NO127606B - - Google Patents
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- Publication number
- NO127606B NO127606B NO04375/69A NO437569A NO127606B NO 127606 B NO127606 B NO 127606B NO 04375/69 A NO04375/69 A NO 04375/69A NO 437569 A NO437569 A NO 437569A NO 127606 B NO127606 B NO 127606B
- Authority
- NO
- Norway
- Prior art keywords
- nicotinic acid
- picolinic
- hydrazine
- picolinoyl
- general formula
- Prior art date
Links
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 17
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- -1 picolinoyl Chemical group 0.000 claims description 14
- 150000002429 hydrazines Chemical class 0.000 claims description 13
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- KFUSANSHCADHNJ-UHFFFAOYSA-N pyridine-3-carbohydrazide Chemical class NNC(=O)C1=CC=CN=C1 KFUSANSHCADHNJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000001968 nicotinic acid Nutrition 0.000 claims description 7
- 229960003512 nicotinic acid Drugs 0.000 claims description 7
- 239000011664 nicotinic acid Substances 0.000 claims description 7
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 7
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 5
- 229940081066 picolinic acid Drugs 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- BAQLNPIEFOYKNB-UHFFFAOYSA-N pyridine-2-carbohydrazide Chemical compound NNC(=O)C1=CC=CC=N1 BAQLNPIEFOYKNB-UHFFFAOYSA-N 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 150000007857 hydrazones Chemical class 0.000 claims description 4
- NHOWLEZFTHYCTP-UHFFFAOYSA-N benzylhydrazine Chemical compound NNCC1=CC=CC=C1 NHOWLEZFTHYCTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims 4
- 150000002576 ketones Chemical class 0.000 claims 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- MAUBFEHMBSQXMM-UHFFFAOYSA-N n'-benzylpyridine-2-carbohydrazide Chemical compound C=1C=CC=NC=1C(=O)NNCC1=CC=CC=C1 MAUBFEHMBSQXMM-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000003672 ureas Chemical class 0.000 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 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 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 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VKHPPPQEBGYWOR-UHFFFAOYSA-N n-(benzylideneamino)pyridine-2-carboxamide Chemical compound C=1C=CC=NC=1C(=O)NN=CC1=CC=CC=C1 VKHPPPQEBGYWOR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- DBNWBEGCONIRGQ-UHFFFAOYSA-N 1,1-diphenylpropan-2-one Chemical compound C=1C=CC=CC=1C(C(=O)C)C1=CC=CC=C1 DBNWBEGCONIRGQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NOXKUHSBIXPZBJ-UHFFFAOYSA-N 1-(4-methylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C)C=C1 NOXKUHSBIXPZBJ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- YEFQQYQCZGBYTP-UHFFFAOYSA-N C(=O)(O)C(O)C(O)C(=O)O.N1=C(C=CC=C1)C(=O)NNCC1=CC=CC=C1 Chemical compound C(=O)(O)C(O)C(O)C(=O)O.N1=C(C=CC=C1)C(=O)NNCC1=CC=CC=C1 YEFQQYQCZGBYTP-UHFFFAOYSA-N 0.000 description 1
- ZXVUSJARFUEZOH-UHFFFAOYSA-N C(C1=CN=CC=C1)(=O)NNCC1=CC=CC=C1 Chemical compound C(C1=CN=CC=C1)(=O)NNCC1=CC=CC=C1 ZXVUSJARFUEZOH-UHFFFAOYSA-N 0.000 description 1
- LKMLUIBOCXKADF-UHFFFAOYSA-N Cl.N1=C(C=CC=C1)C(=O)NNCC1=CC=CC=C1 Chemical compound Cl.N1=C(C=CC=C1)C(=O)NNCC1=CC=CC=C1 LKMLUIBOCXKADF-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 102000010909 Monoamine Oxidase Human genes 0.000 description 1
- 108010062431 Monoamine oxidase Proteins 0.000 description 1
- DUXDFHSXGBULKE-UHFFFAOYSA-N N'-benzylpyridine-2-carbohydrazide hydrobromide Chemical compound Br.N1=C(C=CC=C1)C(=O)NNCC1=CC=CC=C1 DUXDFHSXGBULKE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001729 carbonyl hydrates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- FQYYIPZPELSLDK-UHFFFAOYSA-N ethyl pyridine-2-carboxylate Chemical compound CCOC(=O)C1=CC=CC=N1 FQYYIPZPELSLDK-UHFFFAOYSA-N 0.000 description 1
- PDMBZSKSHXBRSW-UHFFFAOYSA-N hydrazine pyridine-3-carboxylic acid Chemical compound NN.OC(=O)C1=CC=CN=C1 PDMBZSKSHXBRSW-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940098895 maleic acid Drugs 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- LYWOLLFRTPZXFK-UHFFFAOYSA-N n-(benzhydrylideneamino)pyridine-3-carboxamide Chemical compound C=1C=CN=CC=1C(=O)NN=C(C=1C=CC=CC=1)C1=CC=CC=C1 LYWOLLFRTPZXFK-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/022—Melting the material to be shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C17/00—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces
- B05C17/005—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces for discharging material from a reservoir or container located in or on the hand tool through an outlet orifice by pressure without using surface contacting members like pads or brushes
- B05C17/00523—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces for discharging material from a reservoir or container located in or on the hand tool through an outlet orifice by pressure without using surface contacting members like pads or brushes provided with means to heat the material
- B05C17/00526—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces for discharging material from a reservoir or container located in or on the hand tool through an outlet orifice by pressure without using surface contacting members like pads or brushes provided with means to heat the material the material being supplied to the apparatus in a solid state, e.g. rod, and melted before application
- B05C17/0053—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces for discharging material from a reservoir or container located in or on the hand tool through an outlet orifice by pressure without using surface contacting members like pads or brushes provided with means to heat the material the material being supplied to the apparatus in a solid state, e.g. rod, and melted before application the driving means for the material being manual, mechanical or electrical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0225—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work characterised by flow controlling means, e.g. valves, located proximate the outlet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C7/00—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work
- B05C7/04—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work the liquid or other fluent material flowing or being moved through the work; the work being filled with liquid or other fluent material and emptied
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Coating Apparatus (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Pyridine Compounds (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
Fremgangsmåte for fremstilling av pikolinoyl- og nikotinoyl-hydrazinderivater. Process for the preparation of picolinoyl and nicotinoyl hydrazine derivatives.
Foreliggende oppfinnelse angår fremstillingen av heterocykliske hydrazinderivater og salter av disse forbindelser og er karakterisert ved at man fremstiller en forbindelse med den generelle formel: i hvilken Ri betyr pikolinoyl- eller nikotin-oylresten, og R-; en aralkylrest, såvel som deres salter, enten ved kondensasjon av pikolin- eller nikotinsyre med et substituert hydrazin med den generelle formel II: The present invention relates to the preparation of heterocyclic hydrazine derivatives and salts of these compounds and is characterized by the preparation of a compound with the general formula: in which Ri means the picolinoyl or nicotinoyl residue, and R-; an aralkyl residue, as well as their salts, either by condensation of picolinic or nicotinic acid with a substituted hydrazine of the general formula II:
i hvilken R2 har den forannevnte betyd7 ning, i nærvær av et karbodiimid og eventuelt overføring i et salt eller etter i og for seg kjente metoder. in which R2 has the aforementioned meaning, in the presence of a carbodiimide and possibly transfer in a salt or according to methods known per se.
Den forannevnte formel anvendte rest R2 vedrører i det vesentlige mono- og di-arylsubstituerte alkylrester, som f. eks. benzyl, tolylisopropyl, fenylisopropyl, dife-nylmetyl osv. The residue R2 used in the aforementioned formula essentially relates to mono- and di-aryl substituted alkyl residues, which e.g. benzyl, tolylisopropyl, phenylisopropyl, diphenylmethyl, etc.
På den ene side angår foreliggende On the one hand, the present concerns
oppfinnelse en ny fremgangsmåte for fremstilling av heterocykliske hydrazinderivater. Etter denne nye fremgangsmåte kondenseres pikolin- eller nikotinsyre med et aralkylsubstituert hydrazin i nærvær av et karbodiimid. For omsetningen kan syrene eller deres salter direkte anvendes. En omdannelse i de re-aksjonsdyktigere estere, halogenider, an^ hydrider etc. er overflødig. De som konden-sasjonsmirUer anvendte N,N'-disubstituerte karbodiimider kan f. eks. fremstilles ved behandling av disubstituerte urinstoffderi- invention a new process for the production of heterocyclic hydrazine derivatives. According to this new method, picolinic or nicotinic acid is condensed with an aralkyl-substituted hydrazine in the presence of a carbodiimide. For the turnover, the acids or their salts can be directly used. A conversion into the more reactive esters, halides, an^ hydrides etc. is superfluous. The N,N'-disubstituted carbodiimides used as condensation mirrors can e.g. produced by treating disubstituted urea derivatives
vater med p-toluolsulfoklorid i pyridin. Ved reaksjonen etter oppfinnelsen tilbakevin-nes de tilsvarende urinstoffderivater. Ved water with p-toluene sulfochloride in pyridine. In the reaction according to the invention, the corresponding urea derivatives are recovered. By
anvendelse av egnete substituerte karbodiimider f. eks. N,N'-dicykloheksyl-karbodiimid, får man som biprodukter urinstoffderivater, som lett kan skilles fra reak-sjonsproduktet. Reaksjonen kan f. eks. use of suitable substituted carbodiimides, e.g. N,N'-dicyclohexylcarbodiimide, urea derivatives are obtained as by-products, which can be easily separated from the reaction product. The reaction can e.g.
gjennomføres ved en temperatur mellom 0 carried out at a temperature between 0
og 50°, fortrinnsvis ved romtemperatur eller svakt forhøyet temperatur. Det er hen-siktsmessig å anvende et oppløsningsmid-del. Det kan anvendes såvel et organisk oppløsningsmiddel som f. eks. metylenklorid, kloroform, dioksan, tetrahydrofuran, and 50°, preferably at room temperature or slightly elevated temperature. It is expedient to use a solvent. An organic solvent such as e.g. methylene chloride, chloroform, dioxane, tetrahydrofuran,
dimetylformamid eller acetonitril, som og-så vann. dimethylformamide or acetonitrile, as well as water.
På den annen side vedrører foreliggende oppfinnelse fremstillingen av heterocykliske hydrazinderivater etter i og for seg kjente metoder. Uttrykket «kjente metoder» skal forstås som metoder som finnes i den tilgjengelige kjemiske litteratur. Så-ledes kan f. eks. reaksjonsdyktige nikotin-henholdsvis pikolinsyrederivater som f.eks. lavere alkylestere, halogenider eller amider av disse syrer omsettes med et aralkylsubstituert hydrazin. On the other hand, the present invention relates to the preparation of heterocyclic hydrazine derivatives according to methods known per se. The term "known methods" is to be understood as methods found in the available chemical literature. In this way, e.g. reactive nicotine-respectively picolinic acid derivatives such as e.g. lower alkyl esters, halides or amides of these acids are reacted with an aralkyl-substituted hydrazine.
Man kan også omsette nikotinsyre — henholdsvis pikolinsyrehydrazider med en karbonylforbindelse og hydrere de erholdte hydrazoner av karbonylforbindelsen samtidig eller etterpå. Hydreringen foretas hen-siktsmessig i nærvær av katalysatorer som f. eks. platinoksyd, palladiumkull osv., fortrinnsvis i et inert oppløsningsmiddel. Iføl-ge en variant av sistnevnte reaksjon kan man tilsette det dannede hydrazin med en grignardforbindelse og hydrolysere addi-sjonsproduktet. One can also react nicotinic acid — respectively picolinic acid hydrazides with a carbonyl compound and hydrate the obtained hydrazones of the carbonyl compound at the same time or afterwards. The hydrogenation is suitably carried out in the presence of catalysts such as e.g. platinum oxide, palladium charcoal, etc., preferably in an inert solvent. According to a variant of the latter reaction, the formed hydrazine can be added with a Grignard compound and the addition product hydrolysed.
Etter fremgangsmåten kan f. eks. føl-gende derivater utvinnes: 1 -nikotinoyl-2 -benzyl-hy drazin 1 -nikotinoyl-2 - (2 -f enyl-isopropyl) - hydrazin l-nikotinoyl-2-difenylmetyl-hydrazin l-pikolinoyl-2-benzyl-hydrazin l-pikolinoyl-2- (2-f enyl-isopropyl) - hydrazin l-pikolinoyl-2-difenylmetyl- hydrazin According to the procedure, e.g. the following derivatives are recovered: 1-nicotinoyl-2-benzylhydrazine 1-nicotinoyl-2-(2-phenyl-isopropyl)- hydrazine l-nicotinoyl-2-diphenylmethyl-hydrazine l-picolinoyl-2-benzyl-hydrazine l-picolinoyl-2-(2-phenyl-isopropyl)- hydrazine l-picolinoyl-2-diphenylmethyl- hydrazine
De heterocykliske hydrazinderivater som erholdes etter oppfinnelsen danner veldefinerte salter, såvel med anorganiske som med organiske syrer, f. eks. med halo-genvannstoffsyrer, som klorvannstoffsyre, bromvannstoffsyre, jodvannstoffsyre, med andre mineralsyrer, som svovelsyre, fosforsyre, salpetersyre, og med organiske syrer, som vinsyre, sitronsyre, kamfersulfosyre, etansulfosyre, salicylsyre, askorbinsyre, maleinsyre, mandelsyre osv. Foretrukne salter er hydrohalogenider, særlig hydro-klorider. Syreaddisjonssaltene fremstilles fortrinnsvis i et inert oppløsningsmiddel ved behandling av hydrazinderivatet med et overskudd av den tilsvarende syre. The heterocyclic hydrazine derivatives obtained according to the invention form well-defined salts, both with inorganic and organic acids, e.g. with hydrohalic acids, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, with other mineral acids, such as sulfuric acid, phosphoric acid, nitric acid, and with organic acids, such as tartaric acid, citric acid, camphorsulfonic acid, ethanesulfonic acid, salicylic acid, ascorbic acid, maleic acid, mandelic acid, etc. Preferred salts are hydrohalides , especially hydrochlorides. The acid addition salts are preferably prepared in an inert solvent by treating the hydrazine derivative with an excess of the corresponding acid.
Produktene etter oppfinnelsen og deres salter hemmer monoaminoksydase. Enkelte representanter utmerker seg ved deres ut-pregede antidepressive virksomhet og vir-ker ved Kachexia vektøkende. De er en verdifull tilvekst til legemidlene. The products according to the invention and their salts inhibit monoamine oxidase. Certain representatives are distinguished by their pronounced anti-depressant activity and cause weight gain in Kachexia. They are a valuable addition to the medicines.
Eksempel 1. Example 1.
14 g nikotinsyrehydrazid og 14 g p-me-tylfenylaceton kokes i 4 timer i bensol under tilbakeløp. Etter kjøling skilles det utkrystalliserte l-nikotinoyl-2-[2-(p-metyl-fenyl)-isopropyliden]-hydrazin fra og omkrystalliseres fra bensol. s.p. 108—110°. 5 g av det slik erholdte hydrazinderivat løses opp i 180 cm3 alkohol og hydreres under tilsetning av 0,2 g platinoksyd og ved et trykk på ca. 35 atmosfærer inntil opp-tagelse av den beregnede mengde hydrogen. Katalysatoren filtreres derpå, og filtratet inndampes til tørrhet. Resten omkrystalliseres fra metanol, hvorved rent 1-nikotinoyl-2 [ 2 - (p-metylf enyl) -isopropyl] -hydrazin med s.p. 146° erholdes. 14 g of nicotinic acid hydrazide and 14 g of p-methylphenylacetone are boiled for 4 hours in benzol under reflux. After cooling, the crystallized 1-nicotinoyl-2-[2-(p-methyl-phenyl)-isopropylidene]-hydrazine is separated and recrystallized from benzene. s.p. 108-110°. 5 g of the hydrazine derivative thus obtained is dissolved in 180 cm3 of alcohol and hydrated while adding 0.2 g of platinum oxide and at a pressure of approx. 35 atmospheres until absorption of the calculated amount of hydrogen. The catalyst is then filtered, and the filtrate is evaporated to dryness. The residue is recrystallized from methanol, whereby pure 1-nicotinoyl-2 [2-(p-methylphenyl)-isopropyl]-hydrazine with m.p. 146° is obtained.
Eksempel 2. Example 2.
14 g nikotinsyrehydrazin og 30 g fe-nylaceton oppvarmes 15 timer i 200 cm<3>14 g of nicotinic acid hydrazine and 30 g of phenylacetone are heated for 15 hours at 200 cm<3>
bensol under tilbakeløp. Etter kjøling skilles det utkrystalliserte l-nikotinoyl-2-(2-fenylisopropyliden) -hydrazin fra. S.p. 123— 124°. benzol under reflux. After cooling, the crystallized 1-nicotinoyl-2-(2-phenylisopropylidene)-hydrazine is separated. S. p. 123— 124°.
24 g av dette hydrazinderivat oppløses i 200 cm:! alkohol og hydreres under tilsetning av 0,2 g platinoksyd og ved et trykk på ca. 35 atmosfærer inntil oppta-gelse av den beregnede mengde hydrogen. Katalysatoren filtreres fra, filtratet konsentreres til en viskøs olje, og sistnevnte 24 g of this hydrazine derivative are dissolved in 200 cm:! alcohol and hydrated while adding 0.2 g of platinum oxide and at a pressure of approx. 35 atmospheres until the calculated amount of hydrogen is taken up. The catalyst is filtered off, the filtrate is concentrated to a viscous oil, and the latter
løses igjen i 60 cm3 alkohol. Den erholdte dissolve again in 60 cm3 of alcohol. It obtained
oppløsning tilsettes alkoholisk saltsyre inntil en tydelig sur reaksjon overfor kongo-rødt-papir og fortynnes med omtrent det samme volum aceton. I kulden skiller 1-nikotinoyl-2 - (2 -f enylisopropyl) -hydrazin seg langsomt fra, som etter omkrystallisa-sjon fra alkohol/aceton smelter ved 220°. solution, alcoholic hydrochloric acid is added until a distinctly acidic reaction to Congo red paper and diluted with approximately the same volume of acetone. In the cold, 1-nicotinoyl-2-(2-phenylisopropyl)-hydrazine separates slowly, which after recrystallization from alcohol/acetone melts at 220°.
Eksempel 3. Example 3.
14 g nikotinsyrehydrazid og 20 g benzo-fenon oppvarmes i 20 timer i 200 cm<3> xylen under tilbakeløp. Etter kjøling konsentreres den filtrerte reaksjonsblanding til en viskøs olje, løses i alkohol og fortynnes med petroleter. Ved henstand av den erholdte opp-løsning skilles 1-nikotinoyl-2-dif enylmety-len-hydrazin med smeltepunkt 97—99° seg fra. 10 g av dette hydrazinderivat løses i 180 cm<3> alkohol og hydreres under tilsetning av 0,2 g platinoksyd ved et trykk på ca. 35 atmosfærer ved 40° inntil opptagel-sen av den beregnede mengde hydrogen. Katalysatoren filtreres derpå av, og filtratet dampes inn til tørrhet. Etter omkrystallisering fra bensol smelter det erholdte 1-nikotinoyl-2-difenyl-metyl-hydrazin ved 113—115°. 14 g of nicotinic acid hydrazide and 20 g of benzo-phenone are heated for 20 hours in 200 cm<3> xylene under reflux. After cooling, the filtered reaction mixture is concentrated to a viscous oil, dissolved in alcohol and diluted with petroleum ether. When the resulting solution is allowed to stand, 1-nicotinoyl-2-diphenylmethylenehydrazine with a melting point of 97-99° is separated. 10 g of this hydrazine derivative are dissolved in 180 cm<3> of alcohol and hydrated while adding 0.2 g of platinum oxide at a pressure of approx. 35 atmospheres at 40° until the absorption of the calculated amount of hydrogen. The catalyst is then filtered off, and the filtrate is evaporated to dryness. After recrystallization from benzene, the 1-nicotinoyl-2-diphenyl-methyl-hydrazine obtained melts at 113-115°.
Eksempel 4. Example 4.
14 g nikotinsyrehydrazid og 22 g 1,1-difenyl-aceton oppvarmes i 400 cm<3> bensol og 1 cm<3> eddiksyre i 7 timer under tilbake-løp.Etter kjøling skiller l-nikotinoyl-2-(2,2-difenylisopropyliden)-hydrazin seg av, som etter omkrystallisering fra alkohol smelter ved 182°. 10 g av dette hydrazinderivat oppløses i 180 cm<3> alkohol og hydreres ved 30—40° under tilsetning av 0,2 g platinoksyd ved et trykk på ca. 25—35 atmosfærer inntil opp-tagelse av den beregnede mengde hydrogen. Katalysatoren filtreres av, og filtratet dampes inn. Resten omkrystalliseres fra alkohol. 14 g of nicotinic acid hydrazide and 22 g of 1,1-diphenyl-acetone are heated in 400 cm<3> of benzene and 1 cm<3> of acetic acid for 7 hours under reflux. After cooling, 1-nicotinoyl-2-(2,2- diphenylisopropylidene)-hydrazine separates out, which after recrystallization from alcohol melts at 182°. 10 g of this hydrazine derivative is dissolved in 180 cm<3> of alcohol and hydrated at 30-40° while adding 0.2 g of platinum oxide at a pressure of approx. 25-35 atmospheres until absorption of the calculated amount of hydrogen. The catalyst is filtered off, and the filtrate is evaporated. The residue is recrystallized from alcohol.
Eksempel 5. Example 5.
1000 g pikolinsyrehydrazid og 730 g benzaldehyd bringes til kokning i 4000 cm<3 >alkohol i 15 minutter. Etter avkjøling smelter l-pikolinoyl-2-benzyliden-hydrazinet som skiller seg, ut etter omkrystallisering fra alkohol, ved 192—194°. 1000 g of picolinic acid hydrazide and 730 g of benzaldehyde are brought to the boil in 4000 cm3 of alcohol for 15 minutes. After cooling, the 1-picolinoyl-2-benzylidene-hydrazine which separates out, after recrystallization from alcohol, melts at 192-194°.
22,5 g av dette hydrazin løses opp i 175 cm;! etanol og hydreres under tilsetning av 0,2 g platinoksyd ved et trykk på ca. 3—4 atmosfærer først ved 70° og etter at reaksjonen er kommet i gang ved 25°. Etter opp-tagelse av den beregnede mengde hydrogen fjernes katalysatoren, og det erholdte l-pikolinoyl-2-benzylhydr'azin omkrystalliseres fra etanol, s. p. 87—88°. 22.5 g of this hydrazine is dissolved in 175 cm;! ethanol and hydrated while adding 0.2 g of platinum oxide at a pressure of approx. 3-4 atmospheres first at 70° and after the reaction has started at 25°. After absorption of the calculated amount of hydrogen, the catalyst is removed, and the 1-picolinoyl-2-benzylhydrazine obtained is recrystallized from ethanol, mp 87-88°.
Eksempel 6. Example 6.
942 g av det ifølge eksempel 5 erholdte 1- pikolinoyl-2-benzyliden-hydrazin opplø-ses i 5000 cm3 etanol og hydreres under tilsetning av 150 g 10 pst.'s palladiumkuil under et trykk på 3 atmosfærer ved 25°. Temperaturen stiger til 50° under reaksjonen. Man hydrerer videre inntil hydrogen i et overskudd på 20 pst. er blitt opptatt. 942 g of the 1-picolinoyl-2-benzylidene-hydrazine obtained according to example 5 are dissolved in 5000 cm 3 of ethanol and hydrated with the addition of 150 g of 10% palladium ball under a pressure of 3 atmospheres at 25°. The temperature rises to 50° during the reaction. Hydrogenation continues until hydrogen in an excess of 20 per cent has been taken up.
Etter avslutningen av hydreringen filtreres katalysatoren av, og den tilbakebli-vende moderlut konsentreres til 2000 cm<5>. Hydreringsproduktet krystalliserer delvis ut ved avkjøling og filtreres fra. Fra det konsentrerte filtrat kan ytterligere mate-riale utvinnes. De forenede produkter omkrystalliseres i 1800 cm<3> kokende alkohol. Man får ved dette l-pikolinoyl-2-benzyl - hydrazin som fargeløse krystaller med smeltepunkt 87—88°. After the completion of the hydration, the catalyst is filtered off, and the remaining mother liquor is concentrated to 2000 cm<5>. The hydration product partly crystallizes out on cooling and is filtered off. Additional material can be recovered from the concentrated filtrate. The combined products are recrystallized in 1800 cm<3> of boiling alcohol. This gives 1-picolinoyl-2-benzyl hydrazine as colorless crystals with a melting point of 87-88°.
Saltene av denne forbindelse kan fremstilles som følger: 3 g l-pikolinoyl-2-benzylhydrazin opp-løses i 10 cm<3> etanolsk hydrobromid. Ved tilsetning av eter krystalliserer 1-pikolin - oyl-2-benzylhydrazin-hydrobromid ut, som etter gjenoppløsning fra etanol/eter smelter ved 163—164°. 3 g l-pikolinoyl-2-benzylhydrazin tilsettes til 100 cm3 etanol og 5 cm<3> 85 pst.'s fosforsyre. Ved tilsetning av eter skiller 1-pikolinoyl-2-benzylhydrazin-fosfat seg fra som sirupslignende produkt, som ikke krystalliserer. 3 g l-pikolinoyl-2-benzylhydrazin tilsettes til 100 cm<3> etanol og 5 cm3 vinsyre; Ved tilsetning av eter skiller 1-pikolinoyl - 2- benzylhydrazin-tartrat seg ut som amorft produkt, som ikke krystalliserer. The salts of this compound can be prepared as follows: 3 g of 1-picolinoyl-2-benzylhydrazine are dissolved in 10 cm<3> of ethanolic hydrobromide. On addition of ether, 1-picolin-oyl-2-benzylhydrazine hydrobromide crystallizes out, which after redissolution from ethanol/ether melts at 163-164°. 3 g of 1-picolinoyl-2-benzylhydrazine are added to 100 cm3 of ethanol and 5 cm<3> of 85% phosphoric acid. On addition of ether, 1-picolinoyl-2-benzylhydrazine phosphate separates as syrup-like product, which does not crystallize. 3 g of 1-picolinoyl-2-benzylhydrazine are added to 100 cm3 of ethanol and 5 cm3 of tartaric acid; On addition of ether, 1-picolinoyl-2-benzylhydrazine tartrate separates as an amorphous product, which does not crystallize.
Til 10 ig l-pikolinoyl-2-benzylhydrazin i etanol tilsettes 10 cm<3> 20 pst.'s eta- To 10 µg of 1-picolinoyl-2-benzylhydrazine in ethanol is added 10 cm<3> of 20 percent eta-
nolsk saltsyre. Ved tilsetning av eter krystalliserer l-pikolinoyl-2-benzyl-hydrazin-hydroklorid ut. Norwegian hydrochloric acid. On addition of ether, 1-picolinoyl-2-benzyl-hydrazine hydrochloride crystallizes out.
Eksempel 7. Example 7.
En suspensjon av 12,3 g pikolinsyre i 250 cm<3> metylenklorid tilsettes 12,2 g benzylhydrazin og derpå 20,6 g dicykloheksyl-karbodiimid. Man rører om i 3 timer og holder temperaturen mellom 25 og 30°. Den fra det utfallende N,N'-dicykloheksylurin-stoff befridde oppløsning dampes inn. Resten rives med 500 cm3 eter, oppløsningen filtreres og dampes igjen inn. Resten rys-ter man under kjøling med 300 cm<3> 10 pst.'s natronlut, filtrerer uoppløst fra og innstil-ler filtratet med konsentrert saltsyre på pH 8—9. Det utkrystalliserte 1-pikolinoyl-2-benzylhydrazin nutsjes av, vaskes med vann, tørkes og omkrystalliseres fra eter/ petroleter. S. p. 87—88°. A suspension of 12.3 g of picolinic acid in 250 cm<3> of methylene chloride is added to 12.2 g of benzylhydrazine and then 20.6 g of dicyclohexyl carbodiimide. Stir for 3 hours and keep the temperature between 25 and 30°. The solution freed from the precipitated N,N'-dicyclohexyl urin substance is evaporated. The residue is triturated with 500 cm3 of ether, the solution is filtered and evaporated again. The residue is shaken while cooling with 300 cm<3> 10% caustic soda, filtered off undissolved and adjusts the filtrate with concentrated hydrochloric acid to pH 8-9. The crystallized 1-picolinoyl-2-benzylhydrazine is filtered off, washed with water, dried and recrystallized from ether/petroleum ether. pp. 87-88°.
Eksempel 8. Example 8.
76 g pikolinsyreetylester blandes med 61 g benzylhydrazin. Blandingen oppvarmes 76 g of picolinic acid ethyl ester are mixed with 61 g of benzylhydrazine. The mixture is heated
først under omrøring til 100°, hvorved temperaturen stiger til 130°. Reaksjonsblandin-gen får henstå over natt, røres derpå i 1 1/2 time mellom 100 og 130° og tilsettes first with stirring to 100°, whereby the temperature rises to 130°. The reaction mixture is allowed to stand overnight, then stirred for 1 1/2 hours between 100 and 130° and added
til slutt vann. Det smittes nå med 1-pikolinoyl-2-benzylhydrazin, hvorpå den ønske-de forbindelse begynner å krystallisere ut. Etter omkrystallisering fra alkohol smelter det oppnådde l-pikolinoyl-2-benzylhydrazin ved 83—86°. finally water. It is now infected with 1-picolinoyl-2-benzylhydrazine, after which the desired compound begins to crystallize out. After recrystallization from alcohol, the 1-picolinoyl-2-benzylhydrazine obtained melts at 83-86°.
Claims (6)
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| US3810563A (en) * | 1972-07-14 | 1974-05-14 | Mers H | Plastic melting and feeding machine |
| US4032046A (en) * | 1976-11-01 | 1977-06-28 | Usm Corporation | Apparatus for feeding glue to a hot melt glue dispensing appliance |
| US4474311A (en) * | 1981-07-31 | 1984-10-02 | Nordson Corporation | Thermoplastic melting and dispensing apparatus |
| GB8334653D0 (en) * | 1983-12-30 | 1984-02-08 | Dynacast Int Ltd | Injection moulding and casting method |
| US4613062A (en) * | 1984-04-17 | 1986-09-23 | Continental Can Company, Inc. | Hot melt material dispenser |
| EP0225943A1 (en) * | 1985-12-03 | 1987-06-24 | Clarence H. Drader | Apparatus for and process of welding thermoplastics material |
| US4804110A (en) * | 1986-01-08 | 1989-02-14 | Charles R. Sperry | Apparatus, method and article for applying a melted adhesive |
| US4953755A (en) * | 1988-10-03 | 1990-09-04 | Minnesota Mining And Manufacturing Company | Automated thermoplastic dispensing device |
| FR2646108B1 (en) * | 1989-04-21 | 1994-01-21 | Puy Creation Philippe | ADHESIVE DISPENSER AND APPLICATION TO A GLUING DEVICE |
| US5027976A (en) * | 1989-10-10 | 1991-07-02 | Nordson Corporation | Multi-orifice T-bar nozzle |
| DE9305421U1 (en) * | 1993-04-09 | 1993-06-17 | Fagus-Grecon Greten GmbH & Co KG, 3220 Alfeld | Device for applying glue |
| US20030165793A1 (en) * | 2001-10-27 | 2003-09-04 | Dan Yobel | System for dispensing viscous materials |
| US7086861B2 (en) * | 2002-03-01 | 2006-08-08 | Pitz Richard J | System for dispensing viscous materials |
| JP3963750B2 (en) * | 2002-03-25 | 2007-08-22 | 日本電産サンキョー株式会社 | Curved cutting method |
| US20070049886A1 (en) * | 2005-08-31 | 2007-03-01 | Kimberly-Clark Worldwide, Inc. | Absorbent web with improved integrity and methods for making the same |
| US20070270750A1 (en) * | 2006-05-17 | 2007-11-22 | Alcon, Inc. | Drug delivery device |
| CN109834014B (en) * | 2017-11-28 | 2021-01-08 | 深圳市腾盛精密装备股份有限公司 | Dispensing valve applied to dispensing equipment and dispensing equipment |
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| US2972670A (en) * | 1959-09-04 | 1961-02-21 | United Shoe Machinery Corp | Cement handling apparatus |
| US3337093A (en) * | 1964-04-06 | 1967-08-22 | United Shoe Machinery Corp | Electrically heated cement extruders |
| US3285475A (en) * | 1965-02-08 | 1966-11-15 | United Shoe Machinery Corp | Cement extruders |
| US3399665A (en) * | 1967-05-24 | 1968-09-03 | United Shoe Machinery Corp | Apparatus for melting and dispensing thermoplastic material |
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| SE343237B (en) | 1972-03-06 |
| FR2022800A1 (en) | 1970-08-07 |
| AT304735B (en) | 1973-01-25 |
| NL6916808A (en) | 1970-05-11 |
| GB1175650A (en) | 1969-12-23 |
| BE741391A (en) | 1970-05-08 |
| JPS5010268B1 (en) | 1975-04-19 |
| ES373252A1 (en) | 1971-12-16 |
| CH498659A (en) | 1970-11-15 |
| FI51066B (en) | 1976-06-30 |
| DE1955452A1 (en) | 1970-06-11 |
| FI51066C (en) | 1976-10-11 |
| US3653552A (en) | 1972-04-04 |
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