pharmaceutical Co | Procede de preparation de derives d'acide thiazolylacetique et nouveaux produits ainsi obtenus |
US4341775A (en) * | 1978-09-11 | 1982-07-27 | Fujisawa Pharmaceutical Co., Ltd. | Cephem compounds |
EP0010667B1 (en) * | 1978-10-17 | 1983-07-20 | Fujisawa Pharmaceutical Co., Ltd. | Cepham compounds, pharmaceutical compositions containing them and processes for the preparation thereof and of known cephem compounds |
DE2945248A1 (de) * | 1978-11-13 | 1980-05-22 | Fujisawa Pharmaceutical Co | Cephem-verbindungen, verfahren zu ihrer herstellung und sie enthaltende antibakterielle pharmazeutische mittel |
FR2448543A1 (fr) * | 1979-02-09 | 1980-09-05 | Roussel Uclaf | Nouvelles oximes o-substituees par un radical comportant un ammonium quaternaire et derivees de l'acide 7-amino thiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
FR2461713A1 (fr) * | 1979-07-19 | 1981-02-06 | Roussel Uclaf | Nouvelles alcoyloximes substituees derivees de l'acide 7-(2-amino 4-thiazolyl) acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
FR2462439A1 (fr) * | 1979-07-26 | 1981-02-13 | Roussel Uclaf | Nouveau procede de preparation de produits derives de l'acide 7-/(2-aryl) 2-hydroxyimino acetamido/cephalosporanique |
IL61458A0 (en) * | 1979-12-07 | 1980-12-31 | Erba Farmitalia | N-substituted thiazolyl derivatives of oximino-substituted cephalosporins, their preparation and pharmalceutical compositions containing them |
FR2506307A1 (fr) * | 1981-05-22 | 1982-11-26 | Roussel Uclaf | Nouveaux derives substitues de l'acide 2-(2-amino 4-thiazolyl) 2-hydroxyimino acetique et leur procede de preparation |
US4426528A (en) * | 1982-04-01 | 1984-01-17 | Eli Lilly And Company | Purification of syn-(2-aminothiazol-4-yl)methoxyimino)acetic acid |
FR2532936A1 (fr) * | 1982-09-13 | 1984-03-16 | Roussel Uclaf | Nouveaux derives de l'acide 2-amino-thiazolyl-4-yl acetique comportant une fonction oxime substituee et leur procede de preparation |
GB8324152D0 (en) * | 1983-09-09 | 1983-10-12 | Glaxo Group Ltd | Chemical process |
IT8448798A0 (it) * | 1983-09-12 | 1984-09-05 | Biochemie Gmbh | Procedimento per la preparazione di antibiotici del tipo cefalosporina |
GB2161476B (en) * | 1984-05-25 | 1988-01-27 | Toyama Chemical Co Ltd | 2-aminothiazolyl-2-methoxyimino acetamides and their use in preparing cephalosporins |
ATE110386T1 (de) * | 1986-04-14 | 1994-09-15 | Banyu Pharma Co Ltd | Cephalosporinderivate, verfahren zu ihrer herstellung und antibakterielle präparate. |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1399086A (en) * | 1971-05-14 | 1975-06-25 | Glaxo Lab Ltd | Cephalosporin compounds |
NZ176206A (en) * | 1973-12-25 | 1978-03-06 | Takeda Chemical Industries Ltd | Cephalosporins |
DK154939C (da) * | 1974-12-19 | 1989-06-12 | Takeda Chemical Industries Ltd | Analogifremgangsmaade til fremstilling af thiazolylacetamido-cephemforbindelser eller farmaceutisk acceptable salte eller estere deraf |
NO760358L (en, 2012) * | 1975-02-04 | 1976-08-05 | Fujisawa Pharmaceutical Co | |
FR2346014A1 (fr) * | 1976-01-23 | 1977-10-28 | Roussel Uclaf | Nouvelles oximes derivees de l'acide 7-amino thiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
DE2760123C2 (de) * | 1976-01-23 | 1986-04-30 | Roussel-Uclaf, Paris | 7-Aminothiazolyl-syn-oxyiminoacetamidocephalosporansäuren, ihre Herstellung und sie enthaltende pharmazeutische Zusammensetzungen |
SE440655B (sv) * | 1976-01-23 | 1985-08-12 | Roussel Uclaf | Sett att framstella nya oximderivat av 7-amino-tiazolyl-acetamido-cefalosporansyra |
FR2345153A1 (fr) * | 1976-03-25 | 1977-10-21 | Roussel Uclaf | Nouvelles alcoyloximes derivees de l'acide 7-amino thiazolyl acetamido cephalosporanique, leur procede de preparation et leur application comme medicaments |
DE2760484C2 (en, 2012) * | 1976-04-14 | 1992-12-03 | Takeda Chemical Industries, Ltd., Osaka, Jp |
-
1977
- 1977-02-21 DK DK075077A patent/DK162391C/da active
- 1977-02-22 SE SE7701964A patent/SE443981B/xx not_active IP Right Cessation
- 1977-02-22 DE DE19772707565 patent/DE2707565A1/de active Granted
- 1977-02-23 CA CA000272430A patent/CA1337522C/en not_active Expired - Lifetime
- 1977-02-25 CH CH244777A patent/CH638532A5/de not_active IP Right Cessation
- 1977-02-28 HU HU77FU348A patent/HU177441B/hu unknown
- 1977-03-01 IE IE440/77A patent/IE45597B1/en not_active IP Right Cessation
- 1977-03-02 AT AT138477A patent/AT358728B/de not_active IP Right Cessation
- 1977-03-10 FR FR7707173A patent/FR2348219A1/fr active Granted
- 1977-03-25 ES ES457191A patent/ES457191A1/es not_active Expired
- 1977-04-11 MX MX775624U patent/MX4985E/es unknown
- 1977-04-12 NL NL7703969A patent/NL191259C/xx not_active IP Right Cessation
- 1977-04-20 AR AR257178A patent/AR227864A1/es active
-
1978
- 1978-03-27 AR AR271541A patent/AR223143A1/es active
- 1978-04-12 ES ES468719A patent/ES468719A1/es not_active Expired
-
1979
- 1979-02-15 ES ES477741A patent/ES477741A1/es not_active Expired
- 1979-10-16 ES ES485064A patent/ES485064A1/es not_active Expired
- 1979-10-16 ES ES485061A patent/ES485061A1/es not_active Expired
- 1979-10-16 ES ES485063A patent/ES485063A1/es not_active Expired
- 1979-10-16 ES ES485062A patent/ES485062A1/es not_active Expired
-
1983
- 1983-07-26 CH CH409583A patent/CH643557A5/de not_active IP Right Cessation
- 1983-08-17 SE SE8304465A patent/SE457351B/sv not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ES468719A1 (es) | 1979-10-16 |
NL191259B (nl) | 1994-11-16 |
IE45597B1 (en) | 1982-10-06 |
ES485064A1 (es) | 1980-10-01 |
ES485063A1 (es) | 1980-06-16 |
AT358728B (de) | 1980-09-25 |
CA1337522C (en) | 1995-11-07 |
AR227864A1 (es) | 1982-12-30 |
DK75077A (da) | 1977-10-13 |
FR2348219B1 (en, 2012) | 1982-12-03 |
SE7701964L (sv) | 1977-10-13 |
ES485061A1 (es) | 1980-06-16 |
DK162391C (da) | 1992-03-09 |
ES477741A1 (es) | 1980-04-01 |
ES485062A1 (es) | 1980-06-16 |
ES457191A1 (es) | 1978-08-16 |
SE443981B (sv) | 1986-03-17 |
DE2707565C2 (en, 2012) | 1988-06-30 |
IE45597L (en) | 1977-10-12 |
DE2707565A1 (de) | 1978-02-23 |
SE8304465D0 (sv) | 1983-08-17 |
ATA138477A (de) | 1980-02-15 |
MX4985E (es) | 1983-01-31 |
CH643557A5 (en) | 1984-06-15 |
AR223143A1 (es) | 1981-07-31 |
NL7703969A (nl) | 1977-10-14 |
CH638532A5 (de) | 1983-09-30 |
FR2348219A1 (fr) | 1977-11-10 |
SE457351B (sv) | 1988-12-19 |
DK162391B (da) | 1991-10-21 |
NL191259C (nl) | 1995-04-18 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
HU90 | Patent valid on 900628 |