CA1060455A - Procede catalytique de deshydrogenation pour la preparation de pyrazoles substitues en 3 et 5 - Google Patents

Procede catalytique de deshydrogenation pour la preparation de pyrazoles substitues en 3 et 5

Info

Publication number: CA1060455A
Authority: CA; Canada
Prior art keywords: mixture; reaction mixture; palladium; catalyst; reaction
Prior art date: 1975-02-12
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired

Application number

CA242,256A

Other languages

English (en)

Inventor

Murray Garber

Walter J. Stepek

Lawrence J. Ross

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Wyeth Holdings LLC

Original Assignee

American Cyanamid Co

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1975-02-12

Filing date

1975-12-22

Publication date

1979-08-14

1975-02-12 Priority claimed from US05/549,219 external-priority patent/US3952010A/en

1975-12-22 Application filed by American Cyanamid Co filed Critical American Cyanamid Co

1979-08-14 Application granted granted Critical

1979-08-14 Publication of CA1060455A publication Critical patent/CA1060455A/fr

Status Expired legal-status Critical Current

Links

-1 3,5-disubstituted pyrazoles Chemical class 0.000 title claims abstract description 34
238000000034 method Methods 0.000 title claims abstract description 30
238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 22
238000002360 preparation method Methods 0.000 title claims abstract description 11
230000003197 catalytic effect Effects 0.000 title claims abstract description 9
239000011541 reaction mixture Substances 0.000 claims abstract description 55
OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 22
238000006243 chemical reaction Methods 0.000 claims abstract description 22
KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 16
HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 12
150000002576 ketones Chemical class 0.000 claims abstract description 11
150000001299 aldehydes Chemical class 0.000 claims abstract description 6
QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 6
KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
239000000203 mixture Substances 0.000 claims description 43
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
239000003054 catalyst Substances 0.000 claims description 33
239000002904 solvent Substances 0.000 claims description 27
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
239000008096 xylene Substances 0.000 claims description 25
238000010992 reflux Methods 0.000 claims description 23
JXHKUYQCEJILEI-UHFFFAOYSA-N 3,5-diphenyl-1h-pyrazole Chemical compound C=1C(C=2C=CC=CC=2)=NNC=1C1=CC=CC=C1 JXHKUYQCEJILEI-UHFFFAOYSA-N 0.000 claims description 21
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 20
BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
238000001914 filtration Methods 0.000 claims description 11
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
229910052757 nitrogen Inorganic materials 0.000 claims description 10
239000011261 inert gas Substances 0.000 claims description 9
239000002253 acid Substances 0.000 claims description 8
NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
125000000217 alkyl group Chemical group 0.000 claims description 6
150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
238000001816 cooling Methods 0.000 claims description 6
JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 6
239000000706 filtrate Substances 0.000 claims description 6
150000003738 xylenes Chemical class 0.000 claims description 6
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
229910052786 argon Inorganic materials 0.000 claims description 5
239000001569 carbon dioxide Substances 0.000 claims description 5
229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
239000001307 helium Substances 0.000 claims description 5
229910052734 helium Inorganic materials 0.000 claims description 5
SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
229910052763 palladium Inorganic materials 0.000 claims description 5
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
125000003545 alkoxy group Chemical group 0.000 claims description 4
239000003849 aromatic solvent Substances 0.000 claims description 4
239000001257 hydrogen Substances 0.000 claims description 4
229910052739 hydrogen Inorganic materials 0.000 claims description 4
229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
239000011707 mineral Substances 0.000 claims description 4
229910052697 platinum Inorganic materials 0.000 claims description 4
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
125000001188 haloalkyl group Chemical group 0.000 claims description 3
229910052736 halogen Inorganic materials 0.000 claims description 3
150000002367 halogens Chemical class 0.000 claims description 3
229910052727 yttrium Inorganic materials 0.000 claims description 3
230000001476 alcoholic effect Effects 0.000 claims description 2
150000004292 cyclic ethers Chemical class 0.000 claims description 2
125000005843 halogen group Chemical group 0.000 claims description 2
238000010438 heat treatment Methods 0.000 claims description 2
150000002431 hydrogen Chemical class 0.000 claims description 2
125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
239000003880 polar aprotic solvent Substances 0.000 claims description 2
239000002244 precipitate Substances 0.000 claims description 2
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 6
150000001875 compounds Chemical class 0.000 claims 2
238000005406 washing Methods 0.000 claims 2
230000000694 effects Effects 0.000 claims 1
125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims 1
FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 claims 1
150000003217 pyrazoles Chemical class 0.000 abstract description 7
DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 abstract description 6
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 5
DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 abstract description 5
235000005513 chalcones Nutrition 0.000 abstract description 5
230000020477 pH reduction Effects 0.000 abstract description 3
DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 abstract description 3
150000001788 chalcone derivatives Chemical class 0.000 abstract description 2
150000003219 pyrazolines Chemical class 0.000 abstract description 2
239000004009 herbicide Substances 0.000 abstract 1
239000000047 product Substances 0.000 description 12
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
239000002585 base Substances 0.000 description 8
238000007792 addition Methods 0.000 description 7
239000007787 solid Substances 0.000 description 7
VJFQJTFADLQQNS-UHFFFAOYSA-N 3,5-diphenyl-4,5-dihydro-1h-pyrazole Chemical compound C1C(C=2C=CC=CC=2)NN=C1C1=CC=CC=C1 VJFQJTFADLQQNS-UHFFFAOYSA-N 0.000 description 6
WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
238000004458 analytical method Methods 0.000 description 5
125000004432 carbon atom Chemical group C* 0.000 description 5
VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
238000002844 melting Methods 0.000 description 5
230000008018 melting Effects 0.000 description 5
WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
229910052783 alkali metal Inorganic materials 0.000 description 4
230000002152 alkylating effect Effects 0.000 description 4
239000003153 chemical reaction reagent Substances 0.000 description 4
239000006184 cosolvent Substances 0.000 description 4
239000012044 organic layer Substances 0.000 description 4
239000003960 organic solvent Substances 0.000 description 4
238000000926 separation method Methods 0.000 description 4
239000000243 solution Substances 0.000 description 4
SVDTUJAQNAQGGW-UHFFFAOYSA-N 1-methyl-3,5-diphenylpyrazole Chemical compound CN1N=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 SVDTUJAQNAQGGW-UHFFFAOYSA-N 0.000 description 3
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
229910019142 PO4 Inorganic materials 0.000 description 3
150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
150000001340 alkali metals Chemical class 0.000 description 3
150000001350 alkyl halides Chemical class 0.000 description 3
239000008346 aqueous phase Substances 0.000 description 3
150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
125000003118 aryl group Chemical group 0.000 description 3
239000012298 atmosphere Substances 0.000 description 3
229940077388 benzenesulfonate Drugs 0.000 description 3
238000009835 boiling Methods 0.000 description 3
229910052799 carbon Inorganic materials 0.000 description 3
150000008050 dialkyl sulfates Chemical class 0.000 description 3
238000004821 distillation Methods 0.000 description 3
235000021317 phosphate Nutrition 0.000 description 3
XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 3
RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 2
PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
150000001298 alcohols Chemical class 0.000 description 2
239000002168 alkylating agent Substances 0.000 description 2
229940100198 alkylating agent Drugs 0.000 description 2
230000029936 alkylation Effects 0.000 description 2
238000005804 alkylation reaction Methods 0.000 description 2
PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
150000001450 anions Chemical class 0.000 description 2
239000000010 aprotic solvent Substances 0.000 description 2
GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
229910052794 bromium Inorganic materials 0.000 description 2
238000005119 centrifugation Methods 0.000 description 2
239000000460 chlorine Substances 0.000 description 2
229910052801 chlorine Inorganic materials 0.000 description 2
JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
229910052731 fluorine Inorganic materials 0.000 description 2
239000011737 fluorine Substances 0.000 description 2
150000004820 halides Chemical class 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
239000000543 intermediate Substances 0.000 description 2
239000010410 layer Substances 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
239000010452 phosphate Substances 0.000 description 2
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
239000002002 slurry Substances 0.000 description 2
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
229940086542 triethylamine Drugs 0.000 description 2
XQEMNBNCQVQXMO-UHFFFAOYSA-M 1,2-dimethyl-3,5-diphenylpyrazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C[N+]=1N(C)C(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 XQEMNBNCQVQXMO-UHFFFAOYSA-M 0.000 description 1
SXVRSCIZJBGJGB-UHFFFAOYSA-N 1-chloropropan-2-ylbenzene Chemical compound ClCC(C)C1=CC=CC=C1 SXVRSCIZJBGJGB-UHFFFAOYSA-N 0.000 description 1
QVPQRGOYJIVNKG-UHFFFAOYSA-N 2-(2-methyl-3-phenyl-3,4-dihydropyrazol-5-yl)phenol Chemical compound CN1N=C(C=2C(=CC=CC=2)O)CC1C1=CC=CC=C1 QVPQRGOYJIVNKG-UHFFFAOYSA-N 0.000 description 1
SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
QWLMQJYXUPWMAH-UHFFFAOYSA-N 3,5-diphenyl-1H-pyrazole 1-phenylethanone Chemical compound C(C)(=O)C1=CC=CC=C1.C1(=CC=CC=C1)C1=NNC(=C1)C1=CC=CC=C1 QWLMQJYXUPWMAH-UHFFFAOYSA-N 0.000 description 1
ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
235000007320 Avena fatua Nutrition 0.000 description 1
244000075850 Avena orientalis Species 0.000 description 1
CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
241000196324 Embryophyta Species 0.000 description 1
240000005979 Hordeum vulgare Species 0.000 description 1
235000007340 Hordeum vulgare Nutrition 0.000 description 1
241000243251 Hydra Species 0.000 description 1
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
241000209056 Secale Species 0.000 description 1
235000007238 Secale cereale Nutrition 0.000 description 1
241000209140 Triticum Species 0.000 description 1
235000021307 Triticum Nutrition 0.000 description 1
235000005373 Uvularia sessilifolia Nutrition 0.000 description 1
BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
150000005224 alkoxybenzenes Chemical class 0.000 description 1
150000004996 alkyl benzenes Chemical class 0.000 description 1
239000007864 aqueous solution Substances 0.000 description 1
229910052788 barium Inorganic materials 0.000 description 1
DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
229940040544 bromides Drugs 0.000 description 1
150000001649 bromium compounds Chemical class 0.000 description 1
AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
239000000920 calcium hydroxide Substances 0.000 description 1
229910001861 calcium hydroxide Inorganic materials 0.000 description 1
BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
239000000292 calcium oxide Substances 0.000 description 1
ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
235000013339 cereals Nutrition 0.000 description 1
239000007810 chemical reaction solvent Substances 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
125000004122 cyclic group Chemical group 0.000 description 1
125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
238000001035 drying Methods 0.000 description 1
HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
230000009969 flowable effect Effects 0.000 description 1
239000007789 gas Substances 0.000 description 1
XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
238000005984 hydrogenation reaction Methods 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
239000011630 iodine Substances 0.000 description 1
229910052740 iodine Inorganic materials 0.000 description 1
QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical class CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
230000002147 killing effect Effects 0.000 description 1
238000004811 liquid chromatography Methods 0.000 description 1
GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical class COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
239000012299 nitrogen atmosphere Substances 0.000 description 1
239000011356 non-aqueous organic solvent Substances 0.000 description 1
239000012074 organic phase Substances 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
238000010979 pH adjustment Methods 0.000 description 1
229960004838 phosphoric acid Drugs 0.000 description 1
235000011007 phosphoric acid Nutrition 0.000 description 1
229960005235 piperonyl butoxide Drugs 0.000 description 1
229910000027 potassium carbonate Inorganic materials 0.000 description 1
BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
238000001556 precipitation Methods 0.000 description 1
230000002035 prolonged effect Effects 0.000 description 1
IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
238000005956 quaternization reaction Methods 0.000 description 1
150000003254 radicals Chemical group 0.000 description 1
239000000376 reactant Substances 0.000 description 1
239000011369 resultant mixture Substances 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
239000011734 sodium Substances 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
239000011877 solvent mixture Substances 0.000 description 1
241000894007 species Species 0.000 description 1
239000007858 starting material Substances 0.000 description 1
239000000725 suspension Substances 0.000 description 1
JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
238000005303 weighing Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Catalysts (AREA)

CA242,256A 1975-02-12 1975-12-22 Procede catalytique de deshydrogenation pour la preparation de pyrazoles substitues en 3 et 5 Expired CA1060455A (fr)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
US05/549,219 US3952010A (en)	1973-09-17	1975-02-12	Catalytic dehydrogenation process for the preparation of 3,5-disubstituted pyrazoles

Publications (1)

Publication Number	Publication Date
CA1060455A true CA1060455A (fr)	1979-08-14

Family

ID=24192112

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA242,256A Expired CA1060455A (fr)	1975-02-12	1975-12-22	Procede catalytique de deshydrogenation pour la preparation de pyrazoles substitues en 3 et 5

Country Status (19)

Country	Link
JP (2)	JPS51101979A (fr)
AT (1)	AT350549B (fr)
BE (1)	BE838408R (fr)
BR (1)	BR7600847A (fr)
CA (1)	CA1060455A (fr)
CH (1)	CH608004A5 (fr)
CS (1)	CS192554B2 (fr)
DD (1)	DD124249A6 (fr)
DE (1)	DE2602965A1 (fr)
DK (1)	DK55276A (fr)
ES (1)	ES445094A2 (fr)
FR (1)	FR2300763A2 (fr)
GB (1)	GB1537859A (fr)
IL (1)	IL48724A (fr)
IT (1)	IT1053296B (fr)
NL (1)	NL178075C (fr)
SE (1)	SE7601544L (fr)
SU (1)	SU799657A3 (fr)
ZA (1)	ZA757986B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE3029160A1 (de) *	1980-08-01	1982-03-04	Basf Ag, 6700 Ludwigshafen	Verfahren zur herstellung von pyrazolen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
JPS5855148A (ja) *	1981-09-29	1983-04-01	Hino Motors Ltd	成形用金型の製造方法

1975
- 1975-12-22 CA CA242,256A patent/CA1060455A/fr not_active Expired
- 1975-12-23 ZA ZA00757986A patent/ZA757986B/xx unknown
- 1975-12-24 IL IL48724A patent/IL48724A/xx unknown
1976
- 1976-01-09 IT IT47573/76A patent/IT1053296B/it active
- 1976-01-16 NL NLAANVRAGE7600445,A patent/NL178075C/xx not_active IP Right Cessation
- 1976-01-27 DE DE19762602965 patent/DE2602965A1/de active Granted
- 1976-02-03 DD DD191069A patent/DD124249A6/xx unknown
- 1976-02-10 FR FR7603642A patent/FR2300763A2/fr active Granted
- 1976-02-10 JP JP51012890A patent/JPS51101979A/ja active Pending
- 1976-02-10 BE BE164196A patent/BE838408R/fr not_active IP Right Cessation
- 1976-02-11 BR BR7600847A patent/BR7600847A/pt unknown
- 1976-02-11 CH CH166976A patent/CH608004A5/xx not_active IP Right Cessation
- 1976-02-11 SE SE7601544A patent/SE7601544L/xx unknown
- 1976-02-11 CS CS76899A patent/CS192554B2/cs unknown
- 1976-02-11 AT AT96276A patent/AT350549B/de not_active IP Right Cessation
- 1976-02-11 DK DK55276*#A patent/DK55276A/da unknown
- 1976-02-11 SU SU762319859A patent/SU799657A3/ru active
- 1976-02-12 ES ES445094A patent/ES445094A2/es not_active Expired
- 1976-02-12 GB GB5650/76A patent/GB1537859A/en not_active Expired
1985
- 1985-02-27 JP JP60036705A patent/JPS60222463A/ja active Granted

Also Published As

Publication number	Publication date
SE7601544L (sv)	1976-08-13
SU799657A3 (ru)	1981-01-23
DE2602965C2 (fr)	1988-11-17
JPS6227068B2 (fr)	1987-06-12
JPS60222463A (ja)	1985-11-07
NL178075B (nl)	1985-08-16
JPS51101979A (fr)	1976-09-08
AU8790475A (en)	1977-06-30
DK55276A (da)	1976-08-13
FR2300763A2 (fr)	1976-09-10
NL178075C (nl)	1986-01-16
ZA757986B (en)	1976-12-29
CS192554B2 (en)	1979-08-31
IL48724A (en)	1979-07-25
ATA96276A (de)	1978-11-15
FR2300763B2 (fr)	1982-09-03
NL7600445A (nl)	1976-08-16
BE838408R (fr)	1976-08-10
IT1053296B (it)	1981-08-31
CH608004A5 (en)	1978-12-15
IL48724A0 (en)	1976-02-29
DE2602965A1 (de)	1976-08-26
ES445094A2 (es)	1977-06-16
DD124249A6 (fr)	1977-02-09
AT350549B (de)	1979-06-11
BR7600847A (pt)	1976-09-14
GB1537859A (en)	1979-01-04

Publication	Publication Date	Title
US4996327A (en)	1991-02-26	Preparation of pyrazole and its derivatives
JP2011519899A (ja)	2011-07-14	芳香族アルファ−ヒドロキシケトンの調製方法
CA1037048A (fr)	1978-08-22	Un procede de deshydrogenation catalytique lors de la preparation de pyrazoles substitues en 3,5
US4632999A (en)	1986-12-30	Process for the preparation of oxiranes
US3952010A (en)	1976-04-20	Catalytic dehydrogenation process for the preparation of 3,5-disubstituted pyrazoles
US4014896A (en)	1977-03-29	Catalytic dehydrogenation process for the preparation of 3,4,5-trisubstituted pyrazoles
CA1060455A (fr)	1979-08-14	Procede catalytique de deshydrogenation pour la preparation de pyrazoles substitues en 3 et 5
JPH0723351B2 (ja)	1995-03-15	テトラクロロ−２−シアノ安息香酸アルキルエステルの製造方法
AU703688B2 (en)	1999-04-01	Process for producing 3,5-diaryl pyrazolene
EP0070231A1 (fr)	1983-01-19	Nouveau procédé de préparation de dérivés du diphényl-3,4 méthyl-5 pyrazole
EP1844019B1 (fr)	2009-09-02	Procede pour produire du losartane
KR20010102956A (ko)	2001-11-17	폴리할로겐화 파라트리플루오로메틸아닐린의 제조 방법
US4550175A (en)	1985-10-29	Process for the stereospecific preparation of (Z)-1-(2,4-dichlorophenyl)-2-(imidazol-1-yl)-0-(2,4-dichlorobenzyl)-ethanone oxime ether
US4236017A (en)	1980-11-25	Process for synthesizing 2-substituted semicarbazones and carbalkoxy hydrazones
CA1051439A (fr)	1979-03-27	Synthese industrielle de methylsulfate de dimethyl-1,2 diphenyl-3,5 pyrazolium
CA1052383A (fr)	1979-04-10	Derives de triazole-1,2,4
US4980489A (en)	1990-12-25	2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone
GB1589334A (en)	1981-05-13	Process for the preparation of aromatic amines from a, -unsaturated cycloaliphatic ketoximes
US6121492A (en)	2000-09-19	Method for preparing 2-trifluoro-methoxy-aniline
KR890000420B1 (ko)	1989-03-17	4-벤조일피라졸 유도체의 제법
US4510314A (en)	1985-04-09	Preparation of 1-azolyl-3,3-dimethyl-1-phenoxybutan-2-ols
US5498725A (en)	1996-03-12	Process for preparing 5-aminodihydropyrrole intermediate thereof and process for preparing said intermediate
US4501897A (en)	1985-02-26	Process for the preparation of E-isomers of 1-cyclohexyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one derivatives
US4388465A (en)	1983-06-14	Preparation of phenoxy-azolyl-butanone derivatives
JPS6097920A (ja)	1985-05-31	置換１‐フエニルインダンの製造方法