NO791413L - PROCEDURE FOR PREPARING 5- (2-ANILINOALKYLAMINO-1-HYDROXYALKYL) SALICYLAMIDES - Google Patents
PROCEDURE FOR PREPARING 5- (2-ANILINOALKYLAMINO-1-HYDROXYALKYL) SALICYLAMIDESInfo
- Publication number
- NO791413L NO791413L NO791413A NO791413A NO791413L NO 791413 L NO791413 L NO 791413L NO 791413 A NO791413 A NO 791413A NO 791413 A NO791413 A NO 791413A NO 791413 L NO791413 L NO 791413L
- Authority
- NO
- Norway
- Prior art keywords
- hydroxyethyl
- salicylamide
- formula
- methylanilino
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 27
- -1 trimethylene, tetramethylene Chemical group 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229960000581 salicylamide Drugs 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 239000004480 active ingredient Substances 0.000 claims description 9
- 125000002015 acyclic group Chemical group 0.000 claims description 9
- 125000006239 protecting group Chemical group 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000008194 pharmaceutical composition Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- YKAVVWFTRZKVQQ-UHFFFAOYSA-N 2-hydroxy-5-[1-hydroxy-2-[1-(n-methylanilino)propan-2-ylamino]ethyl]benzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CN(C)C1=CC=CC=C1 YKAVVWFTRZKVQQ-UHFFFAOYSA-N 0.000 claims description 4
- DMSYDLSFECSZPJ-UHFFFAOYSA-N 2-hydroxy-5-[1-hydroxy-2-[4-(n-methylanilino)butan-2-ylamino]ethyl]benzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CCN(C)C1=CC=CC=C1 DMSYDLSFECSZPJ-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005236 alkanoylamino group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- JCJIIRGLSFLORQ-UHFFFAOYSA-N 5-[2-[4-(4-fluoro-n-methylanilino)butan-2-ylamino]-1-hydroxyethyl]-2-hydroxybenzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CCN(C)C1=CC=C(F)C=C1 JCJIIRGLSFLORQ-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- 206010020772 Hypertension Diseases 0.000 claims description 3
- 241000124008 Mammalia Species 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 3
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims description 3
- 239000003937 drug carrier Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 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 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 claims description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 235000020357 syrup Nutrition 0.000 claims description 2
- 239000006188 syrup Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 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 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 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 claims description 2
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 239000012458 free base Substances 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims 1
- 208000024891 symptom Diseases 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- 239000012141 concentrate Substances 0.000 description 15
- 235000008504 concentrate Nutrition 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WOEISFSYHVAQTR-UHFFFAOYSA-N 5-(2-amino-1-hydroxyethyl)-2-hydroxybenzamide Chemical compound NCC(O)C1=CC=C(O)C(C(N)=O)=C1 WOEISFSYHVAQTR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 4
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UDSFWJDAWBZMIZ-UHFFFAOYSA-N 2-hydroxy-5-[1-hydroxy-2-[5-(n-methylanilino)pentan-2-ylamino]ethyl]benzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CCCN(C)C1=CC=CC=C1 UDSFWJDAWBZMIZ-UHFFFAOYSA-N 0.000 description 3
- LUHGJYJXVQZQDW-UHFFFAOYSA-N 5-[2-[4-(4-chloro-n-methylanilino)butan-2-ylamino]-1-hydroxyethyl]-2-hydroxybenzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CCN(C)C1=CC=C(Cl)C=C1 LUHGJYJXVQZQDW-UHFFFAOYSA-N 0.000 description 3
- XZLXKLMNJMALHM-UHFFFAOYSA-N 5-[2-[4-(n,4-dimethylanilino)butan-2-ylamino]-1-hydroxyethyl]-2-hydroxybenzamide Chemical compound C=1C=C(O)C(C(N)=O)=CC=1C(O)CNC(C)CCN(C)C1=CC=C(C)C=C1 XZLXKLMNJMALHM-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000008101 lactose Substances 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 125000005837 1,2-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([*:2])C1([H])[H] 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- COZRGYKMRBVBEK-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-5-[1-hydroxy-2-[4-(n-methylanilino)butan-2-ylamino]ethyl]benzamide Chemical compound C1=C(C(N)=O)C(OCCOCC)=CC=C1C(O)CNC(C)CCN(C)C1=CC=CC=C1 COZRGYKMRBVBEK-UHFFFAOYSA-N 0.000 description 1
- OFERIRWCHSOJJT-UHFFFAOYSA-N 2-(3-chloropropyl)-2-methyl-1,3-dioxolane Chemical compound ClCCCC1(C)OCCO1 OFERIRWCHSOJJT-UHFFFAOYSA-N 0.000 description 1
- DVYVBENBIMEAJZ-UHFFFAOYSA-N 2-(n-methylanilino)acetic acid Chemical compound OC(=O)CN(C)C1=CC=CC=C1 DVYVBENBIMEAJZ-UHFFFAOYSA-N 0.000 description 1
- WAYXSAURCFBBCW-OOCDHZDVSA-N 2-hydroxy-5-[1-hydroxy-2-[1-[(1r,2r)-2-[(n-methylanilino)methyl]cyclohexyl]ethylamino]ethyl]benzamide Chemical compound CC([C@H]1[C@@H](CCCC1)CN(C)C=1C=CC=CC=1)NCC(O)C1=CC=C(O)C(C(N)=O)=C1 WAYXSAURCFBBCW-OOCDHZDVSA-N 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229960003010 sodium sulfate Drugs 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- LMJSLTNSBFUCMU-UHFFFAOYSA-N trichlormethiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NC(C(Cl)Cl)NS2(=O)=O LMJSLTNSBFUCMU-UHFFFAOYSA-N 0.000 description 1
- 229960004813 trichlormethiazide Drugs 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008215 water for injection Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse angår nye 5-(2-anilinoalkyl-amino-l-hydroxyalkyl)-salicylamider med verdifulle farmakologiske egenskaper, i særdeleshet antihypertensiv aktivitet, fremgangs- The present invention relates to new 5-(2-anilinoalkyl-amino-1-hydroxyalkyl)-salicylamides with valuable pharmacological properties, in particular antihypertensive activity, progress-
måte for fremstilling av disse og farmasøytiske komposisjoner inneholdende disse. method for producing these and pharmaceutical compositions containing them.
Oppfinnelsen tilveiebringer således 5-(2-anilino-alkyl-amino-l-hydroxyalkyl)salicylamider av formelen The invention thus provides 5-(2-anilino-alkyl-amino-1-hydroxyalkyl)salicylamides of the formula
13 13
hvori R og R er uavhengige hydrogenatomer eller lavere alkylgrupper, wherein R and R are independent hydrogen atoms or lower alkyl groups,
2 2
R er et hydrogenatom eller en lavere alkyl-, lavere alkoxylavere-alkyl- eller hydrolavere alkylgruppe-, R is a hydrogen atom or a lower alkyl, lower alkyl lower alkyl or hydro lower alkyl group,
Alk er en acyklisk eller cyklisk alkylenbro inneholdende 2-10 carbonatomer, forutsatt at det er 2 - 6 carbonatomer som skiller nitrogenatomene som danner bro, Alk is an acyclic or cyclic alkylene bridge containing 2-10 carbon atoms, provided there are 2-6 carbon atoms separating the bridging nitrogen atoms,
Z er et hydrogenatom eller en lavere alkyl, lavere alkanoyl, Z is a hydrogen atom or a lower alkyl, lower alkanoyl,
lavere alkylsulfonyl, arylsulfonyl, laverealkoxylaverealkyl, 2,2,2-trifluorethyl eller benzylgruppe, lower alkylsulfonyl, arylsulfonyl, lower alkoxylower alkyl, 2,2,2-trifluoroethyl or benzyl group,
1 2 1 2
Y og Y er uavhengig hydrogen eller halogenatomer eller hydroxy, trifluormethyl, lavere alkyl, lavere alkoxy, nitro, amino, monolaverealkylamino, di-laverealkylamin, laverealkanoylamino, laverealkylsulfonylamino, arylsulfonylamino, N-laverealkyl-N-laverealkanoylamino eller N-lavérealkyl-N-laverealkylsulfinylaminogrupper, Y and Y are independently hydrogen or halogen atoms or hydroxy, trifluoromethyl, lower alkyl, lower alkoxy, nitro, amino, monolower alkylamino, di-lower alkylamine, lower alkanoylamino, lower alkylsulfonylamino, arylsulfonylamino, N-lower alkyl-N-lower alkanoylamino or N-lower alkyl-N-lower alkylsulfinylamino groups ,
og farmasøytisk akseptable syreaddisjonssalter derav. and pharmaceutically acceptable acid addition salts thereof.
De lavere alkylgrupper som angitt ovenfor inneholder 1-6 carbonatomer og eksemplifiseres ved methyl, ethyl, propyl, butyl, pentyl, hexyl og de tilsvarende forgrenede isomerer derav. De lavere alkoxygrupper inneholder likeledes 1-6 carbonatomer The lower alkyl groups indicated above contain 1-6 carbon atoms and are exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl and the corresponding branched isomers thereof. The lower alkoxy groups also contain 1-6 carbon atoms
og kan typisk være methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sek-butoxy og t-butoxy. and can typically be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and t-butoxy.
De lavere alkanoylgrupper inneholder 1-6 carbonatomer og eksemplifiseres ved formyl, acetyl, butyryl og valeryl. The lower alkanoyl groups contain 1-6 carbon atoms and are exemplified by formyl, acetyl, butyryl and valeryl.
1 2 1 2
Halogenatomene representert ved Y og Y innbefatter fluor, klor, brom og jod. The halogen atoms represented by Y and Y include fluorine, chlorine, bromine and iodine.
Alk-broene med 2-6 carbonatomer som skiller nitrogenatomene er representert ved acykliske grupper slik som ethylen, trimethylen, tetramethylen og pentamethylengrupper eventuelt sub-stituert med lavere alkylgrupper. Således er representative acykliske Alk-grupper ifølge oppfinnelsen ethylen, 1-methylethylen, trimethylen, 2-methylethylen, 1-methyltrimethylen, tetramethylen, 1-methyltetramethylen, 1,1-dimethyltrimethylen, 1,2-dimethyltrimethylen, 1-ethyltrimethylen, l-methyl-2-ethyltetramethylen,-pentamethylen og 1,l-dimethyl-3-methylpentamethylen. (Nummererin-gen av Alk-broen starter ved carbonatomet bundet til nitrogenatomet i ethanolaminresten i 5-stilling av salicylamiddelen i formel The alk bridges with 2-6 carbon atoms that separate the nitrogen atoms are represented by acyclic groups such as ethylene, trimethylene, tetramethylene and pentamethylene groups optionally substituted with lower alkyl groups. Thus, representative acyclic Alk groups according to the invention are ethylene, 1-methylethylene, trimethylene, 2-methylethylene, 1-methyltrimethylene, tetramethylene, 1-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 1-ethyltrimethylene, l-methyl -2-ethyltetramethylene, -pentamethylene and 1,1-dimethyl-3-methylpentamethylene. (The numbering of the Alk bridge starts at the carbon atom bound to the nitrogen atom in the ethanolamine residue in the 5-position of the salicyl agent in formula
I.) IN.)
En gruppe av foretrukne forbindelser med en acyklisk A group of preferred compounds with an acyclic
bro Alk kan representeres ved formelen: bro Alk can be represented by the formula:
hvori n er 1 - 4, og R<1>, R<2>, R<3>, z, Y<1>og Y<2>er som tidligere definert. En særlig foretrukket bro er av formelen: wherein n is 1 - 4, and R<1>, R<2>, R<3>, z, Y<1> and Y<2> are as previously defined. A particularly preferred bridge is of the formula:
dvs. n er 2 i formel II. i.e. n is 2 in formula II.
En gruppe av foretrukne forbindelser med en cyklisk bro Alk kan representeres ved formelen A group of preferred compounds with a cyclic bridge Alk can be represented by the formula
hvori n-j^ er 0 - 2, n2er 1 - 5, n-^+ n2er 2 - 6, n^og n4er uavhengig 0 eller 1, R, R og R er uavhengig hydrogenatomer eller lavere alkylgrupper, forutsatt at det totale antall carbonatomer i Alk-broen ikke overstiger ti, wherein n-j^ is 0 - 2, n2 is 1 - 5, n-^+ n2 is 2 - 6, n^ and n4 are independently 0 or 1, R, R and R are independently hydrogen atoms or lower alkyl groups, provided that the total number of carbon atoms in The Alk bridge does not exceed ten,
12 3 12 12 3 12
og R , R , R , Z, Y og Y er som tidligere definert. and R , R , R , Z, Y and Y are as previously defined.
Det er en direkte binding fra nitrogenatomet til carbonatomet i ringen når ng eller n^er lik'null, og en direkte binding mellom to ringcarbonatomer som bærer radikalene R og R^ når n^er lik null. There is a direct bond from the nitrogen atom to the carbon atom in the ring when ng or n^ is equal to zero, and a direct bond between two ring carbon atoms carrying the radicals R and R^ when n^ is equal to zero.
Cykliske Alk-broer kan ha lavere alkylsubstituenter og innbefatter 1,2-cyclopentylen, 1,3-cyclopentylen, 1,2-cyclohexylen, 1,3-cyclohexylen, 1,4-cyclohexylen, 1-methyl-l,4-cyclohexylen og 1,4-cycloheptylen, i deres trans- og cis-former. Cykliske Alk-broer som inneholder acykliske deler innbefatter de av føl-gende formler (i deres cis- og trans-former): Cyclic Alk bridges may have lower alkyl substituents and include 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-methyl-1,4-cyclohexylene and 1,4-cycloheptylene, in their trans and cis forms. Cyclic Alk bridges containing acyclic moieties include those of the following formulas (in their cis and trans forms):
I en foretrukket gruppe av forbindelser av formel I 2 3 1 er R og R hydrogenatomer og R er en methylgruppe eller spesielt 1 2 et hydrogenatom, Y er et hydrogenatom, Y er en methylgruppe eller et hydrogen- eller halogenatom, Z er et hydrogenatom eller en methyl- eller benzylgruppe og Alk er en trimethylen, tetramethylen eller 1,4-.cyclohexylengruppe (spesielt i trans-f ormen) eller en gruppe av formelen In a preferred group of compounds of formula I 2 3 1 R and R are hydrogen atoms and R is a methyl group or especially 1 2 a hydrogen atom, Y is a hydrogen atom, Y is a methyl group or a hydrogen or halogen atom, Z is a hydrogen atom or a methyl or benzyl group and Alk is a trimethylene, tetramethylene or 1,4-cyclohexylene group (especially in the trans form) or a group of the formula
hvori n er 1 - 4. where n is 1 - 4.
Spesielt foretrukneforbindelser ifølge oppfinnelsen er 5-{2-[3-(N-methylanilino)-2-propylamino]-1-hydroxyethyl}salicylamid, Particularly preferred compounds according to the invention are 5-{2-[3-(N-methylanilino)-2-propylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamid, 5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[5-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}salicylamid, 5-{2-[5-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(4,N-dimethylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(4,N-dimethylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-fluor-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, og 5-{2-[4-(4-fluoro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide, and
5-{2-[4-(4-klor-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid. 5-{2-[4-(4-chloro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide.
De farmasøytisk akseptable syreaddisjonssalter av forbindelsene av formel I kan avledes fra organiske og uorganiske syrer slik som svovelsyre, fosforsyre, saltsyre, hydrobromsyre, sulfamsyre, sitronsyre, melkesyre, oljesyre, ravsyre, vinsyre,0cinnaminsyre, eddiksyre, benzoesyre, gluconsyre, ascorbinsyre og beslektede syrer. The pharmaceutically acceptable acid addition salts of the compounds of formula I may be derived from organic and inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, sulfamic acid, citric acid, lactic acid, oleic acid, succinic acid, tartaric acid, cinnamic acid, acetic acid, benzoic acid, gluconic acid, ascorbic acid and related acids. .
Forbindelsene av formel I og deres farmasøytisk akseptable syreaddisjonssalter kan fremstilles for eksempel ved føl-gende metoder: The compounds of formula I and their pharmaceutically acceptable acid addition salts can be prepared, for example, by the following methods:
a) Reduksjon av en forbindelse av formel a) Reduction of a compound of formula
hvori X er et ocygenatom eller (H,OH), Alk, R og R<3>er som ovenfor definert, Pg er et hydrogenatom eller en reduktivt fjernbar wherein X is an oxygen atom or (H,OH), Alk, R and R<3> are as defined above, Pg is a hydrogen atom or a reductively removable
2a a 2 2a a 2
beskyttende gruppe, R og Z er respektivt R og Z som ovenfor definert eller en reduktivt f jernbar beskyttende gruppe, og Y"<*>"<a>2a 12 protecting group, R and Z are respectively R and Z as defined above or a reductively f ironable protecting group, and Y"<*>"<a>2a 12
og Y er Y og Y som ovenfor angitt, and Y is Y and Y as above,
eller en hydroxy eller en aminogruppe (innbefattet usubstituerte og mono-substituerte aminogrupper, men ikke innbefattet di-substituerte aminogrupper, tidligere definert for Y 1 og Y 2), bærende en reduktivt fjernbar beskyttende gruppe, or a hydroxy or an amino group (including unsubstituted and mono-substituted amino groups, but not including di-substituted amino groups, previously defined for Y 1 and Y 2 ), bearing a reductively removable protecting group,
forutsatt at når R 2a , Pg, Z a, Y la og Y 2a er gruppene R 2, H, Z, provided that when R 2a , Pg, Z a, Y la and Y 2a the groups R 2 , H, Z,
1 2 1 2
Y og Y , er X et oxygenatom, Y and Y , X is an oxygen atom,
i et egnet løsningsmiddel. in a suitable solvent.
Reduksjonen av gruppen CX når X er et oxygenatom til gruppen CHOH kan utføres med et utall reduksjonsmidler. Reduk-sjonsmidlet er fortrinnsvis et borhydrid, f.eks. lithiumborhydrid, kaliumborhydrid eller spesielt- natriumborhydrid. Reduksjonen utføres fortrinnsvis i en vann-blandbar alkohol som løsningsmid-del, f.eks. methanol, ethanol eller isopropanol. The reduction of the group CX when X is an oxygen atom to the group CHOH can be carried out with a number of reducing agents. The reducing agent is preferably a borohydride, e.g. lithium borohydride, potassium borohydride or especially sodium borohydride. The reduction is preferably carried out in a water-miscible alcohol as solvent, e.g. methanol, ethanol or isopropanol.
Gruppen CX kan også reduseres ved hjelp av hydrogen og en katalysator, f.eks. palladium, spesielt 5 - 10 % Pd-C, i nær vær av et organisk løsningsmiddel slik som en lavere alkanol, f.eks. methanol eller ethanol. The group CX can also be reduced using hydrogen and a catalyst, e.g. palladium, especially 5 - 10% Pd-C, in the presence of an organic solvent such as a lower alkanol, e.g. methanol or ethanol.
Det skal bemerkes at mange reduksjonsprosesser, spesielt de som anvender hydrogen og en katalysator, ikke er egnet for fremstilling av forbindelser hvori Y 1 og/eller Y 2 er en nitrogruppe. Envidere er prosesser som gjør bruk av hydrogen og en katalysator ikke egnet for fremstilling av forbindelser hvori Z er en benzylgruppe. It should be noted that many reduction processes, especially those using hydrogen and a catalyst, are not suitable for the preparation of compounds in which Y 1 and/or Y 2 is a nitro group. Furthermore, processes which make use of hydrogen and a catalyst are not suitable for the preparation of compounds in which Z is a benzyl group.
Reduktivt fjernbare beskyttende grupper som kan fore- Reductively removable protecting groups that can pre-
la 2a 2a let 2a 2a
ligge i Y eller Y eller kan være til stede som R , Pg eller Z innbefatter benzyl, benzhydryl, trityl og benzyloxycarbonyl. Disse grupper kan alle fjernes ved hjelp av hydrogen og en kata-lystor, fortrinnsvis som ovenfor beskrevet. lie in Y or Y or may be present as R , Pg or Z include benzyl, benzhydryl, trityl and benzyloxycarbonyl. These groups can all be removed using hydrogen and a catalyst, preferably as described above.
En særlig foretrukket utførelsesform av denne prosess omfatter reduksjonen av en forbindelse av formel A particularly preferred embodiment of this process comprises the reduction of a compound of formula
hvori R<1>,R<2a>, R<3>, Pg, Alk, X, Y"1" og Y<2>er som ovenfor definert, og Z° er gruppen Z definert ovenfor unntatt en benzylgruppe, wherein R<1>, R<2a>, R<3>, Pg, Alk, X, Y"1" and Y<2> are as defined above, and Z° is the group Z defined above except for a benzyl group,
2a 2 2a 2
forutsatt at når R<2>a og Pg er R og et hydrogenatom, er X et oxygenatom. Når X er et oxygenatom og R<2a>og/eller Pg er en reduktivt fjernbar beskyttende gruppe, kan denne utførelsesform utføres i et trinn ved hjelp av hydrogen og en katalysator, eller i to trinn ved hjelp av et borhydrid og deretter hydrogen og en katalysator, idet reaksjonsbetingelsene er som ovenfor definert. Når mer enn én reduktiv fjernbar gruppe er til stede, er alle slike grupper fortrinnsvis identiske, f.eks. alle er benzyl-grupper eller alle er benzyloxycarbonylgrupper. provided that when R<2>a and Pg are R and a hydrogen atom, X is an oxygen atom. When X is an oxygen atom and R<2a>and/or Pg is a reductively removable protecting group, this embodiment can be carried out in one step using hydrogen and a catalyst, or in two steps using a borohydride and then hydrogen and a catalyst, the reaction conditions being as defined above. When more than one reductive leaving group is present, all such groups are preferably identical, e.g. all are benzyl groups or all are benzyloxycarbonyl groups.
Forbindelsene av formel V eller VI kan fremstilles etter standard metoder. Eksempelvis kan forbindelser av formel The compounds of formula V or VI can be prepared by standard methods. For example, compounds of the formula
VI fremstilles ved en.kondensasjon av en forbindelse av formel med en forbindelse av formel VI is prepared by a condensation of a compound of formula with a compound of formula
hvori R"*",R<2a>,R<3>,Alk,Pg, Y"*", Y2 og Z*3 er som ovenfor definert og Hal er et klor- eller bromatom. Denne kondensasjon utføres i nærvær av en syreakseptor og et organisk løsningsmiddel. En organisk base, f.eks. pyridin eller triethylamin, kan tjene som in which R"*",R<2a>,R<3>,Alk,Pg, Y"*", Y2 and Z*3 are as defined above and Hal is a chlorine or bromine atom. This condensation is carried out in the presence of an acid acceptor and an organic solvent. An organic base, e.g. pyridine or triethylamine, can serve as
løsningsmiddel og syreakseptor. Hvis et nøytralt løsningsmiddel slik som et dialkylamid, f.eks. dimethylformamid eller alkohol anvendes, kan en uorganisk base slik som natrium eller kaliumcarbonat anvendes som syreakseptor. solvent and acid acceptor. If a neutral solvent such as a dialkylamide, e.g. dimethylformamide or alcohol is used, an inorganic base such as sodium or potassium carbonate can be used as acid acceptor.
I særdeleshet de etterfølgende forbindelser kan fremstilles ved denne prosess: 5-{2-[4-(N-methylanilino)-2-(2-methyl)-butylamino]-1-hydroxye ethyl}salicylamid, 5-{2-[trans-4-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl } salicylamid , sm.p. 159 - 161° C, In particular, the following compounds can be prepared by this process: 5-{2-[4-(N-methylanilino)-2-(2-methyl)-butylamino]-1-hydroxyethyl}salicylamide, 5-{2-[trans -4-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl } salicylamide , m.p. 159 - 161° C,
5-{2- [cis-4-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamid , 5-{2- [cis-4-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamide,
5-{2-[trans-4-(N,4-dimethylanilino)-1-cyclohexylamino]-1-hydroxyethyl } salicylamid , 5-{2-[trans-4-(N,4-dimethylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamide,
5-[2-(trans-4-anilino-l-cyclohexylamino)-1-hydroxyethyl]-salicylamid, 5-[2-(trans-4-anilino-1-cyclohexylamino)-1-hydroxyethyl]-salicylamide,
5-{2-[trans-3-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamid , 5-{2-[trans-3-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamide,
5-{2-[cis-3-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-3-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[trans-3-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl} salicylamid, 5-{2-[trans-3-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl} salicylamide,
5-{2-[cis-3-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl}-salicylamid,5-{2-[trans-3-(N,4-dimethylanilino)-1-cyclopentylami-no] -1-hydroxyethyl} sjjiicylamid, 5-{2-[cis-3-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl}-salicylamide, 5-{2-[trans-3-(N,4-dimethylanilino)-1-cyclopentylami- no] -1-hydroxyethyl} sylcylamide,
5-[2-(trans-3-anilino-l-cyclopentylamino)-1-hydroxyethyl]-salicylamid, 5-[2-(trans-3-anilino-1-cyclopentylamino)-1-hydroxyethyl]-salicylamide,
5-{2-[trans-3-(N-methylanilino)-1-cyclobutylamino]-1-hydroxyethyl } salicylamid , 5-{2-[trans-3-(N-methylanilino)-1-cyclobutylamino]-1-hydroxyethyl} salicylamide,
5-{2-[cis-3-(N-methylanilino)-1-cyclobutylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-3-(N-methylanilino)-1-cyclobutylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[trans-3-(N,4-dimethylanilino)-1-cyclobutylamino]-1-hydroxyethyl } salicylamid , 5-{2-[trans-3-(N,4-dimethylanilino)-1-cyclobutylamino]-1-hydroxyethyl} salicylamide,
5-[2-trans-3-anilino-l-cyclobutylamino)-1-hydroxyethyl]salicylamid , 5-[2-trans-3-anilino-1-cyclobutylamino)-1-hydroxyethyl]salicylamide,
5-{2-[trans-2-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl }salicylamid, 5-{2-[trans-2-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl }salicylamide,
5-{2-[cis-2-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-2-(N-methylanilino)-1-cyclopentylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[cis-4-(N-methylanilino)-1-cycloheptylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-4-(N-methylanilino)-1-cycloheptylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[trans-4-(N-methylanilino)-1-cycloheptylamino]-1-hydroxyethyl } salicylamid , 5-{2-[trans-4-(N-methylanilino)-1-cycloheptylamino]-1-hydroxyethyl} salicylamide,
5-{2-[trans-2-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl } salicylamid , 5-{2-[trans-2-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl} salicylamide,
5-{2-[cis-2-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-2-(N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[trans-2-(N-methylanilino)-1-methyl-l-r-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-2-(N-methylanilino)-1-methyl-1-r-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-2-(N-methylanilino)-1-methyl-l-r-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-2-(N-methylanilino)-1-methyl-1-r-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-4-(4-fluor-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-4-(4-fluoro-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(4-fluor-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-4-(4-fluoro-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-4-(4-trifluormethyl-N-methylanilino)-1-cyclohexyl-amino] -1-hydroxyethyl}salicylamid, 5-{2-[trans-4-(4-trifluoromethyl-N-methylanilino)-1-cyclohexyl-amino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(4-trifluormethyl-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-4-(4-trifluoromethyl-N-methylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-4-(N-acetylanilino)-1-cyclohexylamino]-1-hydroxyethyl }salicylamid, 5-{2-[trans-4-(N-acetylanilino)-1-cyclohexylamino]-1-hydroxyethyl }salicylamide,
5- {2- ["Cis-4- (N-acetylanilino) -1-cyclohexylamino] -1-hydroxyethyl }-salicylamid, 5-{2-[trans-4-(N-ethylanilino)-1-cyclohexylamino]-1-hydroxyethyl }salicylamid , 5- {2- ["Cis-4-(N-acetylanilino)-1-cyclohexylamino]-1-hydroxyethyl }-salicylamide, 5-{2-[trans-4-(N-ethylanilino)-1-cyclohexylamino]- 1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(N-ethylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[cis-4-(N-ethylanilino)-1-cyclohexylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[trans-4-(N-methansulfonylanilino)-1-cyclohexylamino)-1-hydroxyethyl}salicylamid, 5-{2-[trans-4-(N-methanesulfonyl anilino)-1-cyclohexylamino)-1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(N-methansulfonylanilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-4-(N-methanesulfonyl anilino)-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl}salicylamid. 5-{2-[cis-4-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl}salicylamide.
5-{2-[trans-4-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl)salicylamid, 5-{2-[trans-4-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl)salicylamide,
5-{2-[cis-3-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-3-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-3-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-3-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-2-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-2-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-2-(N-methylanilino)-methyl-l-cyclohexylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-2-(N-methylanilino)-methyl-1-cyclohexylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-3-(N-methylanilino)-methyl-l-cyclopentylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-3-(N-methylanilino)-methyl-1-cyclopentylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-3-(N-methylanilino)-methyl-l-cyclopentylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-3-(N-methylanilino)-methyl-1-cyclopentylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-2-(N-methylanilino)-methyl-l-cyclopentylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-2-(N-methylanilino)-methyl-1-cyclopentylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-2-(N-methylanilino)-methyl-l-cyclopentylamino]-1-hydroxyethyl)salicylamid, 5-{2-[trans-2-(N-methylanilino)-methyl-1-cyclopentylamino]-1-hydroxyethyl)salicylamide,
5-{2-[cis-3-(N-methylanilino)-methyl-l-cyclobutylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-3-(N-methylanilino)-methyl-1-cyclobutylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-3-(N-methylanilino)-methyl-l-cyclobutylamino]-1-hydroxyethyl}salicylamid, 5-{2-[trans-3-(N-methylanilino)-methyl-1-cyclobutylamino]-1-hydroxyethyl}salicylamide,
5-{2-[cis-4-(N-methylanilino)-methyl-l-cycloheptylamino]-1-hydroxyethyl}salicylamid, 5-{2-[cis-4-(N-methylanilino)-methyl-1-cycloheptylamino]-1-hydroxyethyl}salicylamide,
5-{2-[trans-4-(N-methylanilino)-methyl-l-cycloheptylamino(-1-hydroxyethyl}salicylamid, 5-{2-[trans-4-(N-methylanilino)-methyl-1-cycloheptylamino(-1-hydroxyethyl}salicylamide,
5-{2-[1-(cis-4-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[1-(cis-4-(N-methylanilino)methyl-1-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[l-trans-4-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[l-trans-4-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[l-cis-3-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[l-cis-3-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(trans-3-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[1-(trans-3-(N-methylanilino)methyl-1-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(cis-2-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[1-(cis-2-(N-methylanilino)methyl-1-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(trans-2-(N-methylanilino)methyl-l-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamid , 5-{2-[1-(trans-2-(N-methylanilino)methyl-1-cyclohexyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(cis-3-(N-methylanilino)methyl-l-cyclopentyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[1-(cis-3-(N-methylanilino)methyl-1-cyclopentyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(trans-3-(N-methylanilino)methyl-l-cyclopentyl)-ethylamino] -1-hydroxyethyl}salicylamid, 5-{2-[1-(trans-3-(N-methylanilino)methyl-1-cyclopentyl)-ethylamino]-1-hydroxyethyl}salicylamide,
5-{2- [1- (cis-2- (N-methylanilino)meth.yl-l-cyclopentyl) ethylamino] - 1-hydroxyethyl}salicylamid, 5-{2- [1- (cis-2-(N-methylanilino)meth.yl-1-cyclopentyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(trans-2-(N-methylanilino)methyl-l-cyclopentyl)-ethylamino (-1-hydroxyethyl}salicylamid, 5-{2-[1-(trans-2-(N-methylanilino)methyl-1-cyclopentyl)-ethylamino (-1-hydroxyethyl}salicylamide,
5-{2-[1-(cis-3-(N-methylanilino)methyl-l-cyclobutyl)ethylamino] - 1-hydroxyethyl}salicylamid, 5-{2-[1-(cis-3-(N-methylanilino)methyl-1-cyclobutyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2- [1-(trans-3-(N-methylanilino)methyl-l-cyclobutyl)ethylamino] -1-hydroxyethyl}salicylamid, 5-{2- [1-(trans-3-(N-methylanilino)methyl-1-cyclobutyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(cis-4-(N-methylanilino(methyl-l-cycloheptyl)ethylamino]-1-hydroxyethyl}salicylamid, 5-{2-[1-(cis-4-(N-methylanilino(methyl-1-cycloheptyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2-[1-(trans-4-(N-methylanilino)methyl-l-cycloheptyl)ethylamino ]-1-hydroxyethyl}salicylamid, 5-{2-[1-(trans-4-(N-methylanilino)methyl-1-cycloheptyl)ethylamino]-1-hydroxyethyl}salicylamide,
5-{2- [1- (cis-4- (N-methylanilino) -1-cyclohexyl).-ethylamino] -1-hydroxyethyl}salicylamid, 5-{2- [1- (cis-4-(N-methylanilino)-1-cyclohexyl).-ethylamino]-1-hydroxyethyl}salicylamide,
5- 2-[1-(trans-4-(N-methylanilino)-1-cyclohexyl)ethylamino]-1-hydroxyethyl salicylamid, 5- 2-[1-(trans-4-(N-methylanilino)-1-cyclohexyl)ethylamino]-1-hydroxyethyl salicylamide,
5- 2-[3-(N-methylanilino)-1-propylamino]-1-hydroxyethy11-salicylamid, sm.p. 149 - 150° C og 5- 2-[3-(N-methylanilino)-1-propylamino]-1-hydroxyethyl-11-salicylamide, m.p. 149 - 150° C and
5- 2-[4-(N-methylanilino)-butylamino]-1-hydroxyethyl salicylamid, sm.p. 156 - 158° C. 5- 2-[4-(N-methylanilino)-butylamino]-1-hydroxyethyl salicylamide, m.p. 156 - 158° C.
b) Forbindelser av formel IA: b) Compounds of formula IA:
12 3 12 12 3 12
hvori R , R , R , Y , Y og Z er som ovenfor definert og Alk<1>in which R , R , R , Y , Y and Z are as defined above and Alk<1>
H H
er en acyklisk eller cyklisk alkylenbro som ovenfor definert for Alk forutsatt at det angitte hydrogenatom i Alk' og nitrogenato-t is an acyclic or cyclic alkylene bridge as defined above for Alk provided that the indicated hydrogen atom in Alk' and nitrogen atom-t
H H
met i ethanolamindelen -CHOH.CHR"'" er bundet til samme carbonatom, met in the ethanolamine part -CHOH.CHR"'" is attached to the same carbon atom,
kan fremstilles ved reduktiv kondensasjon av en forbindelse av formel can be prepared by reductive condensation of a compound of formula
hvori Alk', Y 1 , Y 2 og Z er som ovenfor definert, med en forbindelse av formel hvori R<1>, R2 og R<3>er som ovenfor definert, i nærvær av et organisk løsningsmiddel, fortrinnsvis en lavere alkanol slik som methanol, ethanol eller propanol. Reduksjonen kan utføres ved hjelp av katalytisk hydrogenering (som beskrevet for prosess a)), eller lithium-thexyllimonyl-borhydrid eller 9-borbicyclo[3,3,1]-nonan, men fortrinnsvis ved hjelp av natriumborhydrid eller natriumcyanoborhydrid. Ved'en særlig foretrukket utførelsesform av denne prosess fremstilles en forbindelse av formel II ved reduktiv kondensasjon av en forbindelse av formel med en forbindelse av formel X, hvori R<1>, R<2>, R<3>, Y1, Y2, Z og n er som definert for formel II. Denne prosess er foretrukket fremfor fremgangsmåte a) for fremstilling av forbindelser av formel II; i særdeleshet kan følgende forbindelser fremstilles ved denne prosess: 5-{2-[5- (4-fluor-N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamid, sm.p. (kvart-hydrat), 160 - 162° C, wherein Alk', Y 1 , Y 2 and Z are as defined above, with a compound of formula wherein R<1>, R2 and R<3> are as defined above, in the presence of an organic solvent, preferably a lower alkanol such such as methanol, ethanol or propanol. The reduction can be carried out by means of catalytic hydrogenation (as described for process a)), or lithium-thexyllimonylborohydride or 9-borbicyclo[3,3,1]-nonane, but preferably by means of sodium borohydride or sodium cyanoborohydride. In a particularly preferred embodiment of this process, a compound of formula II is prepared by reductive condensation of a compound of formula with a compound of formula X, wherein R<1>, R<2>, R<3>, Y1, Y2, Z and n are as defined for formula II. This process is preferred over process a) for preparing compounds of formula II; in particular, the following compounds can be prepared by this process: 5-{2-[5-(4-fluoro-N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamide, m.p. (quarter-hydrate), 160 - 162° C,
5-{2-[5-(N-benzylanilino)-2-pentylamino]-1-hydroxyethyl}salicylramid, sm.p. (hemihydrat) 144 146° C, 5-{2-[5-(N-benzylanilino)-2-pentylamino]-1-hydroxyethyl}salicylamide, m.p. (hemihydrate) 144 146° C,
5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamid, sm.p. 150 - 152° C, 5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide, m.p. 150 - 152° C,
5-{2-[4-(4,N-dimethylanilino)-2-butylamino]-1-hydroxyethyl}-salycylamid, sm.p. 123 - 126° C, 5-{2-[4-(4,N-dimethylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide, m.p. 123 - 126° C,
5-{2-[4-(4-klor-N-methylanilino)-2-butylamino]-1-hydroxy-ethyl}-salicylamid, sm.p. 127° C, 5-{2-[4-(4-chloro-N-methylanilino)-2-butylamino]-1-hydroxy-ethyl}-salicylamide, m.p. 127°C,
5-{2-[4-(3-klor-4-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamid, 5-{2-[4-(3-chloro-4-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(4-fluor-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(4-fluoro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-hydroxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl } salicylamid , 5-{2-[4-(4-hydroxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl} salicylamide,
5-{2-[4-(4-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamid, 5-{2-[4-(4-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(4-nitro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(4-nitro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-amino-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(4-amino-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-acetamido-N-methylanilino)-2-butylamino]-1-hydroxyethyl } salicylamid , 5-{2-[4-(4-acetamido-N-methylanilino)-2-butylamino]-1-hydroxyethyl} salicylamide,
5-{2-[4-(4-methylamino-N-methylanilino)-2-butylamino]-1-hydroxyethyl } salicylamid , 5-{2-[4-(4-methylamino-N-methylanilino)-2-butylamino]-1-hydroxyethyl} salicylamide,
5-{2-[4-(4-methansulfonamido-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamid, 5-{2-[4-(4-methanesulfonamido-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(4-trifluormethyl-N-methylanilino)-2-butylamino]-1-hydroxyethy1}salicylamid, 5-{2-[4-(4-trifluoromethyl-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(3-trifluormethyl-N-methylanilino)-2-butylamino]-1-hydroxyethy1}salicylamid, 5-{2-[4-(3-trifluoromethyl-N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
5-{2-[4-(3-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamid, 5-{2-[4-(3-methoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamide,
5-{2-[4-(3-hydroxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamid, 5-{2-[4-(2,N-dimethylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(3-hydroxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamide, 5-{2-[4-(2,N-dimethylanilino)-2-butylamino]- 1-hydroxyethyl}-salicylamide,
5-{2-[4-(2-klor-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(2-chloro-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-ethoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(4-ethoxy-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(4-isopropyl-N-methylanilino)-2-butylamino]-1-hydroxyethyl } salicylamid 5-{2-[4-(4-isopropyl-N-methylanilino)-2-butylamino]-1-hydroxyethyl } salicylamide
5-{2-[4-(N-methylanilino)-2-butylamino]-l-hydroxy-2-methylethyl}-salicylamid, 5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxy-2-methylethyl}-salicylamide,
5-[2-(4-anilino-2-butylamino)-1-hydroxyethyl]salicylamid, 5-{2-[4-(N-methansulfonylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamid, 5-[2-(4-anilino-2-butylamino)-1-hydroxyethyl]salicylamide, 5-{2-[4-(N-methanesulfonylanilino)-2-butylamino]-1-hydroxyethyl}-salicylamide,
5-{2-[4-(N-acetylanilino)-2-butylamino]-l-hydroxyethyll-salicylamid, 5-{2-[4-(N-acetylanilino)-2-butylamino]-1-hydroxyethyl-salicylamide,
5-{2-[4-(N-(2,2,2-trifluorethyl)anilino)-2-butylamino]-1-hydroxyethyl }salicylamid, 5-{2-[4-(N-(2,2,2-trifluoroethyl)anilino)-2-butylamino]-1-hydroxyethyl }salicylamide,
5-{2-14-(N-ethylanilino)-2-butylamino]-1-hydroxyethylIsalicylamid, 5-{2-[3-(N-methylanilino)-2-propylamino]-1-hydroxyethyl}-salicylamid, sm.p. 143 - 145° C, 5-{2-14-(N-ethylanilino)-2-butylamino]-1-hydroxyethylIsalicylamide, 5-{2-[3-(N-methylanilino)-2-propylamino]-1-hydroxyethyl}-salicylamide, sm. p. 143 - 145° C,
5-{2-[3-(N,4-dimethylanilino)-2-propylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[3-(N,4-dimethylanilino)-2-propylamino]-1-hydroxyethyl}-salicylamide,
5-[2-(3-anilino-2-propylamino)-1-hydroxyethyl]salicylamid, 5-{2-[5-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamid, sm.p. 155 - 157° C, 5-[2-(3-anilino-2-propylamino)-1-hydroxyethyl]salicylamide, 5-{2-[5-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamide, m.p. . 155 - 157° C,
5-{2-[5-(N,4-diméthylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[5-(N,4-dimethylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamide,
5-[2-(5-anilino-2-pentylamino)-1-hydroxyethyl]-salicylamid, sm.p. 138 - 140° C, 5-[2-(5-anilino-2-pentylamino)-1-hydroxyethyl]-salicylamide, m.p. 138 - 140° C,
5-{2-[6-(N-methylanilino)-2-hexylamino]-1-hydroxyethyl }salicyl-' amid, sm.p. 15 7 - 160° C, 5-{2-[6-(N-methylanilino)-2-hexylamino]-1-hydroxyethyl }salicyl-' amide, m.p. 15 7 - 160° C,
5-{2-[6-(N,4-dimethylanilino)-2-hexylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[6-(N,4-dimethylanilino)-2-hexylamino]-1-hydroxyethyl}-salicylamide,
5- [2-(6-anilino-2-hexylamino)-1-hydroxyethyl]salicylamid, 5-{2-[4-(N-methylanilino)-2-(3-methy1)butylamino]-1-hydroxyethyl }salicylamid, 5- [2-(6-anilino-2-hexylamino)-1-hydroxyethyl]salicylamide, 5-{2-[4-(N-methylanilino)-2-(3-methyl1)butylamino]-1-hydroxyethyl }salicylamide ,
5-{2-[4-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamid, 5-{2-[4-(N-methylanilino)-2-pentylamino]-1-hydroxyethyl}-salicylamide,
5- {2-[3-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamid, 5- {2-[3-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}salicylamide,
2-methoxy-5- {2-[4-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-benzamid, 2-methoxy-5- {2-[4-N-methylanilino)-2-butylamino]-1-hydroxyethyl}-benzamide,
2-(2-ethoxy)ethoxy-5- {2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }benzamid, 2-(2-ethoxy)ethoxy-5- {2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }benzamide,
2-(2-hydroxy)ethoxy-5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }benzamid, 2-(2-hydroxy)ethoxy-5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }benzamide,
5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}-N-methyl-salicylamid, og 5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}-N-methyl-salicylamide, and
5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}N-ethyl-salicylamid.. 5-{2-[4-(N-methylanilino)-2-butylamino]-1-hydroxyethyl}N-ethyl-salicylamide..
Forbindelsene av formel I kan isoleres fra de ovenfor angitte prosesser som de fri baser eller som deres farmasøytisk akseptable syreaddisjonssalter. The compounds of formula I can be isolated from the above processes as the free bases or as their pharmaceutically acceptable acid addition salts.
Forbindelsene ifølge oppfinnelsen utviser en eller flere asymmetriske carbonatomer og fremstilles ved de ovenfor angitte fremgangsmåter som stereoisomere blandinger. Forbindelsene kan anvendes som slike blandinger eller separeres i deres enantiomere og diastereoisomere rene former under anvendelse av vanlige metoder for separering av slike blandinger, slik som fraksjonert krystallisering og kromatografi, f.eks. på silicagel. I tillegg kan en ønsket diastereoisomer erholdes ved syntese under anvendelse av rene chirale forbindelser. The compounds according to the invention exhibit one or more asymmetric carbon atoms and are produced by the above-mentioned methods as stereoisomeric mixtures. The compounds can be used as such mixtures or separated in their enantiomeric and diastereoisomeric pure forms using conventional methods for separating such mixtures, such as fractional crystallization and chromatography, e.g. on silica gel. In addition, a desired diastereoisomer can be obtained by synthesis using pure chiral compounds.
De etterfølgende' eksempler illustrerer oppfinnelsen. Enkelte av de anilino-alkanoner som anvendes som utgangsmateria-ler i eksemplene ble fremstilt ifølge Craig et al., J.Org. Chem. 29 , 410 (1964) . The following examples illustrate the invention. Some of the anilino-alkanones used as starting materials in the examples were prepared according to Craig et al., J.Org. Chem. 29, 410 (1964).
Eksempel 1 Example 1
5-{ 2-[ 4-( N- methylanilino)- 2- butylamino]- 1- hydroxyethyl} salicylamid 5-{ 2-[ 4-( N- methylanilino)- 2- butylamino]- 1- hydroxyethyl} salicylamide
Tilsett til en løsning av 3,92 g (20 mmol) 5-(2-amino-1-hydroxyethyl)-salicylamid og 3,54 g (20 mmol) 4-(N-methylanilino) -2-butanon i 100 ml ethanol, 1,26 g (20 mmol) natriumcyanoborhydrid. Omrør i 16 timer, konsentrer og del blandingen mellom ethylacetat og IN natriumbicarbonatløsning. Tørk og konsentrer det organiske lag. Omkrystalliser residuet fra methanol under dannelse av et hvitt fast materiale med sm.p. 150 - 152° C. Add to a solution of 3.92 g (20 mmol) 5-(2-amino-1-hydroxyethyl)-salicylamide and 3.54 g (20 mmol) 4-(N-methylanilino)-2-butanone in 100 ml ethanol , 1.26 g (20 mmol) of sodium cyanoborohydride. Stir for 16 hours, concentrate and partition the mixture between ethyl acetate and IN sodium bicarbonate solution. Dry and concentrate the organic layer. Recrystallize the residue from methanol to form a white solid of m.p. 150 - 152° C.
Eksempel 2 Example 2
5-{ 2-[ 3-( N- methylanilino)- 2- propylamino]- 1- hydroxyethyl} salicylamid 5-{ 2-[ 3-( N- methylanilino)- 2- propylamino]- 1- hydroxyethyl} salicylamide
Tilsett til en løsning av 20 mmol 5-(2-amino-l-hydroxyethyl)-salicylamid og 3,26 g (20 mmol) N-methylanilino-acetat i 100 ml methanol, 2,51 g (40 mmol) natriumcyanoborhydrid. Omrør i 16 timer, konsentrer og del blandingen mellom ethylacetat og IN natriumbicarbonatløsning. Tørk og konsentrer det organiske lag. Oppløs det resulterende skum i kloroform og vask med vann. Filtrer fra det faste materiale som dannes og omkrystalliser dette fra ethylacetat under' dannelse av et hvitt fast materiale med sm. p. 143 - 145° C. To a solution of 20 mmol of 5-(2-amino-1-hydroxyethyl)-salicylamide and 3.26 g (20 mmol) of N-methylanilino-acetate in 100 ml of methanol, add 2.51 g (40 mmol) of sodium cyanoborohydride. Stir for 16 hours, concentrate and partition the mixture between ethyl acetate and IN sodium bicarbonate solution. Dry and concentrate the organic layer. Dissolve the resulting foam in chloroform and wash with water. Filter from the solid material that forms and recrystallize this from ethyl acetate to give a white solid with sm. b. 143 - 145° C.
Eksempel 3 Example 3
5-{ 2-[ 5-( N- methylanilino)- 2- pentylamino]- 1- hydroxyethyl}-salicylamid 5-{ 2-[ 5-( N- methylanilino)- 2- pentylamino]- 1- hydroxyethyl}- salicylamide
(a) 5-( N- methylanilino)- 2- pentanon (a) 5-(N-methylanilino)-2-pentanone
Tilsett til 49,4 g (0,30 mol) 5-klor-2-pentanon-ethylen-ketal og 64,2 g (0,60 mol) N-methylanilin i 100 ml toluen, 27,7 g (0,33 mol) natriumbicarbonat og 2,0 g kaliumjodid. Kok under tilbakeløpskjøling med en vannseparator over natten. La blandingen avkjøles, filtrer og konsentrer. Destiller ved 50°C/0,1 mm for å fjerne N-methylanilin. Omrør restvæsken med 175 ml IN saltsyre i 2 timer. Nøytraliser med natriumbicarbonat og ekstraher med ether. Tørk, konsentrer og destiller for å oppsamle en frak-sjon med k.p. 103 - 110° C/0,1 mm. Add to 49.4 g (0.30 mol) 5-chloro-2-pentanone-ethylene ketal and 64.2 g (0.60 mol) N-methylaniline in 100 ml toluene, 27.7 g (0.33 mol) of sodium bicarbonate and 2.0 g of potassium iodide. Boil under reflux with a water separator overnight. Allow the mixture to cool, filter and concentrate. Distill at 50°C/0.1 mm to remove N-methylaniline. Stir the residual liquid with 175 ml IN hydrochloric acid for 2 hours. Neutralize with sodium bicarbonate and extract with ether. Dry, concentrate and distill to collect a fraction with b.p. 103 - 110° C/0.1 mm.
b) 5-{ 2-[ 5-( N- methylanilino)- 2- pentylamino]- 1- hydroxyethyl } salicylamid b) 5-{ 2-[ 5-( N- methylanilino)- 2- pentylamino]- 1- hydroxyethyl } salicylamide
Kombiner det ovenfor angitte keton (4,3 g, 21 mmol) Combine the above ketone (4.3 g, 21 mmol)
med 20 mmol 5-(2-amino-l-hydroxyethyl)salicylamid og 2,0 g 10 %-ig Pd/C i 200 ml methanol. Hydrogener ved 4,2 kg cm i 2 timer. Fiitrer fra katalysatoren, konsentrer og del residuet mellom ethylacetat og IN natriumbicarbonatløsning. Det organiske lag avsettes som et fast materiale. Filtrer fra og omkrystalliser .dette fra methanol under dannelse av et hvitt fast materiale med sm.p. 155 - 157° C. with 20 mmol of 5-(2-amino-1-hydroxyethyl)salicylamide and 2.0 g of 10% Pd/C in 200 ml of methanol. Hydrogenate at 4.2 kg cm for 2 hours. Filter from the catalyst, concentrate and partition the residue between ethyl acetate and 1N sodium bicarbonate solution. The organic layer is deposited as a solid material. Filter off and recrystallize this from methanol to form a white solid with m.p. 155 - 157° C.
Eksempel 4 Example 4
5-{ 2- [ 4- ( 4- klor- N- methylanilino)- 2- butylamino]- 1- hydroxyethyl}-salicylamid 5-{ 2- [ 4-( 4- chloro- N- methylanilino)- 2- butylamino]- 1- hydroxyethyl}- salicylamide
Tilsett til en løsning av 20 mmol 5-(2-amino-l-hydroxy-. ethyl)-salicylamid og 4,22 g (20 mmol) 4-(4-klor-N-methylanilino)-2-butanon (sm.p. 60 - 61° C) i 100 ml methanol, 2,52 g (40 mmol) natriumcyanoborhydrid. Omrør 1 6 dager, konsentrer og del blandingen mellom ethylacetat og IN natriumbicarbonatløsning. Vask det organiske lag med IN saltsyre. Nøytraliser den vandige del med natriumbicarbonat og ekstraher med ethylacetat. Tørk, konsentrer og omkrystalliser residuet fra ethylacetat-hexan under dannelse av et hvitt fast materiale mes sm.p. 127 - 129° C. Add to a solution of 20 mmol of 5-(2-amino-1-hydroxy-.ethyl)-salicylamide and 4.22 g (20 mmol) of 4-(4-chloro-N-methylanilino)-2-butanone (sm. p. 60 - 61° C) in 100 ml methanol, 2.52 g (40 mmol) sodium cyanoborohydride. Stir 1 6 days, concentrate and partition the mixture between ethyl acetate and IN sodium bicarbonate solution. Wash the organic layer with IN hydrochloric acid. Neutralize the aqueous portion with sodium bicarbonate and extract with ethyl acetate. Dry, concentrate and recrystallize the residue from ethyl acetate-hexane to form a white solid m.p. 127 - 129° C.
Eksempel 5 Example 5
5-{ 2-[ 4-( 4, N- dimethylanilino)- 2- butylamino]- 1- hydroxyethyl}-salicylamid 5-{ 2-[ 4-( 4, N-dimethylanilino)- 2- butylamino]- 1- hydroxyethyl}-salicylamide
Tilsett til en løsning av 20 mmol 5-(2-amino-l-hydroxyethyl)-salicylamid og 5,7 g (30 mmol) 4-(N,4-dimethylanilino)-2-butanon (k.p. 93 - 96°C/0,1 mm) i 150 ml methanol, 1,9 g (30 mmol) natriumcyanoborhydrid. Konsentrer etter 20 timer og del blandingen mellom ethylacetat og IN natriumbicarbonatløsning. Tørk og konsentrer. Varm skummet med ethylacetat under dannelse av et hvitt fast materiale med sm.p. 123 - 126° C. Add to a solution of 20 mmol of 5-(2-amino-1-hydroxyethyl)-salicylamide and 5.7 g (30 mmol) of 4-(N,4-dimethylanilino)-2-butanone (b.p. 93 - 96°C/ 0.1 mm) in 150 ml methanol, 1.9 g (30 mmol) sodium cyanoborohydride. Concentrate after 20 hours and partition the mixture between ethyl acetate and IN sodium bicarbonate solution. Dry and concentrate. Heat the foam with ethyl acetate to form a white solid of m.p. 123 - 126° C.
Eksempel 6 Example 6
5-{ 2-[ 6-( N- methylanilino)- 2- hexylamino]- 1- hydroxyethyl}-salicylamid 5-{ 2-[ 6-( N- methylanilino)- 2- hexylamino]- 1- hydroxyethyl}-salicylamide
(a) 2- benzyloxy- 5-{ 2-[ N- benzyl- 6-( N- methylanilino)- 2-hexylamino]- 1- hydroxyethylIbenzamid (a) 2-benzyloxy-5-{2-[N-benzyl-6-(N-methylanilino)-2-hexylamino]-1-hydroxyethylIbenzamide
Tilsett til N-(5-benzylaminohexyl)-N-methylanilin (3,06 g = 10 mmol) og 3,48 g (10 mmol) 2-benzyloxy-5-bromacetylbenzamid i 35 ml dimethylformamid, 2,70 g (20 mmol) kaliumcarbonat. Om-rør i 20 timer og hell over 150 ml vann. La gummien avsettes, dekanter og oppløs gummien i ether. Ekstraher med IN saltsyre og nøytraliser deretter med natriumbicarbonat og ekstraher med ethylacetat. Tørk og konsentrer og oppløs oljen i 50 ml ethanol. Tilsett 0,3 g (8 mmol) natriumborhydrid, omrør i 20 timer, og konsentrer. Oppdel residuet mellom ethylacetat og IN natriumbicarbonat. Tørk det organiske lag og konsentrer under dannelse av et gult skum. Add to N-(5-benzylaminohexyl)-N-methylaniline (3.06 g = 10 mmol) and 3.48 g (10 mmol) of 2-benzyloxy-5-bromoacetylbenzamide in 35 mL of dimethylformamide, 2.70 g (20 mmol ) potassium carbonate. Stir for 20 hours and pour over 150 ml of water. Allow the gum to settle, decant and dissolve the gum in ether. Extract with IN hydrochloric acid and then neutralize with sodium bicarbonate and extract with ethyl acetate. Dry and concentrate and dissolve the oil in 50 ml of ethanol. Add 0.3 g (8 mmol) sodium borohydride, stir for 20 hours, and concentrate. Partition the residue between ethyl acetate and IN sodium bicarbonate. Dry the organic layer and concentrate to form a yellow foam.
(b) 5-{ 2-[ 6-( N- methylanilino)- 2- hexylamino]- 1- hydroxyethyl}-salicylamid (b) 5-{ 2-[ 6-( N- methylanilino)- 2- hexylamino]- 1- hydroxyethyl } salicylamide
Tilsett det ovenfor angitte amin til 250 ml ethanol Add the above amine to 250 ml of ethanol
_2 inneholdende 1,0 g 5 % Pd/C. Hydrogener ved 4,2 kg cm i 20 timer, filtrer og konsentrer. Omkrystalliser det klebrige faste materiale, fra methanol under dannelse av et hvitt fast materiale med sm.p. 157 - 160° C. _2 containing 1.0 g 5% Pd/C. Hydrogenate at 4.2 kg cm for 20 hours, filter and concentrate. Recrystallize the sticky solid from methanol to give a white solid, m.p. 157 - 160° C.
Forbindelsene ifølge oppfinnelsen er anvendbare ved behandling av cardiovasculære forstyrrelser og i særdeleshet ved behandling av hypertensjon i pattedyr. De administreres fortrinnsvis oralt men kan også administreres ved injeksjon. Laboratorietester indikerer at den effektive dose (ED^q) ved oral administrering for en forbindelse ifølge oppfinnelsen typisk vil ligge innen området 0,05 til 10 mg/kg kroppsvekt. The compounds according to the invention are useful in the treatment of cardiovascular disorders and in particular in the treatment of hypertension in mammals. They are preferably administered orally but can also be administered by injection. Laboratory tests indicate that the effective dose (ED^q) upon oral administration for a compound according to the invention will typically lie within the range of 0.05 to 10 mg/kg body weight.
Oppfinnelsen tilveiebringer således farmasøytiske komposisjoner inneholdende som aktiv bestanddel én eller flere forbindelser av formel I eller farmasøytisk akseptable syreaddisjonssalter derav, sammen med en farmasøytisk bærer eller eksipient. Komposisjonene er fortrinnsvis i form av enhetsdoser, f.eks. tabletter, kapsler eller injiserbare preparater i ampuller. Komposisjonene kan også foreligge i form av siruper, eliksirer eller suspensjoner. Den nødvendige daglige dose kan administreres i en enkel eller oppdelt dose. Den nøyaktige dose som skal administreres vil selvsagt være avhengig av forskjellige faktorer slik som den bestemte forbindelse som anvendes, alder og vekt på ..patte-dyret og den individuelle respons. Enhetsdoser inneholder fortrinnsvis fra 2 til 500 mg, helst fra 25 til 250 mg aktiv bestanddel av formel I (eller farmasøytisk akseptabelt syreaddisjonssalt derav). The invention thus provides pharmaceutical compositions containing as active ingredient one or more compounds of formula I or pharmaceutically acceptable acid addition salts thereof, together with a pharmaceutical carrier or excipient. The compositions are preferably in the form of unit doses, e.g. tablets, capsules or injectable preparations in ampoules. The compositions can also be in the form of syrups, elixirs or suspensions. The required daily dose can be administered in a single or divided dose. The exact dose to be administered will of course depend on various factors such as the particular compound used, the age and weight of the mammal and the individual response. Unit doses preferably contain from 2 to 500 mg, more preferably from 25 to 250 mg of active ingredient of formula I (or pharmaceutically acceptable acid addition salt thereof).
Typiske farmasøytiske akseptable bærere for bruk i for-muleringene som ovenfor beskrevet eksemplifiseres ved: sukker slik som lactose, sucrose, mannitol og sorbitol, stivelse slik som maisstivelse, tapioca-stivelse og potetstivelse, cellulose og derivater slik som natriumcarboxymethylcellulose, ethylcellulose og methylcellulose, kalciumfosfater slik som dikalciumfosfat og trikalciumfosfat, natriumsulfat, kalciumsulfat, polyvinylpyrroli-don, polyvinylalkohol, stearinsyre, jordalkalimetallstearater slik som magnesiumstearat og kalciumstearat, vegetabilske oljer slik som peanøttolje, bomullsfrøolje, sesamolje, olivenolje og maisolje, ikke-inoniske, kationiske og anioniske overflateaktive midler, ethylenglycolpolyme-rer, (3-cyclodextr in , f ettalkoholer , hydrolyserte cerealmaterialer og andre ikke-toksiske forenlige fyllstoffer, bindemidler, oppløsnende midler og smøremidler som vanligvis anvendes i farmasøytiske formuleringer. Typical pharmaceutically acceptable carriers for use in the formulations as described above are exemplified by: sugars such as lactose, sucrose, mannitol and sorbitol, starches such as corn starch, tapioca starch and potato starch, cellulose and derivatives such as sodium carboxymethylcellulose, ethylcellulose and methylcellulose, calcium phosphates such as dicalcium phosphate and tricalcium phosphate, sodium sulfate, calcium sulfate, polyvinylpyrrolidone, polyvinyl alcohol, stearic acid, alkaline earth metal stearates such as magnesium stearate and calcium stearate, vegetable oils such as peanut oil, cottonseed oil, sesame oil, olive oil, and corn oil, nonionic, cationic, and anionic surfactants, ethylene glycol polymers -rer, (3-cyclodextrin, fatty alcohols, hydrolysed cereal materials and other non-toxic compatible fillers, binders, solubilizers and lubricants that are commonly used in pharmaceutical formulations.
Ved behandling av visse pasienter med forbindelsene ifølge oppfinnelsen, kan det væreønskelig å innbefatte andre farmasøytiske aktive bestanddeler i samme komposisjon. Ved behandling av for eksempel pasienter for hvilke salt og vannreten-sjon er et problem, kan effektive mengder av et diureticum, for eksempel hydroklorthiazid eller triklormethiazid innbefattes. When treating certain patients with the compounds according to the invention, it may be desirable to include other pharmaceutical active ingredients in the same composition. When treating, for example, patients for whom salt and water retention are a problem, effective amounts of a diuretic, for example hydrochlorothiazide or trichloromethiazide, can be included.
Farmasøytiske formuleringer Pharmaceutical formulations
I de etterfølgende eksempler er den aktive bestanddel fortrinnsvis 5-{2-[5-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamid eller et farmasøytisk akseptabelt syreaddisjonssalt derav, men en ekvivalent mengde av en annen forbindelse (eller mer enn én forbindelse) av formel I, spesielt en forbindelse som angitt heri, kan anvendes i stedet: In the following examples, the active ingredient is preferably 5-{2-[5-(N-methylanilino)-2-butylamino]-1-hydroxyethyl }salicylamide or a pharmaceutically acceptable acid addition salt thereof, but an equivalent amount of another compound (or more than one compound) of formula I, in particular a compound as indicated herein, may be used instead:
Fremstillingsprosedyre: Manufacturing Procedure:
Oppløs p-hydroxybenzoat i en del av vann for injeksjon ved 60 - 70° C og avkjøl løsningen til 25 - 35° C. Tilsett og oppløs alle de andre eksipienter og den aktive bestanddel. Bring løsningen til et sluttvolum, filtrer den gjennom en steriliseren- de membran og fyll den i sterile beholdere. Dissolve p-hydroxybenzoate in a portion of water for injection at 60 - 70° C and cool the solution to 25 - 35° C. Add and dissolve all the other excipients and the active ingredient. Bring the solution to a final volume, filter it through a sterilizer- de membrane and fill it in sterile containers.
Orale formuleringer: Oral formulations:
a) Kapsler: a) Capsules:
Fremstillingsprosedyre: Manufacturing Procedure:
Bland den aktive bestanddel, lactose og maisstivelse inntil det oppnås en jevn blanding, og bland deretter magnesiumstearat i det resulterende pulver. Innkapsl blandingen i egnede todelte harde gelatinkapsler. b) Tabletter Mix the active ingredient, lactose and corn starch until a smooth mixture is obtained, then mix magnesium stearate into the resulting powder. Encapsulate the mixture in suitable two-piece hard gelatin capsules. b) Tablets
Fremstillingsprosedyre Manufacturing procedure
Bland den aktive bestanddel med lactosen inntil det oppnås en jevn blanding. Bland den mindre mengde av maisstivelsen med vann og tilsett den resulterende maisstivelsepasta, bland deretter inntil det oppnås en jevn fuktet masse. Tilsett den gjenværende del av maisstivelsen til den resulterende fuktige masse og bland inntil jevne granuler erholdes. Sikt granulene gjennom en egnet målemaskin under anvendelse av en 19,05 mm's rustfri stålsikt. Tørk de malte granuler i en egnet tørkeovn inntil den ønskede fuktighetsirinhold oppnås. Mal de tørkede granuler gjennom en egnet målemaskin under anvendelse av en 16 mesh rustfri stålsikt. Bland i magnesiumstearatet og press den resulterende blanding til tabletter med ønsket form, tykkelse hardhet og oppløsning. Mix the active ingredient with the lactose until a smooth mixture is obtained. Mix the smaller amount of the cornstarch with water and add the resulting cornstarch paste, then mix until a smooth moistened mass is obtained. Add the remaining part of the cornstarch to the resulting moist mass and mix until smooth granules are obtained. Sieve the granules through a suitable measuring machine using a 19.05 mm stainless steel sieve. Dry the ground granules in a suitable drying oven until the desired moisture content is achieved. Grind the dried granules through a suitable measuring machine using a 16 mesh stainless steel sieve. Mix in the magnesium stearate and press the resulting mixture into tablets of the desired shape, thickness, hardness and dissolution.
Claims (36)
Priority Applications (1)
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NO791413A NO791413L (en) | 1979-04-27 | 1979-04-27 | PROCEDURE FOR PREPARING 5- (2-ANILINOALKYLAMINO-1-HYDROXYALKYL) SALICYLAMIDES |
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NO791413A NO791413L (en) | 1979-04-27 | 1979-04-27 | PROCEDURE FOR PREPARING 5- (2-ANILINOALKYLAMINO-1-HYDROXYALKYL) SALICYLAMIDES |
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NO791413A NO791413L (en) | 1979-04-27 | 1979-04-27 | PROCEDURE FOR PREPARING 5- (2-ANILINOALKYLAMINO-1-HYDROXYALKYL) SALICYLAMIDES |
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